Carbon and silicone enriched new high-chi block copolymers of novel architectures for thin-film self-assembly applications

Abstract

Described is a block copolymer of structure (I) comprising a first copolymer block segment A prepared by anionic polymerization, a second polymer block segments B, prepared by metal catalyzed ring opening polymerization, a linking moiety Z between said first copolymer block segment A, and said second polymer block segment B, and a first and second end groups E1 and E2. Also described is a composition comprised the copolymer of structure (I) and using said composition in lithographic processes which employ self-assembly or directed self-assembly (DSA) in the manufacture of IC devices. (I)

Description

New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCCARBON AND SILICONE ENRICHED NEW HIGH-CHI BLOCK COPOLYMERS OF NOVEL ARCHITECTURES FOR THEN-FILM SELF-ASSEMBLY APPLICATIONSFIELD

[0001] The disclosed subject matter pertains to high Chi styrenic block copolymers which have silicon or carbon-based pendant group for improved orientation and collapse control.BACKGROUND

[0002] Self-assembly of block copolymers is a method useful for generating smaller and smaller patterned features for the manufacture of microelectronic devices in which the critical dimensions (CD) of features on the order of nanoscale can be achieved. Self-assembly methods are desirable for extending the resolution capabilities of microlithographic technology for repeating features such as an array of contact holes or posts. In a conventional lithography approach, ultraviolet (UV) radiation may be used to expose through a mask onto a photoresist layer coated on a substrate or layered substrate. Positive or negative photoresists are useful, and these can also contain a refractory element such as silicon to enable dry development with conventional integrated circuit (IC) plasma processing. In a positive photoresist, UV radiation transmitted through a mask causes a photochemical reaction in the photoresist such that the exposed regions are removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation transmitted through a mask causes the regions exposed to radiation to become less removable with a developer solution or by conventional IC plasma processing. An integrated circuit feature, such as a gate, via or interconnect, is then etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional lithographic exposure processes, the dimensions of features of the integrated circuit feature are limited. Further reduction in pattern dimensions is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, minimum achievable exposure wavelengths and maximum achievable numerical apertures. The need for large-scale integration has led to a continued shrinking of the circuit dimensions and features in the devices. In the past, the final resolution of the features has been dependent upon the wavelength of light used to expose the photoresist, which has its own limitations. Directed (a.k.a. guided) self-assembly techniques, such as graphoepitaxy and chemoepitaxy using block copolymer imaging, which employ a patternedNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC area on a substrate, are highly desirable techniques used to enhance resolution while reducing CD variation. These techniques can be employed to either enhance conventional UV lithographic techniques or to enable even higher resolution and CD control in approaches employing EUV, e- beam, deep UV or immersion lithography. The directed self-assembly block copolymer comprises a block of etch resistant copolymeric unit and a block of highly etchable copolymeric unit, which when coated, aligned, and etched on a substrate give regions of very high-density patterns.

[0003] For directed (guided), or unguided self-assembly, of a block copolymer film, respectively, on a patterned or non-pattemed substrate area, typically the self-assembly process of this block polymer layer occurs during annealing of this film overlying a neutral layer. This neutral layer over a semiconductor substrate may be an unpatterned neutral layer, or in chemoepitaxy or graphoepitaxy, this neutral layer may contain, respectively, graphoepitaxy or chemoepitaxy guiding features (formed through the above-described UV lithographic technique). Neutral layers may be in the form of a grafted brush type neutral layer, or alternatively in the form of a crosslinked neutral layer (neutral layer MAT). During annealing of the block copolymer film, the underlying, neutral layer, directs the nano-phase separation of the block copolymer domains. One example is the formation of phase separated domains which are lamellas or cylinders perpendicular to the underlying neutral layer surface. These nano-phase separated block copolymer domains, form a pre-pattem (e.g., line and space L / S) which may be transferred into the substrate through an etching process (e.g., plasma etching). In graphoepitaxy, or in chemoepitaxy, these guiding features may dictate both pattern rectification and pattern multiplication. In the case of an unpatterned neutral layer this produces a repeating array of for instance L / S or CH. For example, in a conventional block copolymer such as poly(styrene-b-methyl methacrylate (P(S-b-MMA)), in which both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermally annealing the block copolymer on a layer of non-preferential or neutral material that is grafted or cross-linked at the polymer-substrate interface.

[0004] In the graphoepitaxy directed self-assembly method, the block copolymers self organizes around a substrate that is pre-pattemed with conventional lithography (Ultraviolet, Deep UV, e- beam, Extreme UV (EUV) exposure source) to form repeating topographical features such as a line / space (L / S) or contact hole (CH) pattern. In an example of a L / S directed self-assembly array, the block copolymer can form self-aligned lamellar regions which can form parallel line-spaceNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC patterns of different pitches in the trenches between pre-patterned lines, thus enhancing pattern resolution by subdividing the space in the trench between the topographical lines into finer patterns. For example, a diblock copolymer or a triblock copolymer which is capable of microphase separation and comprises a block rich in carbon (such as styrene or containing some other element like Si, Ge, Ti) which is resistant to plasma etch, and a block which is highly plasma etchable or removable, can provide a high-resolution pattern definition. Examples of highly etchable blocks can comprise monomers which are rich in oxygen, and which do not contain refractory elements and can form blocks which are highly etchable, such as methyl methacrylate. The plasma etching gases used in the etching process of defining the self-assembly pattern typically are those used in processes employed to make integrated circuits (IC). In this manner, very fine patterns can be created in typical IC substrates than were definable by conventional lithographic techniques, thus achieving pattern multiplication. Similarly, features such as contact holes can be made denser by using graphoepitaxy in which a suitable block copolymer arranges itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography, thus forming a denser array of regions of etchable and etch resistant domains which when etched give rise to a denser array of contact holes. Consequently, graphoepitaxy has the potential to offer both pattern rectification and pattern multiplication.

[0005] In chemical epitaxy, or pinning chemical epitaxy, the self-assembly of the block copolymer is formed on a surface whose guiding features are regions of differing chemical affinity, having no, or insignificant topography (a.k.a. non-guiding topography) which predicates the directed selfassembly process. For example, the surface of a substrate could be patterned with conventional lithography (UV, Deep UV, e-beam EUV) to create surfaces of different chemical affinity in a line and space (L / S) pattern in which exposed areas whose surface chemistry had been modified by irradiation alternate with areas which are unexposed and show no chemical change. These areas present no topographical difference but do present a surface chemical difference or pinning to direct self-assembly of block copolymer segments. Specifically, the directed self-assembly of a block copolymer whose block segments contain etch resistant (such as styrene repeat unit) and rapidly etching repeat units (such as methyl methacrylate repeat units) would allow precise placement of etch resistant block segments and highly etchable block segments over the pattern. This technique allows for the precise placement of these block copolymers and the subsequent pattern transfer ofNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC the pattern into a substrate after plasma or wet etch processing. Chemical epitaxy has the advantage that it can be fine-tuned by changes in the chemical differences to help improve line-edge roughness and CD control, thus allowing for pattern rectification. Other types of patterns such as repeating contact holes (CH) arrays could also be pattern rectified using chemoepitaxy.

[0006] Neutral layers are layers on a substrate or the surface of a treated substrate which have no affinity for either of the block segment of a block copolymer employed in directed self-assembly. In the graphoepitaxy method of directed self-assembly of block copolymer, neutral layers are useful as they allow the proper placement or orientation of block polymer segments for directed selfassembly which leads to proper placement of etch resistant block polymer segments and highly etchable block polymer segments relative to the substrate. For instance, in surfaces containing line and space features which have been defined by conventional radiation lithography, a neutral layer allows block segments to be oriented so that the block segments are oriented perpendicular to the surface of the substrates, an orientation which is ideal for both pattern rectification and pattern multiplication depending on the length of the block segments in the block copolymer as related to the length between the lines defined by conventional lithography. If a substrate interacts too strongly with one of the block segments it would cause it to lie flat on that surface to maximize the surface of contact between the segment and the substrate; such a surface would perturb the desirable perpendicular alignment which can be used to either achieve pattern rectification or pattern multiplication based on features created through conventional lithography. Modification of selected small areas or pinning of substrate to make them strongly interactive with one block of the block copolymer and leaving the remainder of the surface coated with the neutral layer can be useful for forcing the alignment of the domains of the block copolymer in a desired direction, and this is the basis for the pinned chemoepitaxy or graphoepitaxy employed for pattern multiplication. Neutral layer materials may be of two types, one type is a polymer brush material which forms a grafted layer on a substrate, another type is a crosslinking (MAT type) material which forms a crosslinked polymer layer on a substrate.

[0007] Pinning layers are layers on a substrate which have a preference for either the highly etchable block copolymer segment or the etch resistant block copolymer segments. These materials may, similarly to neutral layer, be either brush type materials which graft on a substrate or a crosslinkable polymer (MAT), which can form a crosslinked pinning layer on a substrate.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0008] Directed self-assembly is a process well-known in photolithography industries for enabling arrays of line & space and contact holes printing on silicon wafer using organic diblock copolymers (ref. 1 to 5). [1. Rahman, Md. S. et al., Multi-pitch tolerance block copolymers with enhanced kinetics for directed self-assembly applications", WO 2022 / 223670 Al; 2. Liu, C. et al., "Chemical patterns for directed self-assembly of lamellae-forming block copolymers with density multiplication of features", Macromolecules, 2013, 46, 1415-1424; 3. Tsai, H. et al., "Two- dimensional pattern forming using graphoepitaxy of PS- / ?-PMMA block copolymers for advanced FinFET device and circuit fabrication. ACS Nano, 8, 5227-5232; 4. Mansky, P. et al., "Controlling polymer-surface interactions with random copolymer brushes", Science, 275, 1458-1460 (2005); 5. Hinsberg et al.," Self-assembling materials for lithographic patterning: Overview, status and moving forward, " Proceedings of SPIE, vol. 7637, 76370G-1 (2010)].

[0009] Although polystyrene-b-polymethyl methacrylates and their derivatives were employed for DSA of pitch multiplication, and rectification applications as a complementary technique in conjunction with 193 immersion and extreme ultraviolet photolithography, self-assembled and printable feature sizes are limited to ~23 nm as their equilibrium domain spacing. The chi parameter of PS-b-PMMA limits the phase separation morphology to ~23 nm (ref. 6-7). [6. Bates, F. S., Fredrickson, G. H., " Block copolymer thermodynamics: Theory and experiment", Annu. Rev. Phys. Chem., 41, 525-557 (1990); 7. Lei Wan et al., " The limits of lamellae-forming PS-b-PMMA block copolymers for lithography", ACS Nano, vol 9, 7506-7514, 2015.] To obtain much lower domain feature sizes, one must use high-chi block copolymers. The problem with most of the high-chi block copolymers is often surface energy mismatch does not allow simple thermal annealing on thin-film coating at air interface. This problem forces one to use more cumbersome methods like solvent annealing or top-coat for proper orientation of high-chi BCPs. (ref.8-12). [8. Park, S. et al, "Macroscopic 10-Terabit-per-square-Inch arrays from block copolymers with lateral order. Science, 323, 1030-1033, 2009; 9. Cushen, J. D. et al., "Thin film self-assembly of poly(trimethylsilylstyrene-b-D,L-lactide) with sub-10 nm domains, Macromolecules, 45, 8722- 8728, 2012; 10. Jeong, J. W, et al., "Highly tunable self-assembled nanostructures from a poly(2- vinylpyridine-b-dimethylsiloxane) block copolymer. Nano. Lett., 11, 4095-4101, 2011; 11. Park, S. et al., Macromolecules, 42(4), 1278-1284, 2009; 12. Jung, Y. S., et al, Nano Lett. 7(7), 2046- 2050, 2007],New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0010] High-chi BCP especially PS- / >-polylactide (PS- / >-PLA) or PS- / >-trimethyl polycarbonate (PS- / >-PTMC) types can be assembled using thermal annealing but requires modification to control perpendicular orientation on neutral substrate and domain stabilization for e-beam scanning and dry etch removal polar block. Although PS- / >-PLA or PS- / >-PTMC BCPs can be oriented perpendicularly on a neutral substrate containing polystyrene and polymethylmethacrylate copolymer layer or pinning layer consisting of either of these block segments, the BCPs can only be annealed at moderate temperature up to 150°C (ref 13). [13. Ankit Vora et al., " Block copolymers with surface-active junction groups, compositions and processes thereof', US 2016 / 0244557 Al], If PS- / >-PLA is annealed above this temperature, the domain flipping is observed due to surface energy mismatch at air / N2 interface. Structural modification or these block copolymer (BCP) to accommodate surface energy stabilization has been described (ref 13-15). [14. Eri Hirahara et al., " Directed self-assembly of topcoat-free, integration-friendly high-x block copolymers", Proceedings of SPIE, vol. 9425 94250P-1, 2015; 15. Durairaj Baskaran, et al., "Tunable high-chi diblock copolymers consisting of alternating copolymer segments for directed self-assembly and application thereof', US2024 / 0002571A1], However, when PLA domain’s critical dimensions are close to 10 nm, interactions with plasma or e-beam of these domain are very different compared to PMMA or other polar polymer segments causes the problem of physical changes causing collapse of assembled polymer domain. Thus, these is a need for assembly of sub 10 nm domains in high-chi block copolymer systems which overcome these issues and provide both good orientation control and pattern transfer. Further, developing a high-chi BCP system which can undergo good orientation on conventional 1stgeneration neutral underlayers under thermal annealing is critical for the application of DS A to sub 10 nm domain sizes.

[0011] Further, orientation control of organic high-chi BCPs via thermal annealing procedure is very limited due to mismatch of surface energies of high-chi block segments. A few cases of high- chi BCPs exhibit closer surface energies of polar and non-polar block segments that can be thermally annealed without a need for solvent annealing or top-coat strategies. Among them are PS- / ?-Polylactide (PS- / ?-PLA) or PS- / ?-trimethyl polycarbonate (PS- / ?-PTMC) type BCPs, which can be oriented thermally at relatively higher temperature provided the BCP is modified with low surface energy moiety at the junction as described in in ref 13. Polymerization of Lactone such as Lactide, or cyclic carbonates to produce polymer segments grown from the hydroxyl terminalNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC polystyrene block using metal catalyzed ring opening anionic coordinative polymerization as described are described in ref 16 to 17. [16. Odile Dechy-Cabaret, et al., "Controlled ring-opening polymerization of lactide and glycolide", Chemical Review, 104, 6147-6176, 2004; 17. Scott C. Schmidt, et al., "Synthesis and characterization of model polyisoprene-polylactide diblock copolymers", Scott C. Schmidt, et al., "Synthesis and characterization of model polyisoprene- polylactide diblock copolymers", Macromolecules, 32, 15, 4794-4801, 1999], Ref 18 gives a recent review of recent advances in metal-catalyzed ring-opening polymerization of lactones such as Lactide” 18. Recent Developments in Metal-Catalyzed Ring-Opening Polymerization of Lactides and Glycolides: Preparation of Polylactides, Polyglycolide, and Poly(lactide-co-glycolide) Saikat Dutta, Wen-Chou Hung, Bor-Hunn Huang, and Chu-Chieh Lin 245: 219-284).

[0012] Although PS- / 1-PLA can be oriented perpendicularly on a neutral substrate containing polystyrene and polymethylmethacrylate copolymer layer or pinning layer consisting of either of these block segments, it can be only annealed at moderate temperature up to 150°C. If PS- / 1-PLA is annealed above this temperature, the domain flipping is observed due to surface energy mismatch at air / N2 interface. Hence, this block copolymer (BCP) must be structurally modified at junction tag moiety to accommodate surface energy stabilization as described in our previous patent (ref- 13). However, if the PLA domain’ s critical dimension is close to 10 nm, it’ s interaction with plasma or e-beam is very different compared to PMMA or other polar polymer segments which leads to physical changes causing collapse of assembled polymer domain (FIG. 1):BRIEF DESCRIPTION OF DRAWINGS

[0013] FIG. 1 SEM images of PS-b(FE)-PLA annealed at 200°C showing e-beam damage (left image) on PLA domain causing well-formation which makes adjacent PS domain collapse (right image).

[0014] FIG. la Schematic diagram for the LiNe Flow chemical pre-pattern and multiplication DSA.

[0015] FIG. lb Schematic diagram for EUV rectification pre-pattem and DSA.

[0016] FIG. 2 Finger-print (FP) images of PS-b-trimethylsilyl styrene-b-PLA conformationally screened BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); (A) sample 1.1, (B) sample 1.2, (C) sample 1.7, (D) sample 1.9 from Table-1 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0017] FIG. 3 5x multiplication DSA of PS-b-trimethylsilyl styrene-b-PLA using (HChi-3) BCP at a film thickness (FT) 35 nm on IMEC xPS LiNe flow pitch 87 nm PP with Neutral underlayer 1 PS 30 % brush backfill after annealing at 200°C / 30 min. / N2. Lo= 18.37 nm DSA exhibiting no collapse lines.

[0018] FIG. 4 Comparison of A) segmented sample 1.7 from table 1 vs B) copolymerized trimethylsilyl styrene units containing BCPs at similar Mn. Finger-print (FP) data which shows the effect of terminal coil screening is evident and present in segmented case as the FP looks normal, whereas for copolymerized system, silicon distribution across the chain causes higher chi, requires lower Mnto get similar Lo, and asymmetric width of non-polar to polar domains.

[0019] FIG. 5 Proton NMR in CD2CI2 solvent of HChi-3 for line and space composition.

[0020] FIG. 6 Proton NMR in CDCh solvent of HChi-3 for Contact hole composition.

[0021] FIG. 7 CH morphology of HChi-3 BCP at FT A) 20 nm, B) 40 nm on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images.

[0022] FIG. 8 Proton NMR in CDCh solvent of HChi-H3 for line and space composition.

[0023] FIG. 9 Proton NMR in CD2CI2 solvent of HChi-3a.

[0024] FIG. 10 Finger-prints of HChi-3a conformationally screened BCP (A) sample 2.1, (B) sample 2.3, (C) sample 2.5, (D) sample 2.12 from table 2 on underlayer) Neutral underlayer 1 (PS 30 %)| FT 6.5 nm, 250°C / 30 min / N2, annealing at 200°C / 60 mm (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0025] FIG. 11 DSA of 5x of HChi-3a at FT 35 nm on IMEC xPS LiNe flow pitch 87 nm PP with Neutral underlayer 1 PS30% brush backfill (A) after annealing at 200°C / 30 min. / N2, (B) after etching for 12 sec at 50 mT, 100W, 80 seem O2, and 20 seem N2 on Trion etcher.

[0026] FIG. 12 DSA Pattern rectification of EUV 24 nm L / S features coated with HChi-3a BCP (75 nm) on 24 nm L / S prepattem, annealed at 200°C / lh (N2). (A) 1 pm X 1 pm NanoSEM image without etch, (B) 0.5pm X 0.5 pm NanoSEM image after etching for 28 sec on Trion etcher.

[0027] FIG. 13 Proton NMR in CD2CI2 solvent of HChi-H3a line and space block copolymer.

[0028] FIG. 14 Finger-print images of HChi-H3a BCP (A) sample 3.1, (B) sample 3.4, (C) sample 3.8, (D) sample 3.10 from table 3 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0029] FIG. 15 EUV rectification DSA of 24 nm HChi-H3a BCP on IMEC prepattern (24 nm pitchNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC prepattern made with pinning underlayer 1), coating 75 nm annealed at 200°C / lh (N2). (A) 1pm X 1pm NanoSEM image without etch, (B) 0.5pm X 0.5pm NanoSEM image after etching for 28 sec on Trion etcher.

[0030] FIG. 16 CH of HChi-H3a BCP, FT = 40 nm (Table 4, sample 4.4) on Neutral Underlayer 2, annealing at 250°C / 15 min (N2); 1FOV SEM images, 12 sec etch at 50 mT, 100W, 50 seem O2, and 50 seem N2 on Trion etcher.

[0031] FIG. 17 Proton NMR in CD2CI2 solvent of HChi-xH3a line and space block copolymer.

[0032] FIG. 18 Finger-print images of HChi-xH3a BCP at 75 nm FT from Table 5 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images. A) sample, 5.2, B) sample 5.8, and C) sample 5.10 from Table 5.

[0033] FIG. 19 EUV rectification DSA of 24 nm HChi-xH3a BCP, at ctg. 75 nm on IMEC prepattern (24 nm pitch prepattern made with pinning underlayer 1), coating 75 nm annealed at 200°C / lh (N2). (A) 1 pm X 1 pm NanoSEM image without etch, (B) 0.5pm X 0.5pm NanoSEM image after etching for 28 sec on Trion etcher.

[0034] FIG. 20 Proton NMR in CDCh solvent of HChi-3b with dimethylsilyl Cl 5 alkyl units in styrenic block.

[0035] FIG. 21 Finger-print images of HChi-3b BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images. (A) sample 6.1, (B) sample 6.2, (C) sample 6.3 from table 6.

[0036] FIG. 22 Proton NMR in CDCh solvent of HChi-3b with dimethylsilyl C12 alkyl units in styrenic block HChi-3b block copolymer (Example 10).

[0037] FIG. 23 Finger-print images (FP) of HChi-3b (DMC12SiS -derivative) block copolymer at FT A) 20 nm, B) 40 nm on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0038] FIG. 24 Proton NMR spectrum in CDCh solvent of HChi-4 block copolymers with siliconoxide units.

[0039] FIG. 25 Finger-print images of HChi-4 BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images. (A) sample 7.1, (B) sample 7.2, (C) sample 7.3, (D) sample 7.4 from table 7.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0040] FIG. 26 Proton NMR of HChi-6 in CDCh solvent with carbon substituted monomers in both the styrenic and lactide blocks and the blocks are randomly copolymerized.

[0041] FIG. 27 Finger-prints image of HChi-6 BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0042] FIG. 28 CH image of P(S-r-tBuS25%)24.2k-P(LA-r-BnzLA2o%)iik (HChi-6 BCP), FT = 40 nm on Neutral Underlayer 2, annealing at 250°C / 15 min (N2); 1FOV SEM images, 12 sec etch at 50 mT, 100W, 50 seem O2, and 50 seem N2on Trion etcher.

[0043] FIG. 29 the GPC profile of each sequential block of PS, PS-PtBuS and PS-b-PtBuS-b-PLA of Example 13.

[0044] FIG. 30 Proton NMR spectrum of Example 13 (HChi-3a).

[0045] FIG. 31 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)- DPECH2OH with 20 wt. % PtBS: (A) Example 22, (B) Example 23, (C) Example 24, (D) Example 25, and (E) Example 26.

[0046] FIG. 32 GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)- DPECH2OH with 20 wt. % PtBS: (A) Example 22, (B) Example 23, (C) Example 24, (D) Example 25, and (E) Example 26.

[0047] FIG. 33 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)- DPECH2OH with 28 wt. % PtBS: (A) Example 27, (B) Example 28, and (C) Example 29.

[0048] FIG. 34 GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)- DPECH2OH with 28 wt. % PtBS: (A) Example 27 (B) Example 28, and (C) Example 29.

[0049] FIG. 35 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS- / ?-PtBS)- DPECH2OH with 20 wt. % PtBS: (A) Example 30, (B) Example 31, (C) Example 32, and (D) Example 33. (a) PS and (b) (PS- / ?-PtBS)-DPECH2OH.

[0050] FIG. 36 GPC curves of the hydroxy benzyl-terminated macro initiators of (PS-r-PtBS)- DPECH2OH with 20 wt. % PtBS: (A) Example 30, (B) Example 31, (C) Example 32, and (D) Example 33.

[0051] FIG. 37 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS- / ?- PtBS)BzAd-OH with 20 wt. % PtBS: Example 34.

[0052] FIG. 38 GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r-New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCPtBS)BzAd-OH with 20 wt. % PtBS: Example 34

[0053] FIG. 39 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40.

[0054] FIG. 40 GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.

[0055] FIG. 41 SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40.

[0056] FIG. 42 SEM images of the contact hole nanostructures formed by direct self-assembly (DSA) of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt% PtBS randomly in PS blocks on the prepattern: (A) Example 37 only, (B) the blending of Examples 39 and 40.

[0057] FIG. 43 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45.

[0058] FIG. 44 GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.

[0059] FIG. 45 shows the images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45. Test conditions: On Si; Neutral Underlayer 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher.

[0060] FIG. 46 shows SEM images of the contact hole nanostructures formed by direct selfassembly (DSA) of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks on the prepattern: (A) Example 44 only, (B) the blending of Example 44 and Example 45 with the wt. % ratio of 41 :59 and 68.0% of PS-r-PtBS.

[0061] FIG. 47 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt% PtBS in the hydrophobic blocks of PS- / ?-PtBS: (A) Example 46 and (B) Example 47.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0062] FIG. 48 GPC curves of the high chi block copolymers (BCPs) of (PS- / ?-PtBS)- / ?-PLA with 20 wt% PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 46 and (B) Example 47. (a) Polystyrene, (b) block type macroinitiator of (PS- / ?-PtBS)-DPECH2OH and (b) high chi BCPs.

[0063] FIG. 49 SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt% PtBS in the hydrophobic blocks of PS-Z>- PtBS: (A) Example 46 and (B) Example 47.

[0064] FIG. 50 SEM images of the contact hole nanostructures formed by direct self-assembly (DSA) of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt% PtBS in the hydrophobic blocks of PS- / ? -PtBS on the prepattern: The blending of Example 46 and Example 47 with the wt% ratio of 80.7:19.3 and 71.4% ofPS-6-PtBS. (FOV1 & FOV2).

[0065] FIG. 51 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (C) Example 49.

[0066] FIG. 52 GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt% PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (D) Example 49. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.

[0067] FIG. 53 SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (D) Example 49. Test conditions: On Si; Neutral Underlayer 2 coat; (FOV1).

[0068] FIG. 54. 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >- PLA with 20 wt. % PtBS: (A) Example 51, (B) Example 52, and (D) Example 53.

[0069] FIG. 55. GPC curves of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 51, (B) Example 52, and (C) Example 53. (a) Polystyrene, (b) block type macroinitiator of (PS- / ?-PtBS)-DPECH2OH and (b) high chi BCPs.

[0070] FIG. 56 SEM images of the lamellar nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- Z>-PtBS: (A) Example 51, (B) Example 52, and (C) Example 53. (FOV1). (The detail procedures are described in Example 54).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0071] FIG. 57 SEM images of the line and space nanostructures formed by direct self-assembly (DSA) of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / ?-PtBS on the prepattern: The blending of Example 52 and Example 53 with the wt. % ratio of 50:50 and 50 % of PS- / >-PtBS.

[0072] FIG. 58.1H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 56 and (B) Example 57.

[0073] FIG. 59 GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 56 and (B) Example 57. (a) random type macroinitiator of (PS-r-PtBS)-BzOH and (b) high chi BCPs.SUMMARY

[0074] To overcome the challenges described in the background section, the disclosed and claimed subject matter pertains to new architectures of ABC type triblock copolymer which has a junction segment modified by copolymerization of diblock with carbon or silicon rich repeat units derived from carbon or silicion rich monomers to help orientation control and line stabilization for etching. The chemical modification is performed to 20- 80 wt. % of these monomers in the BCP of high- chi, enabling orientation control on conventional PS-co-PMMA type underlayers using thermal annealing. Specifically, Schemes 1 and 2 show specific non-limiting examples of the disclosed and claimed subject which is an approach to high Chi block copolymers, where environmentally unfriendly perfluoro alkyl or perfluoro ether attached at the junction group have been eliminated in the disclosed and claimed subject matter approach and where instead, high Chi character is imparted by introducing, for instance, simple alkane (carbon) or dimethyl silicon as low surface energy exerting groups via substituted monomers introduced into the block copolymer, either as junction block or copolymerized randomly with styrene and lactide or trimethyl carbonate diblock copolymer. Scheme 1 shows one aspect of the disclosed and claimed subject using simple alkane (carbon) or dimethyl silicon as low surface energy exerting groups via substituted styrene monomers introduced into a non-polar block segment A. This substituted styrene monomer is copolymerized randomly or as a block segment with styrene to form said non-polar block segment A, then a non polar block segment B is introduced which comprises either a homopolymer of a lactone, or copolymers of different lactions. Non-limiting example of such polar block segments are lactide homopolymers or lactide copolymers, or a copolymer of two different lactones, one ofNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC which is may be substituted with a said low surface energy exercising group or alternatively a homopolymer of a trimethylene carbonate moiety homopolymer segment, or a copolymer of two different trimethylene carbonate moieties one of which is substituted. Scheme 1 shows non-limiting examples of these newly developed high-chi platforms consisting of carbon and silicon rich segments in the block copolymer for orientation control and domain stabilization for application towards line / space and contact hole formation in DSA applications.

[0075] Scheme 1

[0076] Scheme 2 shows some specific non-limiting examples of the disclosed and claimed high Chi block copolymers: HChi-3 (carbon and silicon), HChi-3a (carbon), HChi-4 (silicone), HChi-New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC6 (carbon both sides) and HChi-xH3a (carbon and crosslinker) series, which gave good orientation control and domain stabilization up on SEM (e-beam) scan and dry etch condition.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCHChi-6Scheme 2

[0077] More generally, the disclosed and claimed subject matter relates to a block copolymer of structure (I) comprising a non-polar first block segment A prepared by anionic polymerization, a polar second block segments B, prepared by metal catalyzed ring opening coordinative polymerization, a linking moiety Z between said first block segment A, and said second block segment B, and a first and second end groups Ei and E2.

[0078] Further, in this embodiment, said first block segment A, is either a block copolymer segment of structure (II- 1), or a random copolymer segment of structure (II-2), where Ri is selected from the group consisting of a C1-15 linear alkyl, a C3-15 branched alkyl, a -Si(R3a)2-R3 moiety, and a -Si(R3b)2-R3C[Si(R3b)2-O]ni-R3d-R4 moiety, where R3 is selected from a C1-20 linear alkyl or a C3- 20 branched alkyl, Rsa, Rsb, and R4 are individually selected from a C1-6 linear alkyl or a C3-6 branched alkyl, R?c and vi are individually selected from a direct valence bond, a Ci-s alkylene, or -Si(R3b)2- moiety, nl is an integer ranging from 1 to 10; x is the total wt. % of styrene and 4- vinylbenzocyclobutene repeat units, and y is the wt. % of a styrene repeat unit substituted by Ri in structure (II- 1) and a and b are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4-vinylbenzocyclobutene, where x is from about 40 wt. % to about 80 wt. % and y is from about 60 wt. % to about 20 wt. %, and the sum of x and y is 100 % of the weight of the number average molecular weight (Mn) of the block copolymer segment of structureNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(II- 1), and further where a is from about 94 mol. % to about 100 mol. % and b is from about 6 mol. % to 0 mol. %, where the sum of a and b is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4-vinylbenzocyclobutene.

[0079] Further, in this embodiment, x’ is the total wt. % of styrene and 4-vinylbenzocyclobutene repeat units, y’ is the wt. % of a styrene repeat unit substituted by Ri in structure (II-2) and a’ and b’ are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4-vinylbenzocyclobutene, where x’ is from about 40 wt. % to about 80 wt. % and y’ is from about 60 wt. % to about 20 wt. %, and the sum of x’ and y’ is 100 % of the weight of the Mnof the random copolymer segment of structure (II-2), and further where a’ is from about 94 mol. % to about 100 mol. % and b’ is from about 6 mol. % to 0 mol. %, where the sum of a’ and b’ is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4- vinylbenzocyclobutene.

[0080] Further, in this embodiment, said linking group Z, is an alkoxide comprising moiety of structure (III), (Illa) or (Illb) where Rz2, Rzs and Rz4, Rzs, Rzg, are independently selected from H, a Ci-8 alkyl, and an aryl, Rz, Rzi, are either independently selected from H, a Ci-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1, and further where Rz? is H, a C1-8 alkyl, an aryl, a biphenyl moiety, and Rzs is H or a Ci-s alkyl.

[0081] Further, in this embodiment, said second block segment B is either a homopolymer segment, a di-block copolymer segment, or a random copolymer segment, where when said block segment B is a homopolymer segment it has repeat units of structure (IV).

[0082] Further, in this embodiment, when said block segment B is a di-block copolymer segment, it has structure (IV-2) which comprises a first block with repeat units of structure (IV) and a second block of structure (IV- 1), where structure (IV) and (IV- 1) have different structures.

[0083] Further, in this embodiment, when said block segment B is a random copolymer segment, it has structure (IV-3) which comprises repeat units of structures (IV) and (IV- 1), where (IV) and (IV) are different structures.

[0084] Further, in this embodiment, in structure (IV) X is oxy (-O-) or a direct valence bond, where nb is 1 or 0, nbl is 0 or 1, where when X is oxy, the sum of nb and nbl is 2, and where R2, R2a, R2band R2C, are independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0085] Further, in this embodiment, in structure (IV- 1) X’ is oxy (-O-) or a direct valence bond, where nb’ is 1 or 0, nb’l is 0 or 1, and where when X’ is oxy the sum of nb’ and nb’l is 2, and where R2’, R2’a, R2’b, and R2’care independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, or a -Rs-Aryl moiety, where R5 is a C1-4 alkylene.

[0086] Further, in this embodiment, in structure (IV-2), xa designates the wt. % of the repeat units of structure (IV) and ya designates the wt. % of repeat units of structure (IV- 1), where xa is from about 40 wt. % to about 80 wt. % of the total weight of said second block segment B, and ya is from about 60 wt. % to about 20 wt. %, where the sum of xa and ya equals 100 % of the weight of the Mnof said second block segment B of structure (IV-2).

[0087] Further, in this embodiment, in structure (IV-3) xa’ designates the wt. % of the repeat units of structure (IV) and ya’ designates the wt. % of repeat units of structure (IV-1), where xa‘ is from about 40 wt. % to about 80 wt. % of the total weight of said second block segment B, and ya’ is from about 60 wt. % to about 20 wt. % of said second block segment B, where the sum of xa’ and ya’ equals 100 % of the weight of the weight of the Mnof said second block segment B of structure (IV-3).

[0088] Further, in this embodiment, said first end group, Ei, is a C1-18 alkyl, or a C3-6 branched alkyl and said second end group, E2, is a carbonyl alkyl (-C(=O)-alkyl) moiety, where said alkyl is a Ci- 8 alkyl or aryl, and further where the number average molecular (Mn) of the said block copolymer of structure (I) is from about 2000 g / mol to about 100,000 g / mol, and the ratio of the Mnof said first block segment A to the Mnof said second block segment B ranges from about 0.40 to about 0.75,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(IV) (IV-1) (IV-3).

[0089] Also disclosed and claimed subject matter pertains to a composition comprising said copolymer of structure (I) and using said composition in lithographic processes which employ selfassembly or directed self-assembly (DSA) in the manufacture of IC devices.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCDETAILED DESCRIPTION

[0090] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. In this application, the use of the singular includes the plural, the word "a" or "an" means "at least one", and the use of "or" means "and / or," unless specifically stated otherwise. Furthermore, the use of the term "including," as well as other forms such as "includes" and "included," is not limiting. Also, terms such as "element" or "component" encompass both elements and components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive unless otherwise indicated. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the foregoing elements including using a single element.

[0091] The term Cxwhere x is a positive integer designates the number of carbons in a moiety. Similarly, the term Ci to C4 alkyl or C1-4 alkyl embodies methyl and C2 to C4 linear alkyls and C3 to C4 branched alkyl moieties, for example as follows: methyl (-CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2, n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2, 2-butyl (-CH(CH3)CH2-CH3). Similarly, the term Ci to Cs alkyl or Ci-s alkyl embodies, Ci to Cs linear alkyls (methyl is considered a linear alkyl), C3 to Cs branched alkyls, C4 to Cs cycloalkyls (e.g., cyclopentyl, cyclohexyl etc) or C5-8 alkylenecycloalkyls (e.g., -CH2- cyclohexyl, CFL-CIL-cyclopentyl etc.) Other designation such as C1-20, C1-6, C1-15 are defined in the same way unless otherwise indicated.

[0092] The term C2 to Cs alkylene or C2-8 alkylene embodies C2 to Cs linear alkylene moieties (e.g., ethylene, propylene etc), 1,1 -ethylene and C3 to Cs branched alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc) unless otherwise indicated.

[0093] The term “g / mol” or “g / mole” is an abbreviation of grams per mole.

[0094] The term “CH” is an abbreviation for contact hole lithographic features, the term “L / S” is an abbreviation for line and space lithographic features.

[0095] The term “b” in a copolymer structure indicates that this is a block copolymer. Similarly, the term “co” or “r” in a copolymer structure indicates that this is a random copolymer.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0096] Volume fraction (Vf) expressed in % as Volume % (Vol% ) refers to a value calculated as follows: for example, the polystyrene volume fraction as % in a polystyrene PLA block copolymer (PS-b-PLA) polymer is calculated as follows: Vol % = { Mn(PS block) / density bulk PS} / [{ Mn(PS block) / density of bulk PS} + { Mn(PLA block) / density of bulk PLA}] x 100, where densities are densities as determined by 20 °C. Futher, in the case of styrenic copolymer blocks containing styrene and other styrenic repeat units, an average density based on the molar content of the two repeat units and known or calculated bulk density of the respective homopolymer is employed, for example 1.050 g / cm3for polystyrene and 0.9458 g / cm3for poly(tert-butylstyrene). Similarly, in the case of a PLA block which is a copolymer of PLA and another different PLA derivative the same approach is used where an average density based on the molar content of the two different repeat units and known or calculated bulk density of the respective homopolymer is employed.Block Copolymer

[0097] The disclosed and claimed subject matter pertains to a block copolymer of structure (I) comprising a non-polar first block segment A prepared by anionic polymerization, a polar second block segment B, prepared by metal catalyzed ring opening coordinative polymerization, a linking moiety Z between said first block segment A, and said second block segment B, and a first and second end groups Ei and E2.

[0098] Further, in this embodiment said first block segment A is either a block copolymer segment of structure (11-1), or a random copolymer segment of structure (11-2), where Ri is selected from the group consisting of a C1-15 linear alkyl, a C3-15 branched alkyl, a -Si(R3a)2-R3 moiety, and a -Si(R3b)2-R3C-[Si(R3b)2-O]ni-R3d-R4 moiety, where R3 is selected from a C1-20 linear alkyl or a C3- 20 branched alkyl, FLa, Rsb, and R4 are individually selected from a C1-6 linear alkyl or a C3-6 branched alkyl, FLc and FLd are individually selected from a direct valence bond, a Ci-s alkylene, or -Si(R3b)2- moiety, nl is an integer ranging from 1 to 10, and where x is the total wt. % of styrene and 4-vinylbenzocyclobutene repeat units, and y is the wt. % of a styrene repeat unit substituted by Ri in structure (11-1) and a and b are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4-vinylbenzocyclobutene, where x is from about 40 wt. % to about 80 wt. % and y is from about 60 wt. % to about 20 wt. %, and the sum of x and y is 100 % of the weight of the number average molecular weight (Mn) of the block copolymer segment of structure (11-1), and further where a is from about 94 mol. % to about 100 mol. % and b is from about 6New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC mol. % to 0 mol. %, where the sum of a and b is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4-vinylbenzocyclobutene.

[0099] Further, in this embodiment, x’ is the total wt. % of styrene and 4-vinylbenzocyclobutene repeat units, y’ is the wt. % of a styrene repeat unit substituted by Ri in structure (II-2) and a’ and b’ are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4-vinylbenzocyclobutene, where x’ is from about 40 wt. % to about 80 wt. % and y’ is from about 60 wt. % to about 20 wt. %, and the sum of x’ and y’ is 100 % of the weight of the Mnof the random copolymer segment of structure (II-2), and further where a’ is from about 94 mol. % to about 100 mol. % and b’ is from about 6 mol. % to 0 mol. %, where the sum of a’ and b’ is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4- vinylbenzocyclobutene.

[0100] Further, in this embodiment, said linking group Z, is an alkoxide comprising moiety of structure (III), (Illa) or (Illb) where Rz2, Rzs and Rz4, Rzs, Rzg, are independently selected from H, a Ci-8 alkyl, and an aryl, Rz, Rzi, are either independently selected from H, a Ci-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1, and further where Rz? is H, a C1-8 alkyl, an aryl, a biphenyl moiety and Rzs is H or a C1-8 alkyl. Further, in this embodiment, said second block segment B is either a homopolymer segment, a diblock copolymer segment, or a random copolymer segment, where when said block segment B is a homopolymer segment it has repeat units of structure (IV).

[0101] Further, in this embodiment, when said block segment B is a diblock copolymer segment, it has structure (IV-2) which comprises a first block with repeat units of structures (IV) and a second block of structure (IV- 1), where structure (IV) and (IV- 1) have different structures.

[0102] Further, in this embodiment, when said block segment B is a random copolymer segment, it has structure (IV-3) which comprises repeat units of structures (IV) and (IV- 1), where (IV) and (IV) are different structures.

[0103] Further, in this embodiment, in structure (IV) X is oxy (-O-) or a direct valence bond, where nb is 1 or 0, nbl is 0 or 1, where when X is oxy, the sum of nb and nbl is 2, and where R2, R2a, R2band R2C, are independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0104] Further, in this embodiment, in structure (IV- 1) X’ is oxy (-O-) or a direct valence bond, where nb’ is 1 or 0, nb’l is 0 or 1, and where when X’ is oxy the sum of nb’ and nb’l is 2, and where R2’, R2’a, R2’b, and R2’care independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, or a -Rs-Aryl moiety, where R5 is a C1-4 alkylene.

[0105] Further, in this embodiment, in structure (IV-2), xa designates the wt. % of the repeat units of structure (IV) and ya designates the wt. % of repeat units of structure (IV- 1), where xa is from about 40 wt. % to about 80 wt. % of the total weight of said second block segment B, and ya is from about 60 wt. % to about 20 wt. %, where the sum the xa and ya equals 100 % of the weight of the Mnof said second block segment B of structure (IV-2).

[0106] Further, in this embodiment, in structure (IV-3), xa’ designates the wt. % of the repeat units of structure (IV) and ya’ designates the wt. % of repeat units of structure (IV-1), where xa‘ is from about 40 wt. % to about 80 wt. % of the total weight of said second block B, and ya’ is from about 60 wt. % to about 20 wt. % of said second block segment B, where the sum the xa’ and ya’ equals 100 % of the weight of the weight of the Mnof said second block segment B of structure (IV-3). Further, in this embodiment, said first end group Ei is a Ci-is alkyl, or a C3-6 branched alkyl and said second end group E2 is a carbonyl alkyl (-C(=O)-alkyl) moiety, where said alkyl is a C1-8 alkyl or aryl, and further where the number average molecular (Mn) of the said block copolymer of structure (I) is from about 2000 g / mol to about 100,000 g / mol, and the ratio of the Mnof said first block segment A to the Mnof said second block segment B ranges from about 0.40 to about 0.75;New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(IV) (iv- 1) (IV-3).

[0108] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one where futher said block segment A has an Mnbetween about 1000 g / mole to about about 48,000 g / mole and said block segment B has an Mnfrom about 1000 g / mole to about 52,000 g / mole but where further the sum of the Mnof block segment A and block segment B must add to a value from about 2000 g / mole to about 100,000 g / mole for the block copolymer, excluding values for the Mnof block segment A and block segment B which fall out of the these above individual ranges of Mnfor block segment A and block segment B calculated from a ratio of the Mnof said first block segment Ato the Mnof said second block segment B which ranges from about 0.40 to about 0.75.

[0109] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one which consist of a first block segment A and a second block segment B, a linking moiety Z between said first and second block segments A and B, and a first and second end group El and E2.

[0110] Another embodiment of the disclosed and claimed block copolymer of structure (I),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC discussed above is one wherein the ratio of the Mnof block segment A to the Mnof block segment B is from about 0.47 to about 0.67. More preferably the ratio is 0.48 to about 0.68, more preferably 0.49 to about 0.69, more preferably 0.5 to about 0.7.

[0111] Another embodiment of the disclosed and claimed block copolymer of structure (I), discussed above is one wherein said ratio of the Mnof block segment A to Block segment B is from about 0.40 to about 0.60. More preferably about 0.41 to about 0.60. More preferably about 0.42 to about 0.60. More preferably about 0.43 to about 0.60. More preferably about 0.44 to about 0.60. More preferably about 0.45 to about 0.60. More preferably it is about 0.46 to about 0.60. More preferably it is about 0.47 to about 0.60.

[0112] Another embodiment of the disclosed and claimed block copolymer of structure (I), discussed above is one wherein said ratio of the Mnof block segment A to block segment B is from about 0.61 to about 0.75. In another aspect of this embodiment the ratio is from about 0.61 to about 0.74. In another aspect of this embodiment, it is more preferably from about 0.61 to about 0.73. In another aspect of this embodiment, it is more preferably from about from about 0.61 to about 0.72. In another aspect of this embodiment, it is more preferably from about 0.61 to about 0.71. More preferably it is from about 0.61 to about 0.70.

[0113] In another embodiment of the disclosed and claimed block copolymer of structure (I), it has a number average molecular weight (Mn) from about 3,000 g / mol to about 90,000 g / mol. In another aspect of this embodiment Mnis from about 5,000 g / mol to about 80,000 g / mol. In another aspect of this embodiment the Mnis more preferably, from about 7,000 g / mol to about 60,000 g / mole. In another aspect of this embodiment the Mnis more preferably, from about 9,000 g / mol to about 50,000 g / mole. In another aspect of this embodiment the Mnis more preferably, from about 10,000 g / mol to about 50,000 g / mol.

[0114] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A has an Mnfrom about 2,000 g / mol to about 41,000 g / mol and were said second block segment B, has and Mnwhich is from about 2,250 g / mol to about 44,500 g / mol and excluding values of Mnof said first block segment A and second block segment B calculated from the ratio of the Mnof block segment Ato Block segment B of about 0.40 to about 0.60 second block segment B which fall out of said ranges of Mn for first block segment A and second block segment B.. In another aspect of this embodiment said first block segment A has anNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCMnfrom about 3,000 g / mol to about 34,000 g / mol and were said second block segment B, has and Mnwhich is from about 3,500 g / mol to about 37,000 g / mol. In another aspect of this embodiment, said first block segment A has an Mnfrom about 4,000 g / mol to about 27,000 and were said second block segment B, has and Mnwhich is from about 4,750 g / mol to about 29,500 g / mol. In another aspect of this embodiment, said first block segment A has an Mnfrom about 5,000 g / mol to about 20,000 g / mol and were said second block segment B, has and Mnwhich is from about 6,000 g / mol to about 22,000 g / mol.

[0115] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein its poly dispersity ranges from 1.00 to about 1.15. In another aspect of this embodiment, from 1.00 to about 1.10, or more preferentially from 1.00 to about 1.08. In another aspect of this embodiment, from 1.00 to about 1.07. In another aspect of this embodiment, from 1.00 to about 1.06. In another aspect of this embodiment, from 1.00 to about 1.05. In another aspect of this embodiment, from 1.00 to about 1.04. In another aspect of this embodiment, from 1.00 to about 1.03. In another aspect of this embodiment, from 1.00 to about 1.02. In another aspect of this embodiment, from about 1.00 to about 1.04. In another aspect of this embodiment, from 1.00 to about 1.01.

[0116] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said block segment A has a volume % ranging from about 43 vol. % to about 71 vol. % and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

[0117] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said block segment A has a volume % ranging from about 43 vol. % to about 71 vol. % and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

[0118] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said block segment A, when Ri is a -Si(R3a)2-R3 moiety, has a vol. % from about 47 to about 53 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60. In another aspect of this embodiment Ri is -Si(CH3)2-R3. In another aspect of this embodiment Ri is -Si(CH3)3. In another aspect of this embodiment Ri is -Si(CH3)2-(CH2)i4-CH3.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0119] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said block segment A, when Ri is a -Si(R3a)2-R3 moiety, has a vol. % from about 47 to about 53 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75. In another aspect of this embodiment Ri is -Si(CH3)2-R3. In another aspect of this embodiment Ri is -Si(CH3)3. In another aspect of this embodiment Ri is -Si(CH3)2-(CH2)i4-CH3.

[0120] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said non polar block segment A, when Ri is a - C1-15 linear alkyl or a C3-15 branched alkyl moiety, said non-polar block segment A has a volume % from about 44 vol. % to about 65 vol. % of the total volume of said non polar block segment A and said polar block segment B, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

[0121] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said non polar block segment A, when Ri is a - C1-15 linear alkyl or a C3-15 branched alkyl moiety, said non-polar block segment A has a volume % from about 44 vol. % to about 65 vol. % of the total volume of said non polar block segment A and said polar block segment B, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

[0122] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said non polar block segment A, when Ri is -Si(R3b)2-R3o-[Si(R3b)2-O]ni-R3d-R4 moiety, said non-polar block segment A has a volume % from about 50 vol. % to about 62 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.40 to about 0.60. In another aspect of this embodiment Ri has structure -Si(CH3)2-CH2-CH2— [Si(CH3)2-O]ni-Si(CH3)2-R4. In another aspect of this embodiment Ri more specifically has structure -Si(CH3)2-CH2-CH2— [Si(CH3)2-O]ni-Si(CH3)2-i-Bu, in another aspect of this embodiment nl is an integer from 2 to 5, in another aspect of this embodiment nl is an integer from 2 to 4, in another aspect of this embodiment R4 is a C3-6 branched alkyl.

[0123] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one, where said non polar block segment A, when Ri is -Si(R3b)2-R3o-[Si(R3b)2-O]ni-R3d-R4 moiety, said non-polar block segment A has a volume % from about 50 vol. % to about 62 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the MnNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC of block segment Ato the Mnof block segment B is from about 0.61 to about 0.75. In another aspect of this embodiment Ri has structure -Si(CH3)2-CH2-CH2— [Si(CH3)2-O]ni-Si(CH3)2-R4. In another aspect of this embodiment Ri more specifically has structure -Si(CH3)2-CH2-CH2— [Si(CH3)2-O]ni-Si(CH3)2-i-Bu, in another aspect of this embodiment nl is an integer from 2 to 5, in another aspect of this embodiment nl is an integer from 2 to 4, in another aspect of this embodiment R4 is a C3-6 branched alkyl.

[0124] Another embodiment of the disclosed and claimed block copolymer of structure (I), it is one wherein said first block segment A, has structure (II- 1 ).

[0125] Another embodiment of the disclosed and claimed block copolymer of structure (I), it is one wherein said first block segment A, has structure (II-l ) and x is from about 45 wt. % to 75 wt. % and y is from 55 wt. % to 25 wt. %, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

[0126] Another embodiment of the disclosed and claimed block copolymer of structure (I), it is one wherein said first block segment A, has structure (II-l ) and x is from about 45 wt. % to 75 wt. % and y is from 55 wt. % to 25 wt. %, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

[0127] Another embodiment of the disclosed and claimed block copolymer of structure (I), it is one wherein said first block segment A, has structure (II-l ), and b is 0 mol. %.

[0128] Another embodiment of the disclosed and claimed block copolymer of structure (I), it is one wherein said first block segment A, has structure (II-l) and b ranges from about 0.5 mol. % to about 6 mol. %.

[0129] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A, has structure (II-2).

[0130] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A, has a structure (II-2) were x ranges from about 45 wt. % to about 75 wt. % and y ranges from about 55 wt. % to about 25 wt. %, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

[0131] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A, has a structure (II-2) were x ranges from about 45 wt. % to about 75 wt. % and y ranges from about 55 wt. % to about 25 wt. % and said ratio of the MnofNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

[0132] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A, has structure (II-2) and b’ is 0 mol. %.

[0133] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said first block segment A, has structure (II -2) and b’ ranges from about 0.5 mol. % to about 6 mol. %.

[0134] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein Ri is a CMS linear alkyl. In another aspect of this embodiment, Ri is a Ci-io linear alkyl. In another aspect of this embodiment, Ri is a Ci-s linear alkyl. In another aspect of this embodiment, Ri is a Ci-5 linear alkyl. In another aspect of this embodiment, Ri is methyl or ethyl. In another aspect of this embodiment, Ri is methyl.

[0135] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein Ri is a C3-15 branched alkyl. In another aspect of this embodiment, Ri is a C3-10 branched alkyl. In another aspect of this embodiment, Ri is a C3-5 branched alkyl. In another aspect of this embodiment, Ri is tert-butyl.

[0136] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein Ri is a -Si(R3a)2-R3 moiety. In another aspect of this embodiment, R3 is C1-15 linear alkyl. In another aspect of this embodiment, R3 is C5-15 linear alkyl. In another aspect of this embodiment, In another aspect of this embodiment, R3 is C10-15 linear alkyl. In another aspect of this embodiment, R3 is C15 linear alkyl. In another aspect of this embodiment, R3 is C1-10 linear alkyl. In another aspect of this embodiment, R3 is Ci-s linear alkyl. In another aspect of this embodiment, R3 is C1-5 linear alkyl. In another aspect of this embodiment, R3 is C1-3 linear alkyl. In another aspect of this embodiment, R3 is ethyl or methyl. In another aspect of this embodiment, R3 is methyl. In another aspect of this embodiment, R3 is C3-15 branched alkyl. In another aspect of this embodiment, R3 is C3-10 branched alkyl. In another aspect of this embodiment, R3 is C3-8 branched alkyl. In another aspect of this embodiment, R3 is C3-5 branched alkyl. In another aspect of this embodiment, R3 is tert-butyl. In another aspect of this embodiment, Rsa is C1-15 linear alkyl. In another aspect of this embodiment, Rsais C1-10 linear alkyl. In another aspect of this embodiment, Rsais C1-8 linear alkyl. In another aspect of this embodiment, Rsa is C1-5 linear alkyl. In another aspect of this embodiment, Rsa is C1-3 linear alkyl. In another aspect of this embodiment, Rsais ethyl or methyl. In anotherNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC aspect of this embodiment, Rsa is methyl. In another aspect of this embodiment, R?ais methyl and R3 is a C15 linear alkyl; in one aspect of this embodiment Rsa is C3-15 branched alkyl; in another aspect of this embodiment Rsa is C3-10 branched alkyl; in another aspect of this embodiment Rsa is C3-8 branched alkyl; in another aspect of this embodiment, R?ais C3-5 branched alkyl; in another aspect of this embodiment, Rsa is tert-butyl. In another aspect of this embodiment Ri is -Si(CH3)3.

[0137] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein Ri is a -Si(R3b)2-R3o-[Si(R3b)2-O]ni-R3d-R4 moiety. In another aspect of this embodiment Ri has structure -Si(CH3)2-CH2-CH2— [Si(R3b)2-O]ni-Si(CH3)2-R4. In another aspect of this embodiment Ri more specifically has structure -Si(CH3)2-CH2-CH2-[Si(R3b)2-O]ni-Si(CH3)2-i-Bu, in another aspect of this embodiment nl is an integer from 2 to 5, in another aspect of this embodiment nl is an integer from 2 to 4, in another aspect of this embodiment R4 is a C3-6 branched alkyl. In another aspect of this embodiment, Rsb is a C1-15 linear alkyl. In another aspect of this embodiment, Rsb is a C1-10 linear alkyl. In another aspect of this embodiment, Rsb and R4 are individually selected from a C1-5 linear alkyl. In another aspect of this embodiment, R?b and R4 are individually selected from a C1-4 linear alkyl. In another aspect of this embodiment, R?b and R4 are individually selected from ethyl or methyl. In another aspect of this embodiment, R?b and R4 are methyl.

[0138] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z is an alkoxide moiety of structure (III), where nz is 0.

[0139] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z has structure (III-l ). In another aspect of this embodiment Rz2 is an aryl and Rzi is H. In another aspect of this embodiment, Rz2 is an aryl and Rzi is H. In another aspect of this embodiment Rz2 is an aryl and Rzi is H. In another aspect of this embodiment said linking group Z has stru

[0140] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z has structure (III-3) where Rz2 is a H or a Ci to C4 alkyl. Another aspect of this embodiment is where said linking group Z has structure (III-3a). Another aspect ofNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC this embodiment is where said linking group Z has structure (III-3b). Another aspect of this embodiment is where said linking group has structure (III-3c). Another aspect of this embodiment is where said linking group has structure (III-3d).

[0141] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein Rz, Rzi, form together a C3 to C4 alkylene moiety which forms a 5 to 6 membered ring, and where said linking group Z has structure (III-4). In another aspect of this embodiment is has structure (III-4a).(lll-4a).

[0142] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z is an alkoxide moiety of structure (III), where nz is 1.

[0143] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z has structure (III-5). In another embodiment it has structure (III-6), In another embodiment it has structure (III-6). In another embodiment it has structure (ni-7).

[0144] Another embodiment of the disclosed and claimed block copolymer of structure (I), is one wherein said linking group Z of structure (III) is one wherein Rz2 and Rz4 are H, and Rz, Rzi and Rzs are independently a Cns alkyl and nz is 1. In another aspect of this embodiment, it has structure (III-8).

[0145] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said liking group Z of structure (III), is one wherein Rz, Rzs and Rz4, are H, and Rzl is an aryl, and Rz2 is a Ci-s alkyl and nz is 1. In another aspect of this embodiment, it has structure (Ill-New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0146] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said liking group Z of structure (III), has structure (III- 10).

[0147] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said liking group Z has structure (Illa). In another aspect of this embodiment Rzs and Rzb are individually selected from H or a Cns alkyl. In another aspect of this embodiment, Rzs and Rzb are individually selected from H or an aryl. In another aspect of this embodiment, said linking group Z has structure (IIIa-1). In another aspect of this embodiment, said linking group Z has structure (Illa- 2)

[0148] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said liking group Z has structure (Illb). In another aspect of this embodiment Rz? is H and Rzs is a Ci-8 alkyl. In another aspect of this embodiment, Rz? is a Ci-8 alkyl and Rzs is H. In another aspect of this embodiment, Rz? is a Ci-4 alkyl and Rzs is H. In another aspect of this embodiment, Rz? is a Ci-8 alkyl and Rzs is a Ci-8 alkyl. In another aspect of this embodiment, it has structure (IIIb-1). In another aspect of this embodiment, it has structure (IIIb-2).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0149] In another embodiment of the disclosed and claimed block copolymer of structure (I) wherein said liking group Z has structure (Illb), Rz? is an aryl and Rzs is H. In another aspect of this embodiment, it has structure (IIIc-1). In another embodiment of the disclosed and claimed block copolymer of structure (I) wherein said liking group Z has structure (Illb), Rz? is a biphenyl moiety and Rzs is H. In another aspect of this embodiment, it has structure (IIIc-2).

[0150] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IV).

[0151] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa).

[0152] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-1).

[0153] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, which has a repeat unit of structure (IVa-3), where R2, R2a, and R2bare individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety, and R20 is selected from H, a C1-6 linearNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety.

[0154] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-4), where R2, and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0155] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-5), where R2a and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0156] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-6), where R2, and R2a are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0157] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-7), where R2a is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0158] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-8), where R2b is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0159] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-9), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a - Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC— |-c — CH2— CH — CH2— oj- — |-c — CH2— CH2— CH — oj- — |-c — CH— CH2— CH2— oj-R2a (IVa-7) R2b (IVa-8)R= (IVa-9)

[0160] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-10), where R2a is selected from a Ci-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0161] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-11), where R2 is individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety, and where R2Cis individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety.

[0162] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B is a homopolymer block which has a repeat unit of structure (IVa-12), where R2and R2a are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0163] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-12a).

[0164] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-13), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rj is a C1-4 linear alkylene moiety, and R20 is selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety. In one aspect of this embodiment, it has structure (IVa-14). In another aspect of this embodiment, it has structure (IVa- 14’).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0165] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-15). o 4"_CH2’4(IVa-15).

[0166] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb). In another aspect of this embodiment, R2, R2a and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0167] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb’).

[0168] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb’), where R2, R2a, R2b and R2Care individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0169] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-1).

[0170] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-2), where R2, and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0171] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure(IVb-3), where R2, and R2a are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0172] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure(IVb-4), where R2a, and R2b are individually selected from a Ci-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0173] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-5), where R2a, is individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.oJ — C~ O — CH2— CH — CH2— LR2a (IVb-5)

[0174] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-2), where structure (IV) and (IV- 1) are different structures.(IV) (iv-1) (IV-2)

[0175] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-2a), where structure (IVa) and (IVa-1) areNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC different structures.(IVa) (IVa-1) (IV-2a)

[0176] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV2b), where structures (IVb) and (IVb-1) are different structures.(IVb) (IVb-1) (IV-2b)

[0177] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV2b’), where structures (IVc-2) and (IVc-3) are different structures.(IVc-2) (IVc-3) (IV-2b’)

[0178] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-2b”), where I ’a is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.(IV (ivc-i) (IV-2b”)

[0179] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-2c), where structures (IVa) and (IVb-1) are different structures.(IVa) a™-1) (IV-2c)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0180] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-2d).(IVb) (IVa-1) (IV-2d)

[0181] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2e), where R2, R2a, and R2Care independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0182] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2f), where R2, R2a, and R2Care independently either a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety.

[0183] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2g), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety, and R2Cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and R2’cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety.

[0184] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2h), where R2 selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC where Rs is a Ci-4 linear alkylene moiety, and R2Cis selected from H, a Ci-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety. In one aspect of this embodiment, it has structure (IV-2ha), where R2 selected from a C1-6 linear alkyl, and R2’ is selected from an aryl moiety and a -Rs-Aryl moiety. In another aspect of this embodiment, it has structure (IV-2hb). In another aspect of this embodiment, it has structure (IV-2hb) where R2’ is a -Rs-aryl; in another aspect of this embodiment R2’ is -CH2-aryl; in another aspect of this embodiment, R2’ is benzyl. In another aspect of this embodiment, it has structure (IV-2hb) where R2’ is an aryl; in another aspect of this embodiment R2’ is phenyl.

[0185] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is said random copolymer segment of structure (IV-3).(IV) (IV-1) (IV-3)

[0186] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-3a), where structure (IVa) and (IVa-1) are different structures.

[0187] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one, wherein said second block segment B, has structure (IV3b), where structures (IVb) and (IVb-1) are different structures.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(IVb) (IVb-1) (IV-3b)

[0188] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-3c), where structures (IVa) and (IVb-1) are different structures.(IVa) (IVb-1) (IV-3C).

[0189] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-3d).(IVb) (IVa-1) (IV-3d)

[0190] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, has structure (IV-3e), where R2, R2a, and R2Care independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0191] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3f), where R2, R2a, and R2Care independently either a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety.

[0192] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3g), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC where Rs is a C1-4 linear alkylene moiety, and R2Cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and R2’cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety.

[0193] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3h), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where Rs is a C1-4 linear alkylene moiety, and R2Cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety. In one aspect of this embodiment, it has structure (IV-3ha), where R2 is selected from a C1-6 linear alkyl, and R2’ is selected from an aryl moiety and a -Rs-Aryl moiety. In another aspect of this embodiment, it has structure (IV-3hb). In another aspect of this embodiment, it has structure (IV-3hb), where R2’ is a -Rs-aryl; in another aspect of this embodiment R2’ is -CH2-aryl; in another aspect of this embodiment, R2’ is benzyl. In another aspect of this embodiment, it has structure (IV-3hb), where R2’ is an aryl; in another aspect of this embodiment R2’ is phenyl.

[0194] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3i), where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0195] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said second block segment B has an Mnbetween about 5,000 g / mol to about 17,000 g / mol.

[0196] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said block segment B, is a diblock copolymer segment and is either one of structures (IV- 2), (IV-2a), (IV-2b), (IV-2b’), (IV-2b”), (IV-2c), (IV-2d), (IV-2e), (IV-2f), (IV-2g), or (IV-2h), where xa ranges from about 40 wt. % to about 80 wt. % and ya ranges from about 60 wt. % to about 20 wt. %, and the sum of xa and ya is 100 % of the weight of the Mnof said second block segment B.

[0197] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said block segment B, is a diblock copolymer segment is either one of structures (IV-2g), or (IV-2h), where xa ranges range from about 40 wt. % to about 80 wt. % and ya ranges from about 60 wt. % to about 20 wt. %, and the sum of xa and ya is 100 % of the weight of the Mnof said second block segment B.

[0198] The block copolymer of structure (I), where said block segment B, is a diblock copolymer segment is either one of structures (IV-3), (IV-3a), (IV-3b), (IV-3c), (IV-3d), (IV-3e), (IV-3f), (IV- 3g), (IV-3h), or (IV-3i), where xa’ ranges from about 40 wt. % to about 80 wt. % and ya’ ranges from about 60 wt. % to about 20 wt. %, and the sum of xa’ and ya’ is 100 % of the weight of the Mnof said second block segment B.

[0199] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said block segment B, is a diblock copolymer segment is either one of structures (IV-3g), (IV-3h), or (IV-3i), where xa’ ranges from about 40 wt. % to about 80 wt. % and ya’ ranges from about 60 wt. % to about 20 wt. %, and the sum of xa’ and ya’ is 100 % of the weight of the the Mnof said second block segment B.

[0200] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said end group Ei is a C3-10 alkyl. In one aspect of this embodiment, Ei is a C3-10 alkyl which has structure (IV), where RE is a C1-4 alkyl and R1.11> is a C1-5 alkyl. In another aspect of this embodiment Ei is sec-butyl.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0201] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one wherein said end group E2 is a carbonyl alkyl (-C(=O)-alkyl) where said alkyl is a linear Cns alkyl. In another aspect of this embodiment E2 is a carbonyl alkyl (-C(=O)-alkyl) where said alkyl is methyl.

[0202] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one which has structure (Va), where Ri is selected from and C1-15 linear alkyl, and a C3-15 branched alkyl, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2Cis selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol. In another aspect of this embodiment, it has structure (Va-1). In another aspect of this embodiment, it has structure (Va-2). In another aspect of this embodiment, it has structure (Va-2a). In another aspect of this embodiment, it has structure (Va-3). In another aspect of this embodiment, it has structure (Va-3a). In another aspect of this embodiment, it has structure (Va-4). In another aspect of this embodiment, it has structure (Va-5). In another aspect of this embodiment, it has structure (Va-6). In another aspect of this embodiment, it has structure (Va-7). In another aspect of this embodiment, it has structure (Va-8). In another aspect of this embodiment, it has structure (Va-9). In another aspect of this embodiment, it has structure (Va-10). In another aspect of this embodiment, it has structure (Va-11). In one aspect of this embodiment, y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A. In another aspect of this embodiment y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0203] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one which has structure has structure (Vb), where Ri is selected from a C1-15 linear alkyl, a C3-15 branched alkyl, and a -Si(R3a)2-R3 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2O is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol, and b ranges from about 0.5 mol. % to about 6 mol. %, of the total moles of the repeat units derived from styrene and 4- vinylbenzocyclobutene. In another aspect of this embodiment, it has structure (Vb-1) In another aspect of this embodiment, it has structure (Vb-2). In another aspect of this embodiment, it has structure (Vb-2a). In another aspect of this embodiment, it has structure (Vb-3). In another aspect of this embodiment, it has structure (Vb-3a). In another aspect of this embodiment, it has structure (Vb-4). In another aspect of this embodiment, it has structure (Vb-5). In another aspect of this embodiment, it has structure (Vb-6). In another aspect of this embodiment, it has structure (Vb-7). In another aspect of this embodiment, y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A. In another aspect of this embodiment, y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC).

[0204] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one which has structure (Vc), where Ri is selected from and C1-15 linear alkyl, and a C3-15 branched alkyl, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2Cis selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol. In another aspect of this embodiment, it has structure (Vc-1). In another aspect of this embodiment, it has structure (Vc-2). In another aspect of this embodiment, it has structure (Vc-2a). In another aspect of this embodiment, it has structure (Vc-3). ). In anotherNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC aspect of this embodiment, it has structure (Vc-3a). In another aspect of this embodiment, it has structure (Vc-4). In another aspect of this embodiment, it has structure (Vc-5). In another aspect of this embodiment, it has structure (Vc-6). In another aspect of this embodiment, it has structure (Vc-7). In another aspect of this embodiment, it has structure (Vc-8). In another aspect of this embodiment, it has structure (Vc-9). In another aspect of this embodiment, it has structure (Vc- 10). In another aspect of this embodiment, it has structure (Vc-11). In another aspect of this embodiment, y’ is from about 18 wt. % to about 22 wt. %, of the total weight of the molecular weight of said first block segment A. In another aspect of this embodiment, y’ is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0205] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one which has structure (Vd), where Ri is a -Si(R3a)2-R3 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2Cis selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where theNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol. In another aspect of this embodiment, it has structure (Vd-1). In another aspect of this embodiment, it has structure (Vd-2). In another aspect of this embodiment, it has structure (Vd-2a). In another aspect of this embodiment, it has structure (Vd-3). In another aspect of this embodiment, it has structure (Vd-3a). In another aspect of this embodiment, it has structure (Vd-4). In another aspect of this embodiment, it has structure (Vd-5). In another aspect of this embodiment, it has structure (Vd- 5a). In another aspect of this embodiment, it has structure (Vd-6). In another aspect of this embodiment, it has structure (Vd-6a). In another aspect of this embodiment, it has structure (Vd- 7). In another aspect of this embodiment, it has structure (Vd-8). In another aspect of this embodiment, it has structure (Vd-9). In another aspect of this embodiment, it has structure (Vd- 10). In another aspect of this embodiment, it has structure (Vd-11). In another aspect of this embodiment, it has structure (Vd-12). In another aspect of this embodiment, it has structure (Vd- 13). In another aspect of this embodiment, it has structure (Vd-14). In another aspect of this embodiment, it has structure (Vd-15). In another aspect of this embodiment, it has structure (Vd- 16). In another aspect of this embodiment, it has structure (Vd-17). In another aspect of this embodiment, it has structure (Vd-18). In another aspect of this embodiment, it has structure (Vd- 19). In another aspect of this embodiment, it has structure (Vd-20). In another aspect of this embodiment y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A. In another aspect of this embodiment y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(Vd-7)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0206] Another embodiment of the disclosed and claimed block copolymer of structure (I) is one which has structure (Ve), where Ri is a -Si(R3b)2-R3o[Si(R3b)2-O]ni-R3d-R4 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2Cis selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol.

[0207] In one aspect of this embodiment Ri is a -Si(R3b)2-R3o[Si(R3b)2-O]ni-R3d-R4 moiety, whereNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCRso is a C1-8 alkylene, Rsb is a C1-6 linear alkyl, Rscis a direct valence bond. In another aspect of this embodiment where Rscis a C1-4 alkylene, Rsb is a C1-3 linear alkyl, Rscis a direct valence bond.

[0208] In another aspect of this embodiment Ri has structure -Si(CH3)2-CH2-CH2-[Si(CH3)2-O]ni-Si(CH3)2-R4. In another aspect of this embodiment Ri more specifically has structure -Si(CH3)2-CH2-CH2-[Si(CH3)2-O]ni-Si(CH3)2-i-Bu, in another aspect of this embodiment nl is an integer from 2 to 5, in another aspect of this embodiment nl is an integer from 2 to 4, in another aspect of this embodiment R4 is a C3-6 branched alkyl. In another aspect of this embodiment, it has structure (Ve-1). In another aspect of this embodiment, it has structure (Ve-2). In another aspect of this embodiment, it has structure (Ve-2a). In another aspect of this embodiment, it has structure (Ve-3). In another aspect of this embodiment, it has structure (Ve-3a). In another aspect of this embodiment, it has structure (Ve-4). In another aspect of this embodiment, it has structure (Ve-5). In another aspect of this embodiment, it has structure (Ve-6). In another aspect of this embodiment, it has structure (Ve-7). In another aspect of this embodiment, it has structure (Ve-8). In another aspect of this embodiment, it has structure (Ve-9). In another aspect of this embodiment, it has structure (Ve-9). In another aspect of this embodiment, it has structure (Ve-10). In another aspect of this embodiment, it has structure (Ve-11). In another aspect of this embodiment, y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A. In another aspect of this embodiment, is y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0209] Another aspect of the disclosed and claimed subject matter is a composition which comprises any one of the above disclosed and claimed block copolymers and an organic spin coating solvent.Preferred Embodiments

[0210] One preferred embodiment of the disclosed and claimed block copolymer is one which has structure (Vd-2) and even more specifically structure (Vd-3).

[0211] In one aspect of this embodiment the Mnof block segment A is from about 16,400 to about 20,000, and the Mnof block segment B ranges from about 17,600 to about 21,600, and y is fromNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC about 20 wt. % to about 25 wt. % of the Mnof block A.

[0212] In another aspect of this embodiment the Mnof block segment A is from about 5,200 to about 6,400, and the Mnof block segment B ranges from about 5,900 to about 7,200 and y is from about 20 wt. % to about 25 wt. % of the Mnof block A.

[0213] In a still more preferred aspect of this embodiment the Mnof block segment A is from about 10,500 to about 12,800, and the Mnof block segment B ranges from about 11,500 to about 14,100, and y is from about 20 wt. % to about 25 wt. % of the Mnof block A.

[0214] In another still more preferred aspect of this embodiment, the Mnof block segment A is from about 14,000 to about 17,100, and the Mnof block segment B ranges from about 16,600 to about 20,200, and y is from about 20 wt. % to about 25 wt. % of the Mnof block A.

[0215] Another preferred embodiment of the disclosed and claimed block copolymer is one which has structure (Va-2) and even more specifically structure (Va-3).

[0216] In one aspect of this embodiment the Mnof block segment A is from about 6,500 to about 7,900, and the Mnof block segment B ranges from about 6,700 to about 8,100, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0217] In another aspect of this embodiment the Mnof block segment A is from about 16,700 to about 20,400, and the Mnof block segment B ranges from about 19,000 to about 24,200, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0218] In a still more preferred embodiment, the Mnof block segment A is from about 10,400 to about 12,700, and the Mnof block segment B ranges from about 11,300 to about 13,800, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0219] In another still more preferred embodiment, the Mnof block segment A is from about 11 , 100 to about 13,500, and the Mnof block segment B ranges from about 12,300 to about 15,100, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0220] In another still more preferred embodiment, the Mnof block segment A is from about 12,900 to about 15,730, and the Mnof block segment B ranges from about 12,700 to about 15, 500 and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0221] Another preferred embodiment of the disclosed and claimed block copolymer is one which has structure (Vc-2) and even more specifically structure (Vc-3).

[0222] In one aspect of this embodiment the Mnof block segment A is from about 25.800 to about 31,600, and the Mnof block segment B ranges from about 23,000 to about 28,200, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0223] In another aspect of this embodiment the Mnof block segment A is from about 8,600 to about 10,600, and the Mnof block segment B ranges from about x to about x, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0224] In a still more preferred embodiment, the Mnof block segment A is from about 10,300 to about 12,500 and the Mnof block segment B ranges from about 12,500 to about 15,300, and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.

[0225] In another still more preferred embodiment, the Mnof block segment A is from about 12,100 to about 14,700, and the Mnof block segment B ranges from about 13,700 to about 16,720 and y is from about 36 wt. % to about 44 wt. % of the Mnof block A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0226] Another preferred embodiment of the disclosed and claimed block copolymer is one which has structure (Vc-2) and even more specifically structure (Vc-3) but where the A block segment is much larger than the B block segment.

[0227] In a still more preferred embodiment, the Mnof block segment A is from about 23,800 to about 29,000 and the Mnof block segment B ranges from about 11.300 to about 13,800, and y is from about 20 wt. % to about 25 wt. % of the Mnof block A.

[0228] In another still more preferred embodiment, theMnofblock segment A is from about 23,900 to about 29,300 and the Mnofblock segment B ranges from about 11,200 to about 13,700 y is from about 20 wt. % to about 25 wt. % of the Mnofblock A.Compositions

[0229] Another aspect of the disclosed and claimed subject matter is a composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnofblock segment Ato the Mnofblock segmentB is from about 0.40 to about 0.60. Another aspect of this embodiment is one wherein said block copolymers are one in which said first block segment has structure (II- 1). Another aspect of this embodiment is one wherein said block copolymers are one in which said first block segment has structure (II- 2).

[0230] Another aspect of the disclosed and claimed subject matter is a composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment Ato the Mnofblock segment B is from about 0.61 to about 0.75 or from about 0.61 to about 0.74. Another aspect of this embodiment is one wherein said block copolymers are one in which said first block segment has structure (II- 1). Another aspect of this embodimentNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC is one wherein said block copolymers are one in which said first block segment has structure (II- 2).Organic Spin Coating Solvent

[0231] The organic spin coating solvent for said composition which comprises the disclosed and claimed block copolymer, is any suitable organic solvents for dissolving any of the aforementioned, disclosed and claimed block copolymer. These include a glycol ether derivative such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; a glycol ether ester derivative such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylates of di-basic acids such as di ethyloxy late and diethylmal onate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl-3 -hydroxy propionate; a ketone ester such as methyl pyruvate or ethyl pyruvate; an alkoxy carboxylic acid ester such as methyl 3- methoxypropionate, ethyl 3 -ethoxypropionate, ethyl 2-hydroxy-2-m ethylpropionate, or methylethoxypropionate; a ketone derivative such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; a ketone ether derivative such as diacetone alcohol methyl ether; a ketone alcohol derivative such as acetol or diacetone alcohol; a ketal or acetal like 1,3 dioxalane and diethoxypropane; lactones such as butyrolactone; an amide derivative such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0232] Another aspect of the disclosed and claimed subject matter is a composition where the disclosed and claimed block copolymer is present in a concentration from about 0.5 wt. % to about 3 wt. %.Process of using Compositions

[0233] Another aspect of the disclosed and claimed subject matter is a process of coating these composition on a substrate.

[0234] Another aspect of the disclosed and claimed subject matter is a self-assembly process comprising steps: i) forming a coating of a neutral layer on a substrate,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC ii) coating a composition which comprises any of the aforementioned, disclosed and claimed block copolymers, on to said neutral layer, to form a film of a block copolymer with polar and non-polar polymer segments, iii) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a self-assembled film pattern of the polar and non-polar polymer segments of said film of said block copolymer, iv) using said self-assembled film as a mask, etching said substrate with a plasma to pattern transfer said self-assembled patterned film pattern into said substrate.

[0235] Another aspect of the disclosed and claimed subject matter is a chemoepitaxy directed selfassembly process for pattern multiplication of L / S features comprising steps: ia) forming a coating of crosslinked (x-linked) pinning layer on a substrate, iia) forming a coating of a photoresist on said x-linked pinning layer, iiia) imaging said coating of photoresist with radiation through a mask to form a L / S pattern of exposed areas to radiation, iva) developing said L / S pattern of exposed areas with a developer to form a L / S pattern imaged photoresist over said x-linked layer, va) using a plasma and the L / S imaged photoresist as a mask to transfer said L / S pattern into said x-linked pinning layer, forming a x-linked pinning layer with a L / S pattern over said substrate, via) using said x-linked pinning layer with a L / S pattern, depositing a brush neutral layer selectively on the areas in said x-linked pinning layer with a L / S pattern which are open to the substrate producing a chemoepitaxy L / S pattern of pinning and neutral areas over said substrate, viia) forming a film of block copolymer using the composition comprising any one of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60 on said chemoepitaxy L / S pattern, viiia) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to induce in said film of block copolymer a multiplication of the L / S pattern by directed self-assembly induced by the underlying L / S pattern, ixa) using this film of block copolymer with a multiplication of the L / S pattern as a mask for etching into said substrate a multiplied L / S pattern with a plasma.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0236] Another aspect of the disclosed and claimed subject matter is a chemoepitaxy directed selfassembly process for pattern multiplication of CH features comprising steps: ib) forming a coating of crosslinked pinning layer on a substrate, iib) forming a coating of a photoresist on said x-linked pinning layer, iiib) imaging said coating of photoresist with radiation through a mask to form a CH pattern of exposed areas to radiation, ivb) developing said CH pattern of exposed areas with a developer to form a CH pattern imaged photoresist over said x-linked layer, vb) using a plasma and the CH imaged photoresist as a mask to transfer said CH pattern into said x-linked pinning layer, forming a x-linked pinning layer with a CH pattern over said substrate, vib) using said x-linked pinning layer with a CH pattern, depositing a brush neutral layer selectively on the areas in said linked pinning layer with a CH pattern which are open to the substrate producing a chemoepitaxy CH pattern of pinning and neutral areas over said substrate, viib) forming a film of block copolymer using a composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75, on said chemoepitaxy CH pattern, viiib) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to induce in said film of block copolymer a multiplication of the L / S pattern by directed self-assembly induced by the underlying CH pattern, ixb) using this film of block copolymer with a multiplication of the CH pattern as a mask etching into said substrate a multiplied CH pattern.

[0237] Another aspect of the disclosed and claimed subject matter is a process for forming a CH array into a substrate by self-assembly, comprising steps: ic) forming a coating of a grafted or crosslinked neutral layer on a substrate, iic) coating composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment A to the Mnof block segment B is from about 0.61 to about 0.75, onto said neutral layer, to form a film, iiic) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a self-assembled film contact hole pattern, andNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC ivc) etching said substrate using said self-assembled film contact hole pattern as mask with a plasma forming an array of contact hole in said substrate.

[0238] Another aspect of the disclosed and claimed subject matter is a process for pattern rectification of a EUV L / S pattern, comprising steps: id) forming a coating of a crosslinked pinning layer on a substrate, iid) coating said crosslinked pinning layer with EUV photoresist and imaging said photoresist to form an overlying L / S patterned EUV photoresist, iiid) using said overlying L / S array patterned photoresist as a mask, transferring this L / S array pattern into the neutral layer, forming a neutral layer with a L / S array pattern, ivd) coating the composition of comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment A to the Mnof block segment B is from about 0.40 to about 0.60, onto said neutral layer with a L / S array pattern, to form a film of block copolymer, vd) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a L / S array pattern in the block copolymer film by directed self-assembled chemoepitaxy, vid) etching said substrate, using said L / S array pattern in the film formed by directed selfassembled chemoepitaxy as mask, with a plasma forming a L / S array pattern in said substrate.

[0239] Another aspect of the disclosed and claimed subject matter is a process for forming for pattern rectification of a EUV CH pattern, comprising steps: ie) forming a coating of a crosslinked pinning layer on a substrate, iie) coating said crosslinked pinning layer with EUV photoresist and imaging said photoresist to form an overlying CH patterned EUV photoresist, iiie) using said overlying CH array patterned photoresist as a mask, transferring this CH array pattern into the neutral layer, forming a neutral layer with a CH array pattern, ive) coating the composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75, onto said neutral layer with a CH array pattern, to form a film of block copolymer,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC ve) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a CH array pattern in the block copolymer film by directed self-assembled chemoepitaxy, vie) etching said substrate, using said CH array pattern in the film formed by directed selfassembled chemoepitaxy as mask, forming a CH array pattern in said substrate.

[0240] In another aspect of these disclosed and claimed processes said substrate is a semiconductor coated with a dielectric material. Examples of suitable semiconductor material are silicon, germanium, gallium arsenide, gallium nitride, silicon carbide indium arsenide, indium antimonide and indium phosphide. Example of dielectric materials are silicon dioxide, hafnium silicate, zirconium silicate, titanium oxide, tantalum oxide, silicon nitride.

[0241] In another aspect of these disclosed and claimed processes the plasma used in etching may be one with a mixture of etch gasses and a rate of etching to optimize the etching of the polar B segments of said disclosed and claimed block copolymers having general structure (I) without causing pattern collapse. An examples of such conditions is i80 seem Oxygen and 20 seem Nitrogen mixed gases at pressure 50 mT and bias 100 W. Another aspect of the disclosed and claimed subject matter is the use of the disclosed and claimed block copolymers, the disclosed and claimed compositions or the disclosed and claimed process in the manufacture of integrated circuits.EXAMPLESChemicals and Characterization

[0242] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.

[0243] All chemicals unless otherwise indicated were purchased from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g., “Techniques in High-Vacuum Anionic Polymerization” by David Uhrig and Jimmy Mays and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0244] All synthetic experiments were carried out under N2 atmosphere. Lithographic experimentsNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC were carried out as described in the text.

[0245] Lithographic Experiments and DS A experiments were done using a TEL Clean ACT 12 track for coating and baking either on unpatterned neutral layer substrates to obtain either selfassembled Finger-print patterns or directed self-assembled patterns on prepattemed substrates. The prepatterned substrates used in these DSA experiments were made at Interuniversity Microelectronic Center (IMEC) at Leuven Belgium and are described in more detail for specific examples.

[0246] EUV patterns for pattern rectification experiments obtained at IMEC using a standard IMEC EUV resist were prepared and exposed with ASML NXE3400B 0.33 NA exposure tool.

[0247] All Finger-print (FP) SEM pictures or DSA SEM pictures were taken with an applied Materials NanoSEM_3D Scanning electron microscope, and pictures are shown at either 1 FOV magnification or 0.5 FOV magnification (Field of view (FOV) = 5 pm).

[0248] Etching experiments were done using standard isotropic oxygen etching conditions for selfassembled films of block copolymer of methyl methacrylate and styrene.

[0249] Unless otherwise indicated Molecular weight measurements (a.k.a. Mw, Mnand polydispersity) were done by Gel permeation chromatography (PSS Inc. Germany) equipped with 100A, 500 A, 103A, 105A and 106A p-ultrastyragel columns using THF solvent as an eluent. Polystyrene polymer standards were used for calibration. In these measurements the term “K,” is synonymous with 1000 g / mole or 1000 Daltons.

[0250] JH NMR spectra were recorded using Bruker Advanced III 400 MHz spectrometer in CD2CI2 or CDCh.

[0251] DSA of these copolymers was obtained on chemical prepatterns derived from 193 i or EUV lithography with appropriate underlayers. Specifically, DSA of the high-chi block copolymers’ ability to form pitch multiplications for 193i chemical prepattern (IMEC’s LiNe flow), and to rectify EUV printed lines or holes to form defect free roughness controlled with lower LER and LWR. The flow for these applications is given below in FIG. la and FIG. lb.LiNe (Liu-Nealey) flow prepattern for multiplication DSA:

[0252] The guiding prepattern for graphoepitaxy comprise both topography and underlayer as described in FIG. la. A thin (4-20 nm) layer of x-linkable PS polymer MAT was coated on SiNx substrate and then baked at 250°C for 2 min to generate underlayer MAT. On top of the underlayerNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(xPS / SiNx stack), a 60 nm thick film of a ArF photoresist was prepared and exposed with 193 nm interference lithography, then developed in the positive tone with an alkaline developer (0.26N TMAH) to produce trench pre-pattem comprising resist sidewalls and the underlayer modified bottom substrate. The developed resist prepattern was hardened by UV flood exposure with a total exposure dose of 60 mJ / cm2followed by pre-exposure bake at 115°C for 60 sec and 185°C for 120 sec. The pre-pattem was mild dry etched to remove open xPS underlayer and produce trench xPS and SiNx pre-pattern after removal of photoresist by solvent rinse. The open SiNx pattern surface was backfilled with PS-r-PMMA-OH brush polymer by spin coating PS-r-PMMA-OH solution, baked at 250°C for 30 min, and rinse with EBR 70 / 30 solvent to generate trench of xPS and neutral brush prepattern. HChi BCP was spin coated on a LiNe flow pre-pattern substrate with 25 to 100 nm, and then baked at 200°C to 250°C under nitrogen for 30 min to 120 min to generate multiplication DSA.

[0253] Lithographic Exposures for LiNe flow were done with a ASML (ASML Veldhoven, De Run 65015504 DR, Veldhoven The Netherlands) NXT 195 Oi. Etching Experiments were done with a LAM (4650 Cushmg Parkway Fremont, CA 94538 U.S.A.) Kiyo E5. Spinning and development of films and patterns was done with a SCREEN (SCREEN semiconductor solutions Co, Ltd. Tenjinkita-machi 1-1, Teranouchiagaru 4-chome, Horikawa-don, Kamigyo-ku, Kyoto, JAPAN), SOKUDO DUO track or a TEL (Tokyo Electrons Ltd., Akasaka Biz Tower 3-1 Akasaka 5-chome, Minato-ku, Tokyo 107-6325) ACT-12. Stripping of photo resist pattern was done with a SCREEN (SCREEN semiconductor solutions Co, Ltd. Tenjinkita-mach i 1-1, Teranouchi-agaru 4-chome, Horikawa-don, Kamigyo-ku, Kyoto, JAPAN) AQUASPIN Scanning Electron Micrographs were obtained with a Hitachi H-5000 (Hitachi High Technologies America Inc. 10 North Martingale Road, Suite 500 Schaumburg, Illinois 60173-2295).EUV 24 nm prepattern for DSA rectification:

[0254] The 24 nm rectification prepattern comprises underlayer MAT or polymer brush pattern using EUV lithography as described in FIG. 1 b. The rectification pre-pattern was prepared at IMEC facility. A thin (4-20 nm) layer of x-linkable PS polymer MAT or polymer brush was coated on SiNx substrate and then baked at 315°C for 5 min under air for MAT or 250°C for 30 min under nitrogen for brush and then rinsed with with PGMEA (propylene glycol methyl ether acetate) to generate underlayer. On top of the underlayer (xPS / PS brush, Pinning Underlayer 1 a 30 nm thickNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC film of a standard IMEC EUV resist was prepared and exposed to EUV with ASML NXE3400B 0.33NA exposure tool ata dose of 47 mJ / cm2, then developed with the TMAH for 30 sec to produce 24 nm pre-pattern comprising resist sidewalls and the underlayer modified bottom substrate. The pre-pattem was mild dry etched to remove open xPS / brush underlayer and produce trench of underlayer and SiNx pre-pattern after removal of photoresist by solvent rinse. The open SiNx pattern surface was backfilled with PS-r-PMMA-OH brush polymer (Neutral Underlayer 2) by spin coating PS-r-PMMA-OH solution, bake at 250°C for 30 min, and rinse with AZ® EBR 70 / 30 solvent to generate trench of xPS and neutral brush prepattern. HChi BCP was spin coated on a LiNe flow pre-pattern substrate with 25 to 100 nm L / S features, and then baked at 200°C to 250°C under nitrogen for 30 min to 120 min to generate DSA.

[0255] By this new disclosed and claimed subject matter pertaining to conformationally screened junction modification approach, the disclosed and claimed subject matter achieved domain stabilization of both PLA and PS while assembling PS-b-PLA system to enable etch transfer for application towards line / space and contact hole DSA. Advantages of new high-chi BCPs are thermally annealable up to 250°C without any issues of orientation control and domain stabilization up on etching and pattern transfer as shown in DSA flow (FIG. 2). FIG. 2 shows print images of PS-b-trimethylsilyl styrene-b-PLA conformationally screened BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); (A) sample 1.1, (B) sample 1.2, (C) sample 1.7, (D) sample 1.9 from Table-1 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0256] FIG. 3 shows 5x multiplication DSA of PS- / >-trimethylsilyl styrene- / ?-PLA using (HChi-3) BCP at FT of the 35 nm on IMEC xPS LiNe flow pitch 87 nm PP with Neutral Underlayer 1, PS 30 % brush backfill after and annealing at 200°C / 30 min. / N2. Lo= 18.37 nm DSA exhibiting no collapse lines.

[0257] FIG. 4 shows a comparison of A) segmented vs B) copolymerized trimethylsilyl styrene units containing BCPs. Finger-print (FP) data which shows the effect of terminal coil screening evident and present in segmented case as the FP looks normal, whereas for copolymerized system, in homogeneous silicon distribution across the chain causes higher chi, requires lower Mnto get similar Lo, and also seen from the asymmetric width of non-polar to polar domains.

[0258] All the polymers synthesized in this disclosure were characterized by Gel permeationNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC chromatography (PSS Inc. Germany) equipped with 100A, 500 A, 103A, 105A and 106A p- ultrastyragel columns using THF solvent as an eluent (1 mL / min) for molecular weight measurements (Mn,GPc, and MW,GPC) and polydispersity indices using polystyrene standards for calibration as a reference. Composition of polymers and end-functionality were determined using 300 MHz 'H- NMR. Coating studies were performed using blanket dielectric as well as metal coupons. The films were baked at desired temperature and time and rinsed with excess material. All BCP’s formulations were made in PGMEA with 2.3 wt. % which was filtered through a 0.02 um PTFE filter. Subsequently, coated the BCP at 1500 rpm and the wafers were subsequently each soft baked at 110°C for Imin then annealed at 200°C under N2 for 30 minutes (see figures above).

[0259] Synthesis of neutral underlayer 1 consisting of styrene and methyl methacrylate copolymers, using free-radical polymerization with hydroxyl containing AIBN initiator with of 30 mol. % of polystyrene (PS) were made as generally described in Ref 19. (19. US20130330668A1 (Synthesis Example 2 but using instead 1.9 gr of styrene and 4.2 gr of methyl methacrylate)).Preparation of neutral underlayer 2:

[0260] To a 5-L flask equipped with a condenser, temperature controller, heating mantle and mechanical stirrer, 1000 grams (9.60 moles) of styrene, 963 grams (9.6 moles) of methyl methacrylate, 28.9 grams (0.048 moles) of Nitroxide initiator and 1300 grams of anisole were added. Then a mechanical stirrer was set up at about 120 rpm. The reaction solution was degassed by vigorously bubbling nitrogen through the solution for about 30 minutes at room temperature. After 30 minutes degassing a heating mantle and was set up the temperature controller at 140°C. The reaction mixture was refluxing at 130 to 140°C for 20 hours. After this, the heating mantle was turned off and allowed the reaction solution temperature cooling down to about 40°C. The reaction mixture was transferred (100 g / min) into 40 L of IPA during a mechanical stirring. The polymer was precipitated out. The solid polymer was collected by filtration. The polymer was dried in vacuum oven at 40°C to give about 1500 grams of polymer with Mw18 K and poly dispersity (PDI) of 1.1. This neutral layer material is a brush type neutral layer material which forms a grafted neutral layer on a substrate.Preparation of Pinning Underlayer 1

[0261] A 2-L flask equipped with a condenser, temperature controller, heating mantle and mechanical stirrer was charged with 640 grams (6.15 moles) of styrene, 63 grams (0.48 moles) ofNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC4-vinyl benzocyclobutene, 10.9 grams of AIBN initiator and 880 grams of 2-butanone were added to the flask. A mechanical stirrer and was set up at about 120 rpm. The reaction solution was degassed by vigorously bubbling nitrogen through the solution for about 30 minutes at room temperature. After 30 minutes degassing turned on the heating mantle and set up the temperature controller at 80°C. The reaction mixture was kept at 80°C for 20 hours. After 20 h the heating mantle was turned off, the reaction solution temperature was allowed to cool down to about 40°C. The reaction mixture was poured into 15 L of methanol during a mechanical stirring. The polymer was precipitated out. The solid polymer was collected by filtration. The polymer was dried in vacuum oven at 40°C. About 470 grams of the polymer was obtained which had an Mwof 15k and a and PDI of 1.7). This material is crosslinking MAT neutral layer, which form a neutral layer which is crosslinked. This material is a pinning materials which can form a crosslinked Pinning layer (pinning MAT) on a substrate.Preparation of underlayer coatings:

[0262] The underlayer copolymers described herein Neutral Underlayer 1, Neutral Underlayer 2 and Pinning Underlayer 1 were separately dissolved in PGMEA to form 1 wt% solutions. The solution was individually filtered in using a Nylon filter (Entegris, Billerica, Ma). The solution was separately coated at 1500 rpm on SiCh / Si wafer, and the wafer was subsequently baked at 230°C for 5 min under nitrogen. Following the bake, the wafer was rinsed with PGMEA for 2 min to remove any un-grafted polymer from the wafer which were then spun dried by spinning “1,500 rpm,” followed by baking at 110°C for 1 min. Then water contact angle, XPS were measured to understand the grafting efficiency.Orientation of high-chi block copolymer formulation in PGMEA:

[0263] Modified high-chi block copolymer solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated S1O2 / S1 wafers. They were subsequently, baked at different annealing temperature for certain time under nitrogen.Example 1: Synthesis of HChi-3 block copolymer:

[0264] Scheme 3 shows the general scheme for the Synthesis of high-chi copolymers with carbonsilicon units and the nonpolar block is a block copolymer.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 3

[0265] Synthesis of sample 1.1 in Table 1 is given as an example of Scheme 3. 40 g of purified styrene was added to a single neck RB flask with a three-way septum adaptor. Then 500 mL of anhydrous cyclohexane was cannula transferred to RB (round bottomed) flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 6 mL of 1.4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 10 g of purified degassed trimethyl silyl styrene then added and kept the reaction for additional 60 minutes and terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol.

[0266] The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS- / >- PTMSS-OH characterized by NMR and GPC. In the second step, 5g of PS- / ?-PTMSS-OH, and 5.6 g of lactide taken in Schenk flask and degassed under vacuum for Ih. 0.215 g of In(III)C13 (1.13 eq with respect to macroinitiator) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.3 mL triethyl amine (2.5 eq with respect to macroinitiator) was injected after which the indium salt began to dissolve. The reaction was then kept atRT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of triethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer solution was diluted with 1 OOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.5 grams of a polymer. The synthesis of all other polymers was conducted following an identical procedure, wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator (50g scale). Additionally, block copolymers were prepared by using 5 g of first block and by varying the amounts of lactides, indium chloride,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC and triethyl amine, in accordance with the desired molecular weights. The amount of each reagents were used are shown in the Table 1 description.

[0267] Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m- ultrastyragel columns were used for the Mndetermination of first block and NMR for the second block. The proton NMR spectrum of sample 1.2 of Table 1 (HChi-3 for line and space composition) is shown in FIG. 5.

[0268] Table 1:a) wt. / ?-trimethylsilylstyrene in the block copolymerization with respect to the target Mnof nonpolar styrene block A, b) PGMEA solution of polymer was coated on neutral underlayer brush Neutral Underlayer 1 (PS30 mol. %) and baked at 200°C for 1 h, and c) Vol % = { Mn(PS block) / density of bulk PS} / [ { Mn(PS block) / density of bulk PS} + { Mn(PLA block) / density of bulk PLA}] x 100 d) sec-BuLi: 4mL, LA: 5,7g, In(III)Cl3: 0.142g, Et3N: 0.2mL e) sec-BuLi: 3.6mL, LA: 5.6g, In(III)Cl3: 0.128g, Et3N: 0.177mL f) sec-BuLi: 3.6mL, LA: 5.5g, In(III)Cl3: 0.125g, Et3N: 0.174mL g) sec-BuLi: 3mL, LA: 5.55g, In(III)Cl3: 0.108g, Et3N: 0.150mL h) sec-BuLi: 2.75mL, LA: 5.42g, In(III)Cl3: 0.097g, Et3N: 0.135mL i) sec-BuLi: 2.65mL, LA: 5.55g, In(III)Cl3: 0.093g, Et3N: 0.130mL j) sec-BuLi: 2.3mL, LA: 6.1g, In(III)Cl3: 0.080g, Et3N: 0.112mL k) sec-BuLi: 2 mL, LA: 5.5g, In(III)Cl3: 0.067g, EfeN: 0.096mL l) sec-BuLi: 2.38mL, LA: 5.8g, In(III)Cl3: 0.083g, Et3N: 0.115mL

[0269] HChi-3 block copolymer (Example 1) solutions were made using PGMEA (1 to 2.5 wt. %)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated S1O2 / S1 wafers. They were subsequently baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen. For 5x multiplication DSA, HChi-3 block copolymer solutions were spin coated on 87 nm pitch LiNe prepattern wafer and baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2 hr) under nitrogen.

[0270] FIG. 2 shows Finger-print (FP) images of HChi-3 BCP (A) sample 1.1, (B) sample 1.2, (C) sample 1.7, (D) sample 1.9 from Table-1 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.Example 2: Synthesis of HChi-3 block copolymer:

[0271] Scheme 4 shows a general reaction scheme for making of HChi-3 which are copolymers with carbon-silicon units and where the nonpolar block is a block copolymer with this procedure the lactide block was relatively short compared to Examples 3.Scheme 4

[0272] 40 g of purified styrene was added to a single neck RB flask with a three-way septum adaptor. Then 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 2.65 mL of 1 ,4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 10 g of purified degassed trimethyl silyl styrene then added and kept the reaction for additional 60 minutes and terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS- / ?-PTMSS-OH characterized by NMR and GPC. In the second step, 5g of PS- / >-PTMSS-OH, and 2.3 g of lactide taken in Schenk flask and degassed under vacuum for Ih. 0.09 g of In(III)C13 (1.13 eq with respect to macroinitiator) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.130 mL tri ethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 6.1 grams of a polymer with an Mn: 13,500- / >-6,100, PDI: 1.06.

[0273] The synthesis of all other polymers was conducted following an identical procedure, wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator.

[0274] The structure of the polymer and procedure were same as example 1 except the fact that the PLA block length was reduced to obtain contact hole morphology. Gel permeation chromatography equipped with 100A, 500 A, 103A, 105A and 106A m-ultrastyragel columns were used for the Mndetermination of first block and NMR for the second block. The Proton NMR spectrum of sample 1.9 (HChi-3 for Contact hole composition) from Table-1 is shown in FIG. 6.

[0275] HChi-3 block copolymer (Example 2) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2-micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2 hr) under nitrogen. FIG. 7 shows CH morphology of HChi-3 BCP at FT A) 20 nm, B) 40 nm on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images.Example 3: Synthesis of HChi-H3 block copolymer:

[0276] Scheme 4 shows a general reaction scheme for making of HChi-H3 which are copolymers with carbon-silicon units and where the nonpolar block is a random copolymer with this procedure the lactide block was relatively long compared to Examples 2.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 4

[0277] 40 g of purified styrene was added to a three neck RB connected with a three-way septum adaptor and an ampoule filled with 10g of purified trimethyl silyl styrene. 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 4 mL of 1 ,4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. One minute after the addition of sec-butyl lithium, 10 g of purified degassed trimethyl silyl styrene was then added dropwise over the period of 60 minutes. Then the reaction was terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS-co-PTMSS-OH characterized by NMR and GPC. In the second step, 5g of PS-co-PTMSS-OH, and 4.45 g lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.140 g of In(III)C13 (1.13 eq with respect to macroinitiator) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.2 mL triethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.1 grams of a polymer with Mn: 8.7k-7.4k, PDI: 1.06, non-polar volume %: 56, Lo: 24.3

[0278] Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m- ultrastyragel columns were used for the Mndetermination of first block and NMR for the second block. The NMR spectrum of HChi-H3 for line and space compositions is shown in FIG. 8.

[0279] HChi-H3 block copolymer (Example 3) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated S1O2 / S1 wafers. They wereNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen (test results are shown in FIG. 4 above). FIG. 4 show a Comparison of A) segmented sample 1.7 from table 1 vs B) copolymerized trimethylsilyl styrene units containing BCPs at similar Mn. FP data which shows the effect of terminal coil screening is evident and present in segmented case as the FP looks normal, whereas for copolymerized system, silicon distribution across the chain causes higher chi, requires lower Mnto get similar Lo, and asymmetric width of non-polar to polar domains.Example 4: Synthesis of HChi-3a block copolymer:

[0280] Scheme 5 shows the general synthesis of high-chi, HChi-3a with carbon units and the nonpolar block is a block copolymer.Scheme 5

[0281] Synthesis of polymer 2.1 given as an example. 30g of purified styrene was added to a single neck RB flask with a three-way septum adaptor. 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30 sec-one minutes, the RB was back filled with nitrogen. Then 5.1 mL of 1.4M secbutyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 20 g of purified degassed p- tert-butyl styrene then added and kept the reaction for additional 60 minutes. It was then terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS- / >-PtBuS-OH characterized by NMR and GPC. In the second step, 5g of PS-Z>- PtBuS -OH, and 5.2 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.175 g of In(III)C13 (1.13 eq with respect to macroinititor) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for~5 min (macro initiator and lactide should be dissolved by this time). Then 0.240 mL of triethyl amine (2.5 eq with respect to macroinitiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by theNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.7 grams of a polymer with an Mn: 13,500-6-6,100, PDI: 1.06.

[0282] The synthesis of all other polymers was conducted following an identical procedure (50g scale), wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator. Additionally, block copolymers were prepared by using 5g of first block and by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights. The amounts of each reagents used are shown in the Table 2 description.

[0283] Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m- ultrastyragel columns were used for the Mndetermination of first block and NMR for the second block.

[0284] The proton NMR spectrum for the sample 2.1 from Table 2 (HChi-3a) is shown in FIG. 9.

[0285] Table 2: Materials compositions andLoof HChi-3a BCP’s synthesized as described in example 4.a) wt. / -butylstyrene in the block copolymerization with respect to the target Mnof non-polar styreneNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC block A. b) PGMEA solution of polymer was coated on neutral underlayer brush, Neutral underlayer 1 (PS 30 mol. %) and baked at 200°C for 1 h, c) Same equation as in Table 1 d) sec-BuLi: 3.25mL, LA: 5.45g, In(III)Cl3: 0.114g, Et3N: 0.158mL e) sec-BuLi: 3.4mL, LA: 5.33g, In(III)Cl3: 0.120g, Et3N: 0.166mL f) sec-BuLi: 3.1mL, LA: 5.65g, In(III)Cl3: 0.108g, Et3N: 0.151mL g) sec-BuLi: 2.9mL, LA: 5.7g, In(III)Cl3: 0.102g, Et3N: 0.141mL h) sec-BuLi: 2.5mL, LA: 5.06g, In(III)Cl3: 0.087g, Et3N: 0.122mL i) sec-BuLi: 2.2mL, LA: 4.8g, In(III)Cl3: 0.076g, Et3N: 0.106mL j) sec-BuLi: 2.1mL, LA: 5.09g, In(III)Cl3: 0.075g, Et3N: 0.104mL k) sec-BuLi: 2.2mL, LA: 5.57g, In(III)Cl3: 0.080g, Et3N: O.l lOmL l) sec-BuLi: 2.0mL, LA: 6.25g, In(III)Cl3: 0.069g, Et3N: 0.097mL m) sec-BuLi: 2.1mL, LA: 7.5g, In(III)Cl3: 0.075g, Et3N: 0.104mL n) sec-BuLi: 1.92mL, LA: 6.2g, In(III)Cl3: 0.068g, Et3N: 0.094mL

[0286] HChi-3a block copolymer (Example 4) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2-micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen. For 5x multiplication DSA, HChi-3a block copolymer solutions were spin coated on 87 nm pitch LiNe prepattern wafer and baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen.

[0287] FIG. 10 shows Fingerprint (FP) images of HChi-3a conformationally screened BCP (A) sample 2.1, (B) sample 2.3, (C) sample 2.5, (D) sample 2.12 from table 2 on under lay erNeutral underlayer 1 (PS 30 %) FT 6.5 nm, 250°C / 30 min / N2, annealing at200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0288] FIG. 11 shows DSA of 5x of HChi-3a at FT 35 nm on IMEC xPS LiNe flow pitch 87 nm PP with Neutral underlayer 1 PS30% brush backfill (A) after annealing at 200°C / 30 min. / N2, (B) after etching for 12 sec at 50 mT, 100W, 80 seem O2, and 20 seem N2 on Trion etcher.

[0289] FIG. 12 shows the DSA pattern rectification of a EUV 24 nm L / S prepattern using HChi-3a BCP (75 nm coating thickness) on IMEC L / S prepattern annealed at 200°C / lh (N2). (A) 1 pm X 1pm NanoSEM image without etch, (B) 0.5pm X 0.5pm NanoSEM image after etching for 28 sec on Trion etcher.Example 5: Synthesis of HChi-H3a L / S block copolymers:

[0290] Scheme 5 shows the Synthesis of high-chi, HChi-H3a with carbon units and the nonpolarNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC block is a random copolymer.Scheme 5

[0291] Synthesis of block copolymer 3.1 is given as an example of Scheme 5. 30g of purified styrene and 20 g of p-tert-butyl styrene was added to a single neck RB flask with a three-way septum adaptor. 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 3.6 mL of 1.4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued for 60 min. It was then terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS-co-PtBuS-OH characterized by NMR and GPC. In the second step, 5g of PS -c - PtBuS -OH, and 5.3 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.125 g of In(III)C13 (1.13 eq with respect to macroinititor) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.175 mL of tri ethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of triethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.5 grams of a polymer. The synthesis of all other polymers in Table 3 was conducted following an identical procedure, wherein the initial blocks were produced by adjusting the quantity of sec- Butyl lithium initiator. Additionally, block copolymers were prepared by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0292] FIG 13 shows the Proton NMR of HChi-H3a 3.1 which is a line and space block copolymer.

[0293] Table 3:Materials compositions and Loof HChi-H3a BCP’s synthesized as described in example 5.a) wt. / -butylstyrene in the random copolymerization with respect to target Mnof non-polar styrene block A, and b) PGMEA solution of polymer was coated on neutral underlayer brush Neutral underlayer 1 (PS 30 mol. %) and baked at 200°C for 1 h., and c) Same equation as in Table 1 d) sec-BuLi: 3.25mL, LA: 5.6g, In(III)Cl3: 0.111g, Et3N: 0.155mL e) sec-BuLi: 3.25mL, LA: 5.8, In(III)Cl3: 0.111g, Et3N: 0.155mL f) sec-BuLi: 3.1mL, LA: 6.35g, In(III)Cl3: 0.110g, Et3N: 0.152mL g) sec-BuLi: 2.65mL, LA: 5.74g, In(III)Cl3: 0.092g, Et3N: 0.130mL h) sec-BuLi: 2.65mL, LA: 5.4g, In(III)Cl3: 0.092g, Et3N: 0.130mL i) sec-BuLi: 2.4mL, LA: 5.6g, In(III)Cl3: 0.085g, Et3N: 0.118mL j) sec-BuLi: 2.4mL, LA: 5.6g, In(III)Cl3: 0.085g, Et3N: 0.118mL k) sec-BuLi: 2.2mL, LA: 5.62g, In(III)Cl3: 0.078g, Et3N: O.l lOmL l) sec-BuLi: 1.6mL, LA: 5.1g, In(III)Cl3: 0.057g, Et3N: 0.080mL m) sec-BuLi: 1.24mL, LA: 4.6g, In(III)Cl3: 0.043g, Et3N: 0.060mL

[0294] HChi-H3a block copolymer (Example 5) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2-micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC to 2 hr) under nitrogen. FIG. 14 shows Finger-print (FP) images ofHChi-H3a BCP (A) sample 3.1, (B) sample 3.4, (C) sample 3.8, (D) sample 3.10 from table 3 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0295] FIG. 15 shows EUV pattern rectification by DS A of 24 nm HChi-H3a BCP on IMEC prepattern (24 nm pitch prepattern made with pinning underlayer 1) IMEC prepattern coating 75 nm annealed at200°C / lh (N2). (A) 1 pm X 1 pm NanoSEM image without etch, (B) 0.5pm X 0.5pm Nano SEM image after etching for 28 sec on Trion etcher.Example 6: Synthesis of HChi-H3a CH block copolymers:

[0296] Scheme 6 shows the Synthesis of high-chi, HChi-H3a with carbon rich monomer, t- butylstyrene and the nonpolar block is a random copolymer.Scheme 6

[0297] The synthesis of the polymer 4.1 is given as an example. 40g of purified styrene and 10 g of p-tert-butyl styrene was added to a single neck RBF with a three-way septum adaptor. 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 1.35 mL of 1.4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued for 60 min. It was then terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS-co-PtBuS-OH characterized by NMR and GPC. In the second step, 5g of PS-co- PtBuS -OH, and 2.5 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.047 g of In(III)C13 (1.13 eq with respect to macro inititor) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.066 mL of tri ethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chlorideNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC was added followed by the addition of 1.0 mL of triethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 6.45 grams of a polymer with. The synthesis of all other polymers was conducted following an identical procedure (50g scale), wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator. Additionally, block copolymers were prepared by using 5g of first block and by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights. The amount of each reagents were used are shown in the table description.

[0298] The structure of the polymer and procedure are same as example 5 except the fact that the PLA block length was reduced to obtain contact hole morphology. Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m-ultrastyragel columns used for the Mndetermination of first block and NMR for the second block. Table 4 shows HChi-H3a CH BCP’s synthesized as described in example 6.

[0299] Table 4: Materials compositions and / .<> of HChi-H3a CH BCP’s synthesized as described in example 6,a) wt. / -butylstyrene in the random copolymerization with respect to target Mnof non-polar styrene block A. b) PGMEA solution of polymer was coated on neutral underlayer brush Neutral Underlayer 2 (PS51 mol. %) and baked at 250°C for 15 min, c) same equation as in Table 1 d) sec-BuLi: 1.25mL, LA: 2.65g, In(III)Cl3: 0.044g, Et3N: 0.061mL e) sec-BuLi: 1.48mL, LA: 2.68g, In(III)Cl3: 0.052g, Et3N: 0.072mLNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC f) sec-BuLi: 1.35mL, LA: 2.44g, In(III)Cl3: 0.047g, Et3N: 0.066mL

[0300] FIG. 16 shows / H of HChi-H3a BCP, FT = 40 nm (Table 4, sample 4.4) on Neutral Underlayer 2, annealing at 250°C / 15 min (N2); 1FOV SEM images, 12 sec etch at 50 mT, 100W, 50 seem O2, and 50 seem N2 on Trion etcher.Example 7: Synthesis of HChi-xH3a (x-linkable) L / S block copolymers:

[0301] Scheme 7 show the general synthetic pathway for HChi-xH3a with thermally crosslinkable units in styrenic block and the nonpolar block is a random copolymer.Scheme 7

[0302] The synthesis of polymer 5.1 given as an example. 29.5g of purified styrene, 0.5 g 4- vinylbenzocyclobutene (VBCB) and 20 g of p-tert-butyl styrene was added to a single neck RB flask with a three-way septum adaptor. 500 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 3.7 mL of 1.4M sec-butyl lithium was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 90 min and terminated with 4 mL of distilled trimethylene oxide followed by the addition of degassed methanol.

[0303] The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator P(VBCB-co-S-co-tBuS)-OH characterized by NMR and GPC. In the second step, 5g of P(VBCB- co-S-co-tBuS)-OH, and 5.6g of lactide taken in Schenk flask and degassed under vacuum for Ih. 0.093g of In(III)C13 (1.13 eq with respect to macroinititor) was added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.13 mL triethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with 1 OOmL of tetrahydrofuran and precipitated out of solutionNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.8 grams of a polymer with. The synthesis of all other polymers was conducted following an identical procedure (50g scale), wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator. Additionally, block copolymers were prepared by using 5g of first block and by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights. The amount of each reagents used are shown in the table description.

[0304] Gel permeation chromatography equipped with 100A, 500 A, 103 A, 105 A and 106 A m- ultrastyragel columns used for the Mndetermination of first block and NMR for the second block. The NMR spectrum of 5.2 samples in Table 5 is given below. FIG. 17 shows the Proton NMR of HChi-xH3a (5.1) line and space block copolymer.

[0305] Table 5:Materials compositions and / .<> of HChi-xH3a BCP’s synthesized as described in example 7,a)wt. of VBCB monomer in the random copolymerization with respect to target Mnof non-polar styrene block A, b) wt. / -butylstyrene in the random copolymerization with respect to target Mnof non-polar styrene block A, and c) PGMEA solution of polymer was coated on neutral underlayer brush Neutral underlayer 1 (PS 30 mol. %) and baked at 200°C for 1 h, c) Same equation as inNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCTable 1 d) sec-BuLi: 2.46mL, LA: 7.5g, In(III)Cl3: 0.087g, Et3N: 0.122mL e) sec-BuLi: 2.23mL, LA: 6.6g, In(III)Cl3: 0.071g, Et3N: O.lOOmL f) sec-BuLi: 2.38mL, LA: 5.2g, In(III)Cl3: 0.083g, Et3N: 0.116mL g) sec-BuLi: 2.38mL, LA: 6.7g, In(III)Cl3: 0.083g, Et3N: 0.116mL h) sec-BuLi: 3.4mL, LA: 5.66g, In(III)Cl3: 0.118g, Et3N: 0.164mL i) sec-BuLi: 2.1mL, LA: 5.53g, In(III)Cl3: 0.075g, Et3N: 0.105mL j) sec-BuLi: 3.76mL, LA: 6.31g, In(III)Cl3: 0.131g, Et3N: 0.183mL k) sec-BuLi: 2.38mL, LA: 6.1g, In(III)Cl3: 0.084g, Et3N: 0.118mL l) Lowas calculated from 13.5 FOV SEM images.

[0306] HChi-xH3a block copolymer (Example 7) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2-micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2 hr) under nitrogen.

[0307] FIG. 18 shows Finger-print (FP) images of HChi-xH3a BCP at 75 nm FT from Table 5 on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lo was calculated from 13.5 FOV SEM images. A) sample, 5.2, B) sample 5.8, and C) sample 5.10 from Table 5.

[0308] FIG. 19 shows EUV pattern rectification by DSA of 24 nm HChi-xH3a BCP, at ctg. 75 nm on IMEC prepattern (24 nm pitch prepattern made with pinning underlayer 1), coating 75 nm annealed at 200°C / lh (N2). (A) 1 pm X 1 pm NanoSEM image without etch, (B) 0.5pm X 0.5pm NanoSEM image after etching for 28 sec on Trion etcherExample 8: Synthesis of HChi-3b block copolymers:

[0309] Scheme 8 shows the Synthesis of high-chi, HChi-3b with dimethylsilyl Cl 5 alkyl units in styrenic block and the nonpolar block is a block copolymer.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 8

[0310] The synthesis of polymer 6.1 given as an example. The 20 g of styrene was added to a single neck RB flask with a three-way septum adaptor. Then 200 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 2.9 mL of 1 ,4M sec-butyl lithium was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 2g of purified degassed (4- vinyl phenyl) dimethyl silane (target: 3 units) then added and kept the reaction for additional 15 minutes and then terminated with 4 mL of distilled trimethylene oxide followed by the immediate addition of degassed methanol.

[0311] The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS- / >- PSiH-OH characterized by NMR and GPC. In the second step, 5g of PS- / ?-PSiH-OH, and 6.2 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.25g of In(III)C13 (1.13 eq with respect to macroinitiator) was added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.185 mL triethyl amine (2.5 eq with respect to macroinitiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwiseNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours. The final step involves the hydrosilylation of the block copolymer with 1 -pentadecane (3 times excess based on the number of (4-vinyl phenyl) dimethyl silane units) using Pt / C in THF to yield the final product as HChi-3b polymer. The polymer was purified by passing through celite and precipitated into isopropyl alcohol and dried to give 9.5 grams of a polymer. The synthesis of all other polymers was conducted following an identical procedure (20g scale), wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator. Additionally, block copolymers were prepared by using 5g of first block and by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights. The hydrosilylation step used 3 times excess 1 -pentadecende as explained above. The amount of each reagents were used are shown in the Table 6 description.

[0312] Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m- ultrastyragel columns used for the Mndetermination of styrene block and NMR for the Mndetermination for (4-vinyl phenyl) dimethyl silane and the PLA block. FIG 20 shows the proton NMR of 6.1 HChi-3b with dimethylsilyl Cl 5 alkyl units in styrenic block. Table 6 shows the Material composition and Loof HChi-3b BCP’s synthesized as described in example 8.

[0313] HChi-3b block copolymer (Example 8) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCE / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0314] Table 6:Materials compositions and£oof HChi-3b BCP’s synthesized as described in example 8,a) PGMEA solution of polymer was coated on neutral underlayer brush Neutral underlayer 1 (PS 30 mol. %) and baked at 200°C for 1 h. b) wt. with respect to target Mnof non-polar styrene block A, c) sec-BuLi: 2.3 mL, (4-vinyl phenyl) dimethyl silane: 2.6g, LA: 8.6g, In(III)C13: 0.205g, EtsN: 0.285mL d) sec-BuLi: 1.6mL, (4-vinyl phenyl) dimethyl silane: 2.5g, LA: 8 g, In(III)C13: 0.140g, EtsN:0.190mL

[0315] FIG. 21 shows Finger-print (FP) images ofHChi-3b BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images. (A) sample 6.1, (B) sample 6.2, (C) sample 6.3 from table 6.Example 9: Synthesis of HChi-3b (C15-derivative-CH) block copolymers:

[0316] Scheme 9 shows Synthesis of high-chi, HChi-3b with dimethylsilyl Cl 5 alkyl units in styrenic block for contact hole assembly and the nonpolar block is a block copolymer.Scheme 9

[0317] The 20 g of styrene was added to a single neck RB flask with a three-way septum adaptor. Then 200 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RBNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC was back filled with nitrogen. Then 0.66 mL of 1 ,4M sec-butyl lithium was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 0.8g of purified degassed (4-vinyl phenyl) dimethyl silane (target: 5 units) then added and kept the reaction for additional 15 minutes and then terminated with 4 mL of distilled trimethylene oxide followed by the immediate addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS- / ?-PSiH-OH characterized by NMR and GPC. In the second step, 5g of PS- / ?-PSiH-OH, and 2.7 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.056g of In(III)C13 (1.13 eq with respect to macroinitiator) was added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.078 mL triethyl amine (2.5 eq with respect to macroinitiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours. The final step involves the hydrosilylation of the block copolymer with 1 -pentadecane (3 times excess based on the number of (4-vinyl phenyl) dimethyl silane units) using Pt / C in THF to yield the final product as HChi-3b CH polymer. The polymer was purified by passing through celite and precipitated into isopropyl alcohol and dried. Mn: 23,500-11,200 PDI: 1.07.

[0318] Gel permeation chromatography equipped with 100A, 500 A, 103A, 105A and 106A m- ultrastyragel columns used for the Mndetermination of first block and NMR for the second block. The NMR spectrum is similar to example 8.Example 10: Synthesis of HChi-3b (DMCllSiS -derivative) block copolymers:

[0319] Scheme 10 shows the Synthesis of high-chi, HChi-3b with dimethylsilyl C12 alkyl units in styrenic block for line and space assembly and the nonpolar block is a block copolymer.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 10

[0320] 30g of purified styrene was added to a single neck RBF with a three-way septum adaptor. Then 500mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 2.1 mL of 1.4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 20 g of purified degassed Cl 2 silyl styrene then added and kept the reaction for additional 60 minutes and terminated with 4 mL of distilled trimethylene oxide followed by the immediate addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS-b-PSSiC12-OH characterized by NMR and GPC. In the second step, 5 g of PS-b-PSSiC12-OH, and 6 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.125 g of In(III)C13 (1.13 eq with respect to macroinitiator) were added to a RB flask (under nitrogen atmosphere). To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.175 mL triethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with 100 mL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 9.3 grams of a polymer. FIG. 22 shows the Proton NMR of HChi-3b with dimethylsilyl C12 alkyl units in styrenic block HChi-3b block copolymer (Example 10)

[0321] Gel permeation chromatography equipped with 100 A, 500 A, 103A, 105A and 106A m- ultrastyragel columns used for the Mndetermination of styrene block and NMR for the Mndetermination for (4-vinyl phenyl) dimethyl silane and the PLA block.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0322] HChi-3b block copolymer (Example 10) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiO Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen.

[0323] FIG. 23 shows Finger-print (FP) images of HChi-3b (DMC12SiS -derivative) block copolymer at FT A) 20 nm, B) 40 nm on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.Example 11: Synthesis of HChi-4 block copolymers with silicon-oxide units:

[0324] Scheme 11 shows the Synthesis of high-chi, HChi-4 with oligosilicon oxide units in styrenic block for line and space assembly and the nonpolar block is a block copolymer.Scheme 11

[0325] Synthesis of polymer 7.1 is given as an example. 16 g of purified styrene was added to a single neck RBF with a three-way septum adaptor. Then 200 mL of anhydrous cyclohexane was cannula transferred to RB flask under positive nitrogen pressure. After careful degassing under dynamic vacuum for 30sec-one minute, the RB was back filled with nitrogen. Then 1.93 mL of 1 ,4M sec-butyl lithium solution was added using a syringe under nitrogen. The color of reaction medium changed to orange color. The reaction continued further for 60 min. 4 g of purified degassed (4-vinyl phenyl) dimethyl silane then added and kept the reaction for additional 60New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC minutes and terminated with 4 mL of distilled trimethylene oxide followed by the immediate addition of degassed methanol. The polymer was precipitated in isopropyl alcohol and dried and the macroinitiator PS-b-PSiH-OH characterized by NMR and GPC. In the second step, 5g of PS- b-PSiH-OH, and 4.5 g of lactide were taken in Schenk flask and degassed under vacuum for Ih. 0.125 g of In(III)C13 (1.13 eq with respect to macro initiator) were added to a RB flask under nitrogen atmosphere. To this mixture added 40 mL of DCM (8 mL / g of macroinitiator) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then 0.175 mL triethyl amine (2.5 eq with respect to macro initiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 21 hours. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of tri ethyl amine). The polymer solution was diluted with lOOmL of tetrahydrofuran and precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated and fractionated (3-5 times by the reverse addition of hexane or heptane) into the THF solution of the block copolymer, water washed and dried under vacuum at 65-70 degree Celsius 12 hours. The final step involves the hydrosilylation of the block copolymer with vinyl end functionalized oligo dimethyl siloxane using Pt / C in THF to yield the final product as HChi-4 polymer. The reaction was monitored by NMR spectra to ensure complete hydrosilylation of the polymer. The polymer was finally purified by passing through the celite column and precipitated into the isopropyl alcohol and dried to give 7.8 grams of a polymer. The synthesis of all other polymers was conducted following an identical procedure (20g scale), wherein the initial blocks were produced by adjusting the quantity of sec-Butyl lithium initiator. Additionally, block copolymers were prepared by using 5g of first block and by varying the amounts of lactides, indium chloride, and triethyl amine, in accordance with the desired molecular weights. The hydrosilylation step used 3 times excess vinyl end functionalized oligo dimethyl siloxane as explained above. The amount of each reagents were used are shown in the Table 7 description.

[0326] Fig 24 shows the proton NMR spectrum of HChi-4 block copolymers (7.1) with siliconoxide units.

[0327] Table 7 shows the Material compositions of HChi-4 BCP’s synthesized as described in example 11.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0328] Table 7: Materials compositions and£oof HChi-4 BCP’s synthesized as described in example 11.a) wt. oligodimethylsilicone oxide modified styrene in the block copolymerization with respect to target Mnof non-polar styrene block A. b) PGMEA solution of polymer was coated on neutral underlayer brush Neutral underlayer 1 (PS 30 mol. %) and baked at 200°C for 1 h. c) sec-BuLi: 1.7 mL, LA: 7.1g, In(III)Cl3: 0.147g, Et3N: 0.205mL d) sec-BuLi: 1.3mL, LA: 7.5g, In(III)Cl3: 0.113g, Et3N: 0.160mL e) sec-BuLi: 1.6mL, LA: 5.9 g, In(III)Cl3: 0.113g, Et3N: 0.160mL

[0329] HChi-4 block copolymer (Example 11) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2-micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2hr) under nitrogen.

[0330] FIG. 25 shows Finger-print (FP) images of HChi-4 BCP on Neutral underlayer 1 (PS 30 %) underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images. (A) sample 7.1, (B) sample 7.2, (C) sample 7.3, (D) sample 7.4 from table 7.Example 12: Synthesis of HChi-6 block copolymers:

[0331] Scheme 12 shows the synthesis of high-chi, HChi-6 with carbon substituted monomers in both the styrenic and lactide blocks and the blocks are randomly copolymerized.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 12

[0332] 5 g of P(S-b-tBuS)-OH or P(S-co-tBuS)-OH, 4.4 g of lactide, and 1.1 g phenyl lactide were taken in an RB flask and kept under high vacuum under stirring for one hour. Then 0.1g of In(III)C13 (1.13 eq with respect to macroinitiator) was added to the RB flask (under nitrogen atmosphere, glove box). To this mixture added 40 mL of DCM (8 mL / g of initiator polymer) and stirred for ~5 min (macro initiator and lactides should be dissolved by this time). Then 0.15 mL of tri ethyl amine (2.5 eq) was injected after which the indium salt began to dissolve (usually within 10 minutes). The reaction kept at RT for 24hours. Finally, 10 times excess of acetyl chloride was added along with 1 mL of tri ethylamine to end cap the PLA block and kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer was precipitated out of solution upon dropwise addition to methanol or isopropyl alcohol. The material was isolated, fractionated (2 times by the reverse addition of hexane or heptane), water washed and dried under vacuum at 65-70 degree Celsius 12 hours to give 8.8 grams of a polymer.

[0333] Gel permeation chromatography equipped with 100 A, 500 A, 103 A, 105 A and 106 A m- ultrastyragel columns showed that the 1st PS blocks had Mn(GPC) = 12,000 g / mol and Mw / Mn= 1.03 with respect to PS calibration standards. The second block PLA molecular weight is Mn (NMR) 13,000 g / mol with 16% modified lactides. The diblock copolymer molecular weight obtained from GPC and NMR is Mn= 25,000 g / mol and Mw / Mn= 1.08. FIG. 26 shows the proton NMR of HChi-6 with carbon substituted monomers in both the styrenic and lactide blocks and the blocks are randomly copolymerized.

[0334] HChi-6 block copolymer (Example 12) solutions were made using PGMEA (1 to 2.5 wt. %) as solvent. The block copolymer solutions were filtered using 0.2 micron nylon syringe membrane and spin-coated on to different composition of neural brush coated SiCL / Si wafers. They were subsequently, baked at different annealing temperature (170°C to 250°C) for certain time (30 min. to 2 hr) under nitrogen.

[0335] FIG. 27 shows Finger-prints (FP) image of HChi-6 BCP on neutral underlayer 1 (PS 30 %)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC underlayer annealed at 200°C / 60 min (N2); 1FOV SEM images, No etch, Lowas calculated from 13.5 FOV SEM images.

[0336] FIG. 28: shows CH image of P(S-r-tBuS25%)24.2k-P(LA-r-BnzLA2o%)iik (HChi-6 BCP), FT = 40 nm on Neutral Underlayer 2, annealing at 250°C / l 5 min (N2); 1FOV SEM images, 12 sec etch at 50 mT, 100W, 50 seem O2, and 50 seem N2on Trion etcher.

[0337] The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed subject matter has been shown and described with respect to an exemplary embodiment thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in the form and detail thereof may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.Synthesis of HChi-3a, PS-b-PtBuS-(BO)-b-PLA, in THF using butylene oxide (BO) as a crossover unit.

[0338] Scheme 13 shows a non-limiting examples of synthetic pathway to achieve a block copolymer of structure (I) in which Z has structure (Illa) which is derived from 1 ,2-butylene oxide. The synthesis of several of these block copolymers are described in Examples 13 to 21 whose properties as summarized in Table 8.Scheme 13General protocol of anionic polymerization of first block in the tetrahydrofuran and PS-b- PtBuS-b-PLA using ring opening polymerization of DL-lactide.

[0339] In the first step purified styrene (S), and tert-butyl tertbutyl styrene (tBuS), were degassed and ampulized in pressure equilibrating ampule. Ampules were attached to the anionic reactor and a three-way septum adaptor. Then anhydrous tetrahydrofuran was cannula transferred to RB flask under positive nitrogen pressure to make 10-25% solid with monomer. Flask was cooled to -78 °C using dry ice / acetone bath. Then 2-3 mL of 1.4M sec-butyl lithium solution was added using a syringe under nitrogen, until a lemon-yellow color was persistent. Reactor was brought to room temperature to quench the excess .s c-BuLi. After obtaining clear THF solution, flask was again cooled to -78 °C. Required amount of .s c-BuLi was added via glass syringe. Styrene was addedNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC dr op wise over a period of 30 min. After taking aliquot for PS block it was quenched with degassed methanol and analyzed using GPC. Tert-butyl styrene was added over a period 15 min and further stirred for 15 min and terminated with 5-10 times excess butylene oxide (BO) distilled over sec- BuLi. Stirred for 10 min and terminated with addition of degassed methanol. Polymer was isolated by precipitation in isopropanol and after filtration died in vacuum oven at 80 °C. Polymer molecular weight and Mn.Mwwas analyzed using GPC.

[0340] In the second step, required amount of PS-b-PtBuS-OH, and of lactide (LA) were taken in Schenk flask and degassed under vacuum for Ih. Then In(III)C13 (1.1 eq with respect to macro initiator) were added to a RB flask under nitrogen atmosphere. To this mixture cannula transferred required amount of DCM (~20 % solid) and stir for ~5 min (macro initiator and lactide should be dissolved by this time). Then anhydrous triethyl amine (2.5 eq with respect to macroinitiator) was injected after which the indium salt began to dissolve. The reaction was then kept at RT for 6-18h. Finally, 10 times excess of acetyl chloride was added followed by the addition of 1.0 mL of tri ethylamine to end cap the PLA block. It was then kept under stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The polymer was precipitated in excess isopropyl alcohol, filtered, and dried under vacuum at 65-70 °C for 12 hours.

[0341] Gel permeation chromatography equipped with 100A, 500 A, 103 A, 105 A and 106 A m- ultrastyragel columns was used for the Mndetermination of PS-b-PtBuS-OH block and proton NMR for the Mnof the PLA block.Example 13.

[0342] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 50 mL styrene, 13 mL tert-butyl styrene, and 1.8 mL of 1.4M s-BuLi initiator, and 4mL of butylene oxide. PS-b-PtBuS-OH Mn is 24.8k and Mw / Mn =1.04. In the second step 13g of PS-b- PtBuS-0 and 18g of DL-lactide was reacted in presence of 0.12g InC13 and 0.2mL of tri ethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn = 48,400 g / mol and Mw / Mn = 1.06 (FIG. 29). The NMR spectrum is given below (FIG. 30). This white polymer was obtained in near quantitative yield (~95 %).Example 14.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0343] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 50mL styrene, 13mL tert-butyl styrene, and 1.2mL of 1.4M s-BuLi initiator, and 4mL of butylene oxide. PS-b-PtBuS-OH Mnis 32.7k and Mw / Mn =1.04. In the second step 16g of PS-b- PtBuS-0 and 23g of DL-lactide was reacted in presence of 0.12 InC13 and 0.2mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 65,300 g / mol and Mw / Mn = 1.04. This white polymer was obtained in near quantitative yield (~95 %) (Table 8).Example 15.

[0344] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 50mL styrene, 13mL tert-butyl styrene, and 1.8mL of 1.4M s-BuLi initiator, and 4mL of butylene oxide. PS-b-PtBuS-OH Mnis 24.8k and Mw / Mn =1.04. In the second step 24.8g of PS-b- PtBuS-0 and 35g of DL-lactide was reacted in presence of 0.240g InC13 and 0.4mL of tri ethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 51 ,200g / mol and Mw / Mn = 1.06. (This white polymer was obtained in near quantitative yield (~95 %)(Table 8)..Example 16.

[0345] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 50mL styrene, 13mL tert-butyl styrene, and 1.2mL of 1.4M s-BuLi initiator, and 4mL of butylene oxide. PS-b-PtBuS-OH Mnis 32.7k and Mw / Mn =1.04. In the second step 16g of PS-b- PtBuS-0 and 23g of DL-lactide was reacted in presence of 0.120g InC13 and 0.2mL of tri ethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 65,000 g / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).Example 17.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0346] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 50mL styrene, 13mL tert-butyl styrene, and 1.2mL of 1.4M s-BuLi initiator, and 4mL of butylene oxide. PS-b-PtBuS-OH Mnis 32.7k and Mw / Mn =1.04. In the second step 16g of PS-b- PtBuS-0 and 23g of DL-lactide was reacted in presence of 0.12g InC13 and 0.2mL of tri ethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 68,900 g / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).Example 18.

[0347] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 18g of styrene, 4.5g of tert-butyl styrene, and 1.46mL of 1.4M s-BuLi initiator, and 3mL of butylene oxide. PS-b-PtBuS-OH Mnis 10,600 and Mw / Mn =1.04. In the second step 10g ofPS-b- PtBuS-0 and 10.9g of DL-lactide was reacted in presence of 0.23g InC13 and 0.3mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 20.5kg / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8)..Example 19.

[0348] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 22.5g of styrene, 5.6g of tert-butyl styrene, and 1.33mL of 1.4M s-BuLi initiator, and 3mL of butylene oxide. PS-b-PtBuS-OH Mnis 15,000 and Mw / Mn =1.04. In the second step 10g of PS- b-PtBuS-0 and 10.9g of DL-lactide was reacted in presence of 0.23g InC13 and 0.3mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 28. Ikg / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).Example 20.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0349] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 22.5g of styrene, 5.6g of tert-butyl styrene, and 1.33mL of 1.4M s-BuLi initiator, and 3mL of butylene oxide. PS-b-PtBuS-OH Mnis 15,000 and Mw / Mn =1.04. In the second step 5g of PS- b-PtBuS-0 and 6.5g of DL-lactide was reacted in presence of 0.113g InC13 and 0.15mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 31.7kg / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).Example 21.

[0350] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 18g of styrene, 4.5g of tert-butyl styrene, and 1.46mL of 1.4M s-BuLi initiator, and 3mL of butylene oxide. PS-b-PtBuS-OH Mnis 10,000 and Mw / Mn =1.04. In the second step 10g ofPS-b- PtBuS-0 and 10.9g of DL-lactide was reacted in presence of 0.23g InC13 and 0.3mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 21.2kg / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).Example 21-a

[0351] The synthesis of first block PS-b-PtbBuS-OH was prepared by anionic polymerization and purification were carried out using all same conditions of anionic polymerization in tetrahydrofuran using 21.6g of styrene, 5.4g of tert-butyl styrene, and 1.02mL of 1.4M s-BuLi initiator, and 3mL of butylene oxide. PS-b-PtBuS-OH Mnis 18,000 and Mw / Mn =1.04. In the second step 10g of PS- b-PtBuS-0 and 10.9g of DL-lactide was reacted in presence of 0.23g InC13 and 0.3mL of triethylamine in dichloromethane. After desired conversion was achieved, polymer was terminated with acetyl chloride and subjected to purification step. The block-copolymer molecular weight obtained from GPC and proton NMR is Mn= 39.5kg / mol and Mw / Mn = 1.04 This white polymer was obtained in near quantitative yield (~95 %)(Table 8).

[0352] FIG. 29 shows the GPC profile of each sequential block of PS, PS-PtBuS and PS-b-New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCPtBuS-b-PLA of Example 13.

[0353] FIG. 30 shows the Proton NMR spectrum of Example 13 (HChi-3a) which was used for line and space photoresist compositions.

[0354] Table 8a) wt. / -butylstyrene in the block copolymerization with respect to the target Mnof non-polar styrene block A. b) Film Thickness in nm c) PS Vol % calculated with same equation as in Table 1 d) The block-copolymer molecular weight obtained from GPC and proton NMR e) Lowas calculated from 13.5 FOV SEM images.Example 22.Synthesis of macroinitiator of hydroxyl methyl terminated polystyrene-ranrfom-poly(4-tert- butyl styrene) (PSsowt. %-r-PtBSiowt. %-OH) with 20wt. % of PtBS.

[0355] Scheme 14 shows a non-limiting examples of synthetic pathway to achieve a hydroxyl methyl terminated polystyrene-ranrfom-poly(4-tert-butyl styrene). Specifically, in this instance it show how this is done with a hydroxy methyl terminated-polystyrene-ra»<7o / «-poly(4- / c / 7-butyl styrene) macroinitiators ((PS-r-PtBS)-DPECH2OH).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 14

[0356] The mixture of styrene (St, 24.54 g, 235.65 mmol) and 4-tert-butyl styrene (tBS, 6.16 g, 38.41 mmol) was added via syringe into the ampule. The monomer mixture was degassed under reduced pressure (10‘6mmHg) until the gas bubble disappeared. In the glovebox, the hydroxy protected 1,1 -diphenylethylene of 2-((3-(l-phenylvinyl)benzyl)oxy)tetrahydro-2H-pyran (DPECH2O-Pn, 0.71 g, 2.41 mmol) was weighed (2.0 molar excess with respect to s-BuLi) in a vial and dissolved in 5 mL toluene. This solution was promptly titrated with dilute hexylDPE-Li solution until an orange color was persistence. After closing the stopcock ampule was removed from glovebox. Both the St / tBS ampule and DPECH2O-Pn ampule were attached to the glass joints of the flask reactor and closed with three way septum adaptor, which was connected with a rubber tubing for access to vacuum / argon. Vacuum was applied to the flask and the reactor was dried using heat-gun. After 10 min, the flask was brought to RT and filled with argon. Under positive pressure -300 mL dry THF was transferred to the flask via cannula transfer. Flask temperature was lowered to -78°C using dry ice / acetone bath. THF solution was titrated with s-BuLi (3 ml, 1 ,4M) until a persistent yellow was obtained. After 5 min, dry ice / acetone bath was removed, and flask was brought to RT. It takes 15-30 min for the complete decay of yellow color. After a colorless solution was obtained, flask temperature was lowered to -78°C and the required amount of initiator s-BuLi (3.24 mL, 0.9923 mmol, 0.306M) was added using gastight glass syringe. After 2-3 min, initiator solution kept under stirring at 300 rpm and St / tBS mixture was added dropwise over 60 minutes. Propagation was continued further for 10 minutes and the titrated DPECH2O-Pn solution was added by shot. The pale orange mixture turned dark red after the addition of the DPECH2O-Pn. This results in color change from pale orange to dark red, a color of active DPECH2O-Pn / living PS-r-PtBS. After 10 min, the living polymer mixture was terminated with 2 mL degassed methanol and brought to RT. MeOH (100 - 150 ml) was added to the solution, followed by adding paratoluenesulfonic acid (pTSA, 4.58 g, 24.09 mmol, 10 fold-excess amount of s-BuLi initiator). The reaction mixture was stirred at room temperature for overnight. The mixture was precipitated in aNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC large amount of methanol and polymer was recovered by vacuum filtration. The dried polymer was dissolved in EtOAc as a 10% solids solution, washed 3 times with 1 wt. % ascorbic acid (aq), and then 3 times DI water. The mixture was precipitated in isopropyl alcohol (IP A, 8 parts volume) and the precipitate was collected by vacuum filtration and dried in a vacuum oven at 70 °C. Quantitative yield was obtained as shown in Table 9.Example 23

[0357] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different concentration of the s-BuLi initiator (3.93 mL, 1.204 mmol, 0.306M). Quantitative yield was obtained as shown in Table 9.Example 24

[0358] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different concentration of the s-BuLi initiator (4.01 mL, 1.2280 mmol, 0.306M). Quantitative yield was obtained as shown in Table 9.Example 25

[0359] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different concentration of the s-BuLi initiator (5.28 mL, 1.6157 mmol, 0.306M). Quantitative yield was obtained as shown in Table 9.Example 26

[0360] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different concentration of the s -BuLi initiator (8.29 mL, 2.5371 mmol, 0.306M). Quantitative yield was obtained as shown in Table 9.

[0361] Table 9. Synthesis of random type macroinitiators of (PS-r-PtBS)-DPECH2OH with 20 wt. % PtBS by living anionic polymerization and termination using 2-((3-(l-phenylvinyl)benzyl)oxy)tetrahydro-2H-pyran (DPECH2O-Pn).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCMnand PDI are measured by GPC

[0362] FIG. 31 show the 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)-DPECH2OH with 20 wt. % PtBS: (A) Example 22, (B) Example 23, (C) Example 24, (D) Example 25, and (E) Example 26.

[0363] FIG. 32 shows the GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r- PtBS)-DPECH2OH with 20 wt. % PtBS: (A) Example 22, (B) Example 23, (C) Example 24, (D) Example 25, and (E) Example 26.Example 27 Synthesis of macroinitiator of hydroxyl methyl terminated polystyrene-ranrfom- poly(4-tert-butyl styrene) (PS-2„t. o / o-r-PtBS2Swt. %-OH) with 28wt. % of PtBS.

[0364] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different monomer weight% ratio of St (23.63 g, 226.92 mmol) to tBS (9.09 g, 56.73 mmol), 72:28 (wt. %:wt. %) and the initiator of s-BuLi (4.82 mL, 1.1900 mmol, 0.247 M). Quantitative yield was obtained as shown in Table 10

[0365] Table 10 also shows a summary of Example 28 and 29 which were made in a similar fashion as follows:Example 28

[0366] The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 22 with the different concentration of the s-BuLi initiator (4.57 mL, 1.1285 mmol, 0.247 M). The yield of 92% was obtained as shown in Table 10.Example 29

[0367] The synthesis by anionic polymerization and purification were carried out using all sameNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC conditions of Example 22 with the different concentration of the s-BuLi initiator (5.18 mL, 1.2999 mmol, 0.247 M). Quantitative yield was obtained as shown in Table 10.

[0368] FIG. 33 shows the1H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS-r-PtBS)-DPECH2OH with 28 wt. % PtBS: (A) Example 27, (B) Example 28 and (C) Example 29.

[0369] FIG. 34 shows the GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r- PtBS)-DPECH2OH with 28 wt. % PtBS: (A) Example 27, (B) Example 28, and (C) Example 29.

[0370] Table 10Synthesis of random type macroinitiators of (PS-r-PtBS)-DPECH2OH with 28 wt. % PtBS by living anionic polymerization and termination using 2-((3-(l-phenylvinyl)benzyl)oxy)tetrahydro- 2H-pyran (DPECH2O-Pn).Mnand PDI are measured by GPC

[0371] Scheme 15 shows the synthesis of hydroxy methyl terminated-polystyrene-block-poly(4- tert-butyl styrene) macroinitiators ((PS- / ?-PtBS)-DPECH2OH).as described in Example 30 as follows:Scheme 15New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCExample 30. Synthesis of macroinitiator of hydroxyl methyl terminated polystyrene-6 / oc^- poly(4-tert-butyl styrene) (PS80wt. » / „- / >-Pt BS2owt. %-OH).

[0372] Each monomer of styrene (St, 23.63 g, 226.92 mmol) and 4-tert

[0373] -butyl styrene (tBS, 9.09 g, 56.73 mmol) was added via syringe into the ampule. Each monomer was degassed under reduced pressure (10‘6mmHg) until the gas bubble disappeared. In the glovebox, the Tetrahydro-2-[[3-(l-phenylethenyl)phenyl]methoxy]-2H-pyran (DPEMTHP) (0.76 g, 2.57 mmol) (Aurora Fine Chemicals) was weighed (2.0 molar excess with respect to s- BuLi) in a vial and dissolved in 5 mL toluene. This solution was promptly titrated with dilute hexylDPE-Li solution until an orange color was persistence. After closing the stopcock ampule was removed from glovebox. Three ampules of St, tBS, and DPEMTHP were attached to the glass joints of the flask reactor and closed with three-way septum adaptor, which was connected with a rubber tubing for access to vacuum / argon. Vacuum was applied to the flask and the reactor was dried using heat-gun. After 10 min, the flask was brought to RT and filled with argon. Under positive pressure -300 mL dry THF was transferred to the flask via cannula transfer. Flask temperature was lowered to -78°C using dry ice / acetone bath. THF solution was titrated with s-BuLi (3 ml, 1 ,4M) until a persistent yellow was obtained. After 5 min, dry ice / acetone bath was removed, and flask was brought to RT. It takes 15-30 min for the complete decay of yellow color. After a colorless solution was obtained, flask temperature was lowered to -78°C and the required amount of initiator s-BuLi (4.65 mL, 1.2280 mmol, 0.264 M) was added using gastight glass syringe. After 2-3 min, initiator solution kept under stirring at 300 rpm. St monomer was added dr op wise for 30 minutes and tBS monomer for 30 min. Propagation for St and tBS was continued further for 10 minutes. The titrated DPEMTHP solution was added by shot. The pale orange mixture turned dark red after the addition of the DPEMTHP. This results in color change from pale orange to dark red, a color of active DPEMTHP / living PS- / ?-PtBS. After 10 min, the living block copolymers (BCPs) end-capped with DPEMTHP was terminated with 2 mL degassed methanol and brought to RT. MeOH (100 - 150 ml) was added to the solution, followed by adding pTSA (4.67 g, 24.56 mmol, 10-fold-excess amount of s-BuLi initiator). The mixture of the BCPs and pTSA was stirred at room temperature for overnight. The mixture was precipitated in a large amount of IP A and BCPs were recovered by vacuum filtration. The dried BCPs were dissolved in EtOAc as a 10% solids solution, washed 3 times with 1 wt. % ascorbic acid (aq), and then 3 times DI water. The mixture was precipitated inNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC isopropyl alcohol (IP A, 8 parts volume) and the precipitate was collected by vacuum filtration and dried in a vacuum oven at 70 °C. Quantitative yield was obtained with 20 wt. % of PtBS of 2ndblocks as shown in Table 11.

[0374] Example 31 The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 30 with the different concentration of the s -BuLi initiator (4.38 m , 1.1584 mmol, 0.264 M). Quantitative yield was obtained as shown in Table 11.

[0375] Example 32 The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 30 with the different concentration of the s -BuLi initiator (6.31 mL, 1.6684 mmol, 0.264 M). Quantitative yield was obtained as shown in Table 11.

[0376] Example 33 The synthesis by anionic polymerization and purification were carried out using all same conditions of Example 30 with the different concentration of the s -BuLi initiator (11.63 mL, 3.0699 mmol, 0.264 M). Quantitative yield was obtained as shown in Table 11.Table 11 shows a summary of the characteristics of the block type macroinitiators of (PS- / ?-PtBS)- DPECH2OH, examples 30 to 33 with 20 wt. % PtBS by living anionic polymerization and termination using 2-((3-(l-phenylvinyl)benzyl)oxy)tetrahydro-2H-pyran (DPECH2O-Pn).

[0377] Table 11.

[0378] FIG. 35 shows the 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS- / ?-PtBS)-DPECH2OH with 20 wt. % PtBS: (A) Example 30, (B) Example 31, (C) Example 32,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC and (D) Example 33. (a) PS and (b)

[0379] FIG. 36 shows GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r- PtBS)-DPECH2OH with 20 wt. % PtBS: (A) Example 30, (B) Example 31, (C) Example 32, and (D) Example 33.

[0380] Scheme 16 shows the synthesis of hydroxy benzyl terminated -polystyrene-ra«r / cwt-poly(4- / e / 7-butyl styrene) macroinitiators ((PS-r-PtBS)-BzOH) as described in Examples 34 as follows:Scheme 16Example 34. Synthesis of macroinitiator of hydroxyl methyl terminated polystyrene-ranrfom- poly(4-tert-butyl styrene) (PSsowt. o / o-r-PtBS20wt. <> / o-BzOH) with 20wt. % of PtBS.

[0381]

[0382] The synthesis of PSsowt. %-r-PtBS20wt. %-BzOH was performed via the anionic polymerization with the different end-capping reagents of benzaldehyde (BzAld, 1.97 g, 18.55 mmol, 10 fold-excess amount of s-BuLi initiator), using the initiator of s-BuLi (7.02 mL, 1.8551 mmol, 0.264 M) in THF under high vacuum conditions (10‘6mmHg) at -78°C, following the procedure of the polymerization and purification as described in Example 22. Quantitative yield was obtained.

[0383] Table 12 give a summary of the characteristics of Example 34 which was made by by living anionic polymerization and termination using terminated using benzaldehyde (BzAd).

[0384] Table 12.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0385] FIG. 37 Shows the 'H-NMR spectra of the hydroxy benzyl-terminated macroinitiators of (PS- / ?-PtBS)BzAd-OH with 20 wt. % PtBS: Example 34.

[0386] FIG. 38 shows the GPC curves of the hydroxy benzyl-terminated macroinitiators of (PS-r- PtBS)BzAd-OH with 20 wt. % PtBS: Example 34.Example 37 Synthesis of high chi block copolymers of [polystyrenesowt. o / 0-ranrfom-poly(4- tert-butyl styrene)2owt. %]m-6 / oc^-polylactiden([PS80wt. o / o-r-PtBS20wt. <> / 0]-6-PLA).

[0387] Scheme 17 shows the synthesis high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA using random type macroinitiators with 20 wt. % PtBS randomly in PS blocks as described in Examples 37 as follows:Scheme 17

[0388] The anionic ring opening polymerization (AROP) were carried out in an inert atmosphere at 25 - 30°C using highly dry chemicals, macroinitiators, solvents, and all glassware. The drying macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 22, 3.0 g, 0.10753 mmol, Mnof 27.9 kg / mmol, PDI of 1.04), latide monomer (LA, 1.50 g, 10.41 mmol), and indium (III) chloride (In(III)C13, 0.029 g, 0.13 mmol) were charged to a flask under nitrogen atmosphere in the glovebox. To this mixture, added dichloromethane (DCM, 24 ml, 8 mL / g of macroinitiator) and stirred for ~5 min until the macroinitiator and lactide are dissolved completely. Tri ethylamine (TEA, 0.03 ml, 0.21 mmol, 2 fold-excess amount of macroinitiator) was added after which the indium salt began to dissolve (usually within 10 minutes). The reaction kept at 25 °C over 5 hours. After the complete conversion of LA monomers by NMR measurement, acetyl chloride (CH3COCI, 0.08 ml, 1.08 mmol, 10 fold-excess amount of macroinitiator) is added along with TEA (0.16 ml, 1,18 mmol) for termination by end-capping and kept stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The mixture was precipitated in isopropyl alcohol (IP A, 8 parts volume) and the precipitate was collected by vacuum filtration. The resulting BCPs were fractionated by the reverse addition of heptane, water-washed, and precipitated in isopropyl alcohol.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCThe purified BCPs were dried in a vacuum oven at 70 °C. The product of [PSsowt. %-r-PtBS20wt. %]- / ?-PLA was obtained as shown in Table 13.Example 38

[0389] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 23, 3.0 g, 0.11459 mmol, weight% ratio of St:tBS = 80:20, Mnof 26.2 kg / mmol, PDI of 1.04), In(III)C13 (0.03 g, 0.14 mmol) and TEA (0.03 ml, 0.23 mmol) in Dichloromethane (DCM, 24 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 13.Example 39

[0390] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 24 4.0 g, 0.1544 mmol, weight% ratio of St:tBS = 80:20, Mnof 25.9 kg / mmol, PDI of 1.06), DL-lactide (2.20 g, 15.26 mmol), In(III)C13 (0.041 g, 0.19 mmol) and TEA (0.04 ml, 0.31 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 13.Example 40

[0391] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 25, 4.0 g, 0.2174 mmol, weight% ratio of St:tBS = 80:20, Mnof 18.4 kg / mmol, PDI of 1.04), DL-lactide (2.30 g, 15.96 mmol), In(III)C13 (0.058 g, 0.26 mmol) and TEA (0.06 ml, 0.43 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 13.

[0392] Table 13. Synthesis of high chi block copolymers using random type macroinitiator (PS-r- PtBS20wt. %)-DPECH2OH by AROP with DL-lactide monomers for contact hole (CH) application.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC* The absolute Mngiven in Table 13 was calculated using GPC Mn of polystyrene and Mnof PLA calculated from1H-NMR.

[0393] FIG. 39 shows the 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r- PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40.

[0394] FIG. 40 shows the GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >- PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.Example 41 Preparation of underlayer coatings.

[0395] The underlayer copolymer described herein Neutral Underlayer 2 PS41%) was separately dissolved in PGMEA to form 2 wt. % solutions. The solution was individually filtered in using a Nylon filter (Entegris, Billerica, Ma). The solution was separately coated at 1,500 rpm on SiO2 / Si wafer, and the wafer was subsequently baked at 250°C for 30 min under nitrogen. Following the bake, the wafer was rinsed with PGMEA for 2 min to remove any un-grafted polymer from the wafer which were then spun dried by spinning 1,500 rpm, followed by baking at 110°C for 1 min.Example 42 The test process for forming a LS array into a substrate by self-assembly.

[0396] This process comprised steps: i) forming a coating of a grafted neutral layer on a substrate prepared by Example 41, ii) coating composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment A to the MnNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC of block segment B varies, onto said neutral layer, to form a film, iii) baking said film, in an inert gas atmosphere, at a temperature selected about 250°C for 15 min, to form a self-assembled film contact hole pattern, and iv) etching said substrate using said self-assembled film contact hole pattern as mask with a plasma forming an array of contact hole in said substrate.Example 43 The process of the EUV LS pattern for rectification.

[0397] This process comprised steps: i) forming a coating of a crosslinked pinning layer on a substrate, ii) coating said crosslinked pinning layer with EUV photoresist and imaging said photoresist to form an overlying CH patterned EUV photoresist, iii) using said overlying CH array patterned photoresist as a mask, transferring this CH array pattern into the neutral layer, forming a neutral layer with a CH array pattern, iv) coating composition which comprises any of the aforementioned, disclosed and claimed block copolymers, where the ratio of the Mnof block segment A to the Mnof block segment B varies, onto said neutral layer with a CH array pattern, to form a film of block copolymer, v) baking said film, in an inert gas atmosphere, at a temperature selected about 250°C for 15 min, to form a CH array pattern in the block copolymer film by directed self-assembled chemoepitaxy, vi) etching said substrate, using said CH array pattern in the film by directed self-assembled as mask, forming a CH array pattern in said substrate.

[0398] FIG. 41 Shows SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 37, (B) Example 38, (C) Example 39, and (D) Example 40. The test conditions: On Si were as follows: Neutral Underlayer 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1).FIG. 42 Shows SEM images of the contact hole nanostructures formed by direct self-assembly (DSA) of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt% PtBS randomly in PS blocks on the prepattem: (A) Example 37 only, (B) the blending of Example 39 and Example 40 with the wt% ratio of 94.9 to 5.1 and 70.7% of PS-r-PtBS. Test conditions: On IMEC 30nm C / H rectification prepattern; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1 & FOV2). (The detail procedures are described in Example 43)

[0399] Table 14 shows DSA test results of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt. % PtBS randomly in PS blocks on the prepattem: Example 37 only, ExampleNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC39&40 of the blending of Example 39 and Example 40 with the wt. % ratio of 94.9 to 5.1 and 70.7% ofPS-r-PtBS.

[0400] Table 14.Synthesis of high chi block copolymers of [polystyrene-ranrfom-poly(4-tert-butyl styrene)28wt. %]m-6 / oc^-polylactiden([PS72wt. o / „-r-PtBS28wt. <> / 0]-6-PLA).

[0401] Scheme 18 shows the synthesis of Synthesis of the high chi block copolymers (BCPs) of (PS-r-PtBS)-b-PLA using random type macroinitiators with 28 wt% PtBS randomly in PS blocks, which is shows in more detail in example 44 as follows:Scheme 18Example 44

[0402] The anionic ring opening polymerization (AROP) were carried out in an inert atmosphere at 25 - 30 °C using highly dry chemicals, macroinitiators, solvents, and all glassware. The drying macroinitiator of PS?2wt. %-r-PtBS28wt. %-OH (Example 27, 3.0 g, 0.10417 mmol, Mnof 28.8 kg / mmol, PDI of 1.04), lactide monomer (LA, 1.60 g, 11.09 mmol), and indium (III) chloride (In(III)C13, 0.028 g, 0.13 mmol) were charged to a flask under nitrogen atmosphere in the glovebox. To this mixture, added dichloromethane (DCM, 28 ml, 8 mL / g of macroinitiator) and stirred for ~5 min until the macroinitiator and lactide are dissolved completely. Tri ethylamine (TEA, 0.03 ml,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC0.21 mmol, 2 fold-excess amount of macroinitiator) was added after which the indium salt began to dissolve (usually within 10 minutes). The reaction kept at 25 °C over 5 hours. After the complete conversion of LA monomers by NMR measurement, acetyl chloride (CH3COCI, 0.07 ml, 1.04 mmol, 10 fold-excess amount of macroinitiator) is added along with TEA (0.22 ml, 1,56 mmol) for termination by end-capping and kept stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The mixture was precipitated in isopropyl alcohol (IP A, 8 parts volume) and the precipitate was collected by vacuum filtration. The resulting BCPs were fractionated by the reverse addition of heptane, water-washed, and precipitated in isopropyl alcohol. The purified BCPs were dried in a vacuum oven at 70 °C. The product of [PS?2wt. %-r-PtBS28wt. %]- / ?-PLA was obtained as shown in Table 15.Example 45

[0403] Synthesis of high chi block copolymers of [polystyrene72wt. %-ra«<7om-poly(4-tert-butyl styrene) 28wt. %]m- / ’ / ocA>polylactiden([PS?2wt. %-r-PtBS28wt. %]-Z>-PLA) with different molecular weight (Mn). The synthesis of 28 wt. % PtBS-containing [PS?2wt. %-r-PtBS28wt. %]-Z>-PLA was performed via the anionic polymerization using all same conditions of Example 44 with the different macroinitiator of PS?2wt. %-r-PtBS28wt. %-OH (Example 28, 3.0 g, 0.12024 mmol, Mnof 24.9 kg / mmol, PDI of 1.09), following the procedure of the polymerization and purification as described in Example 37 The product of [PS?2wt. %-r-PtBS28wt. %]-Z>-PLA was obtained as shown in Table 15.

[0404] Table 15 shows a summary of the properties of the high chi block copolymers using random type macroinitiator (PS-r-PtBS28wt. %)-DPECH2OH by AROP with DL-lactide monomers for contact hole (CH) application.

[0405] Table 15New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC

[0406] FIG. 43 shows the 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r- PtBS)- / ?-PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45.

[0407] FIG. 44 shows the GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >- PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.

[0408] FIG. 45 shows the images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks: (A) Example 44 and (B) Example 45. Test conditions: On Si; Neutral Underlayer layer 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1). (The detail procedures are described in Example 42)

[0409] FIG. 46 shows SEM images of the contact hole nanostructures formed by direct selfassembly (DSA) of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks on the prepattern: (A) Example 44 only, (B) the blending of Example 44 and Example 45 with the wt. % ratio of 41 :59 and 68.0% of PS-r-PtBS. Test conditions: On IMEC 30nm C / H rectification prepattern; BCP 40nm FT at 110°C / 60sec / air; (The detail procedures are described in Example 43)

[0410] Table 16 shows the results obtained with the high chi block copolymers (BCPs) of (PS-r- PtBS)- / >-PLA with 28 wt. % PtBS randomly in PS blocks on the prepattern: Example 44 only, the blending of Example 44 and 45 with the wt. % ratio of 41:59 and 68.0% of PS-r-PtBS.

[0411] Table 16.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC*Test conditions: On IMEC 30nm C / 11 rectification prepattern; BCP40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher Ils (FOV1 & FOV2).Synthesis of high chi block copolymers of [polystyrene-6 / oc£-poly(4-tert-butyl styrene)20wt. %]m-6 / oc£-polylactiden([PSsowt. <> / o-6-PtBS20wt. <> / 0]-6-PLA).

[0412] Scheme 19 shows a non-limiting examples of synthetic pathway for a high chi block copolymers of [polystyrene- / ? Zoc^-poly(4-tert-butyl styrene) 20wt. %]m- / ? / <><7r-polylactiden([PSsowt. %- / >-PtBS2owt. %]-Z>-PLA with 20 % % PtBS (see Examples 46 and 47).Scheme 19Example 46Synthesis of high chi block copolymers of [polystyrene-6 / oc£-poly(4-tert-butyl styrene) 20wt. o / 0]m-6 / oc^-polylactiden([PSsowt. <> / o-6-PtBS20wt. <> / 0]-6-PLA).

[0413] The anionic ring opening polymerization (AROP) were carried out in an inert atmosphere at 25 - 30 °C using highly dry chemicals, macroinitiators, solvents, and all glassware. The drying macroinitiator ofPSsowt. %-Z’-PtBS20wt. %-OH (Example 30, 3.0 g, 0.1193 mmol, Mnof 25.2 kg / mmol, PDI of 1.05), lactide monomer (LA, 1.65 g, 1 1.45 mmol), and indium (III) chloride (In(III)C13, 0.032 g, 0.14 mmol) were charged to a flask under nitrogen atmosphere in the glovebox. To this mixture, added dichloromethane (DCM, 24 ml, 8 mL / g of macroinitiator) and stirred for ~5 min until the macroinitiator and lactide are dissolved completely. Triethylamine (TEA, 0.03 ml, 0.24 mmol, 2 fold-excess amount of macroinitiator) was added after which the indium salt began to dissolve (usually within 10 minutes). The reaction kept at 25 °C over 5 hours. After the complete conversion of LA monomers by NMR measurement, acetyl chloride (CH3COCI, 0.08 ml, 1.19 mmol, 10 fold-excess amount of macroinitiator) is added along with TEA (0.25 ml, 1,79 mmol) for termination by end-capping and kept stirring for 15 minutes (The color will change to yellow upon the addition of triethyl amine). The mixture was precipitated in isopropyl alcohol (IP A, 8 parts volume) and the precipitate was collected by vacuum filtration. The resulting BCPs were fractionated by the reverse addition of heptane, water-washed, and precipitated in isopropyl alcohol.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCThe purified BCPs were dried in a vacuum oven at 70 °C. The product of [PSsowt. %-Z>-PtBS20wt. %]- / ?-PLA was obtained as shown in Table 17.Example 47

[0414] Synthesis of high chi block copolymers of [polystyrenesowt. %- / ’ / ocA>poly(4-tert-butyl styrene) 20wt. %]m- / ? / <><A-polylactiden([PSsowt. %-Z>-PfBS20wt %]-Z>-PLA) with the block type macroinitiators of (PS- / ?-PtBS20wt %)-DPECH2OH. The synthesis of [PSsowt. %-Z>-PtBS20wt. %]- / >- PLA was performed via the AROP using all same conditions of Example 46 with the different macroinitiator of PSsowt. %-Z’-PfBS20wt. %-OH (Example 32, 3.0 g, 0.1658 mmol, Mnof 18.1 kg / mmol, PDI of 1.04), In(III)Cl3, 0.044 g, 0.20 mmol), and TEA (TEA, 0.05 ml, 0.33 mmol) at 25 °C. Quantitative yield was obtained as shown in Table 17.

[0415] Table 17 shows a summary of the characteristics of Examples 46 and 47.

[0416] Table 17. Synthesis of high chi block copolymers using the block type macroinitiator (PS- / >- PtBS20wt. %)-DPECH2OH by AROP with DL-lactide monomers for contact hole (CH) application.

[0417] FIG. 47 shows the 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS- / >- PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / >-PtBS: (A) Example 46 and (B) Example 47.

[0418] FIG. 48 shows the GPC curves of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / ?-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 46 and (B) Example 47. (a) Polystyrene, (b) block type macroinitiator of (PS- / ?-PtBS)-DPECH2OH and (b)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC high chi BCPs.

[0419] FIG. 49 shows SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 46 and (B) Example 47. Test conditions: On Si; NEUTRAL UNDERLAYER 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1). (The detail procedures are described in Example 42)

[0420] FIG. 50 shows SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 46 and (B) Example 47. Test conditions: On Si; NEUTRAL UNDERLAYER 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1). (The detail procedures are described in Example 43.)

[0421] Table 18 shows the DSA test results of the high chi block copolymers (BCPs) of (PS- / >- PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / ?-PtBS on the prepattern: The blending of Example 46 and Example 47 with the wt. % ratio of 80.7:19.3 and 71.4% ofPS- / >-PtBS.

[0422] Table 18*Test conditions: On IMEC 30nm C / 11 rectification prepattern; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher Ils (FOV1 & FOV2).Synthesis of the high chi block copolymers (BCPs) of (PS-6-PtBS)-6-PLA using block type macroinitiators with 20 wt% PtBS.

[0423] Scheme 20. Shows the synthesis of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / ?-PLA using block type macroinitiators with 20 wt% PtBS. Examples 47a to 49 shows details onNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC the synthesis of different polymers of this type.

[0424] Scheme 20Example 47a

[0425] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 24, 4.0 g, 0.1544 mmol, weight% ratio of St:tBS = 80:20, Mnof25.9 kg / mmol, PDI of 1.06), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.041 g, 0.19 mmol) and TEA (0.04 ml, 0.31 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 11.Example 48.

[0426] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 25, 4.0 g, 0.2174 mmol, weight% ratio of St:tBS = 80:20, Mnof 18.4 kg / mmol, PDI of 1.04), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.058 g, 0.26 mmol) and TEA (0.06 ml, 0.43 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 11.Example 49.

[0427] The synthesis by AROP and purification were carried out using all same conditions of Example 37 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 26, 4.0 g, 0.3306 mmol, weight% ratio of St:tBS = 80:20, Mnof 12.1 kg / mmol, PDI of 1.05), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.088 g, 0.40 mmol) and TEA (0.09 ml, 0.66 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 19.

[0428] Table 19 shows the characteristics of high chi block copolymers using random type macroinitiator (PS-r-PtBS20wt. %)-DPECH2OH by AROP with DL-lactide monomers for line and space (L&S) application.

[0429] New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCTable 19*The absolute Mngiven in Table was calculated using GPC Mnof polystyrene and Mnof PLA calculated from 1H-NMR

[0430] FIG. 51 shows the'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r- PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (C) Example 49.

[0431] FIG. 52 shows the GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt% PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (D) Example 49. (a) random type macroinitiator of (PS-r-PtBS)-DPECH2OH and (b) high chi BCPs.

[0432] Example 50. Preparation of the nanostructure formation.

[0433] The test process for forming a Line and Space (LS) array into a substrate by self-assembly are followed by all step of Example 43 exactly.

[0434] FIG. 53 shows SEM images of contact hole nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 47a, (B) Example 48, and (D) Example 49. Test conditions: On Si; NEUTRAL UNDERLAYER 2 coat; Bake 250°C / 30min / N2; 2min PGMEA rinse; BCP 40nm FT at 110°C / 60sec / air; Anneal / 250°C / 15min / N2; Trion etcher I ls (FOV1).Synthesis of the high chi block copolymers (BCPs) of (PS-6-PtBS)-6-PLA using block type macroinitiators with 20 wt. % PtBS for L&S application.

[0435] Scheme 21 summarized the synthesis of the high chi block copolymers (BCPs) of (PS- / >- PtBS)- / >-PLA using block type macroinitiators with 20 wt. % PtBS for L&S application. TheNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC synthesis of these materials is described in examples 51 to 53 as follows:Scheme 21Example 51

[0436] The synthesis by AROP and purification were carried out using all same conditions of Example 44 with the different macroinitiator of PSsowt. %-Z’-PfBS20wt. %-OH (Example 30, 4.0 g, 0.3306 mmol, weight% ratio of St:tBS = 80:20, Mnof25.2 kg / mmol, PDI of 1.05), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.042 g, 0.19 mmol) and TEA (0.04 ml, 0.32 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 20.Example 52

[0437] The synthesis by AROP and purification were carried out using all same conditions of Example 44 with the different macroinitiator of PSsowt. %-Z’-PfBS20wt. %-OH (Example 32, 4.0 g, 0.2209 mmol, weight% ratio of St:tBS = 80:20, Mnof 18.1 kg / mmol, PDI of 1.04), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.059 g, 0.27 mmol) and TEA (0.06 ml, 0.44 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 20.Example 53

[0438] The synthesis by AROP and purification were carried out using all same conditions of Example 44 with the different macroinitiator of PSsowt. %-Z’-PfBS20wt. %-OH (Example 33, 4.0 g, 0.3604 mmol, weight% ratio of St:tBS = 80:20, Mnof 11.1 kg / mmol, PDI of 1.04), DL-lactide (5.20 g, 36.08 mmol), In(III)C13 (0.096 g, 0.43 mmol) and TEA (0.10 ml, 0.72 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 20.

[0439] Table 20. Summarizes the properties of high chi block copolymers using block type macroinitiator (PS- / ?-PtBS20wt. %)-DPECH2OH by AROP with DL-lactide monomers for line and space (L&S) application.

[0440] Table 20.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC*The absolute Mngiven in Table was calculated using GPC Mnof polystyrene and Mnof PLA calculated from 1H-NMR.

[0441] FIG. 54 shows the 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS- / >- PtBS)- / >-PLA with 20 wt. % PtBS: (A) Example 51, (B) Example 52, and (D) Example 53.

[0442] FIG. 55 shows the GPC curves of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / ?-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS-b-PtBS: (A) Example 51, (B) Example 52, and (C) Example 53. (a) Polystyrene, (b) block type macroinitiator of (PS- / ?-PtBS)- DPECH2OH and (b) high chi BCPs.Example 54 The test process for forming a LS array into a substrate by self-assembly.

[0443] All comprising steps for forming LS fingerprint self-assembled nanostructure were followed by most of steps in Example 42, with different baking conditions at 230 °C for 15 min and FT 50 nm. .Example 55 The process of the EUV LS pattern for rectification.

[0444] All comprising steps for forming a LS array pattern in the block copolymer film by directed self-assembled chemoepitaxy were followed by most of steps in Example 43, with different baking conditions at 230 °C for 30 min and FT 50 nm.

[0445] FIG. 56 shows SEM images of the lamellar nanostructures by self-assembly of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / >-PtBS: (A) Example 51, (B) Example 52, and (C) Example 53. Test conditions: On Si;New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCNEUTRAL UNDERLAYER 2 coat; Bake 250°C / 30 min / N2; 2min PGMEA rinse; BCP 50nm FT at 110°C / 60sec / air; Anneal / 230°C / 15min / N2; Trion etcher 18s (FOV1). (The detail procedures are described in Example 54) .

[0446] FIG. 57 shows SEM images of the line and space nanostructures formed by direct selfassembly (DSA) of the high chi block copolymers (BCPs) of (PS- / >-PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / ?-PtBS on the prepattem: The blending of Example 52 and Example 53 with the wt. % ratio of 50:50 and 50 % of PS- / >-PtBS. Test conditions: On IMEC 24nm L / S rectification prepattern; BCP 50nm FT at 110°C / 60sec / air; Anneal / 230°C / 30min / N2; Trion etcher 18s at 75 / 75 W, 10 mTorr, O2 50 seem, N2 50 Seem (FOV1 and FOV2). (The detail procedures are described in Example 55.)

[0447] Table 21 shows the DSA test results of the high chi block copolymers (BCPs) of (PS- / >- PtBS)- / >-PLA with 20 wt. % PtBS in the hydrophobic blocks of PS- / >-PtBS on the rectification prepattern: The blending of Example 52 and Example 53 with the wt. % ratio of 50:50 and 50 % of PS- / ?-PtBS. Test conditions: On IMEC 24nm L / S rectification prepattern; BCP 50nm FT at 110°C / 60sec / air; Anneal / 230°C / 30min / N2; Trion etcher 18s at 75 / 75 W, 10 mTorr, O2 50 seem, N250 Seem (FOV1 and FOV2).

[0448] Table 21Synthesis of the high chi block copolymers (BCPs) of (PS-r-PtBS)-6-PLA using random type macroinitiators with 20 wt. % PtBS randomly in PS blocks.

[0449] Scheme 22 shows the synthesis of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?- PLA using random type macro initiators with 20 wt. % PtBS randomly in PS blocks which is give in more details in Examples 56 and 57 as follows:New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PCScheme 22Example 56

[0450] The synthesis by AROP and purification were carried out using all same conditions of Example 44 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 34, 4.0 g, 0.1576 mmol but actual 0.0730 mmol due to the efficiency of end-capping reaction with 68%, weight% ratio of St:tBS = 80:20, Mnof 25.8 kg / mmol, PDI of 1.05), DL-lactide (2.31 g, 16.04 mmol), In(III)C13 (0.019 g, 0.09 mmol) and TEA (0.02 ml, 0.15 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 22.

[0451] Example 57 The synthesis by AROP and purification were carried out using all same conditions of Example 44 with the different macroinitiator of PSsowt. %-r-PtBS20wt. %-OH (Example 34, 4.0 g, 0.1576 mmol but actual 0.0730 mmol due to the efficiency of end-capping reaction with 68%, weight% ratio of St:tBS = 80:20, Mnof 25.8 kg / mmol, PDI of 1.05), DL-lactide (1.36 g, 9.44 mmol), In(III)C13 (0.028 g, 0.13 mmol) and TEA (0.03 ml, 0.21 mmol) in Dichloromethane (DCM, 32 ml, 8 mL / g of macroinitiator). Quantitative yield was obtained as shown in Table 22.

[0452] Table 22 shows a summary of the characteristics of the high chi block copolymers made using random type macroinitiator (PS-r-PtBS20wt. %)-BzOH by AROP with DL-lactide monomers for contact hole (CH) application (example 56 and 57).

[0453] Table 22.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC*The absolute Mngiven in Table was calculated using GPC Mnof polystyrene and Mn of PLA calculated from1H-NMR.

[0454] FIG. 58 shows 'H-NMR spectra of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / ?-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 56 and (B) Example 57.

[0455] FIG. 59 shows GPC curves of the high chi block copolymers (BCPs) of (PS-r-PtBS)- / >-PLA with 20 wt. % PtBS randomly in PS blocks: (A) Example 56 and (B) Example 57. (a) random type macroinitiator of (PS-r-PtBS)-BzOH and (b) high chi BCPs.

Claims

New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PCWhat is claimed is:

1. A block copolymer of structure (I) comprising a non-polar first block segment A prepared by anionic polymerization, a polar second block segment B, prepared by metal catalyzed ring opening coordinative polymerization, a linking moiety Z between said first block segment A, and said second block segment B, and a first and second end groups Ei and E2, where said first block segment, A, is either a block copolymer segment of structure (II- 1), or a random copolymer segment of structure (II-2), where Ri is selected from the group consisting of a Ci-15 linear alkyl, a C3-15 branched alkyl, a -Si(R3a)2-R3 moiety, and a -Si(R3b)2-R3c- [Si(R3b)2-O]ni-R3d-R4 moiety, where R3, is selected from a C1-20 linear alkyl or a C3-20 branched alkyl, Rsa, Rsb, and R4are individually selected from a C1-6 linear alkyl or a C3-6 branched alkyl, Rsc and Rsa are individually selected from a direct valence bond, a C1-8 alkylene, or -Si(R3b)2- moiety, nl is an integer ranging from 1 to 10, and where x is the total wt. % of styrene and 4- vinylbenzocyclobutene repeat units, and y is the wt. % of a styrene repeat unit substituted by Ri in structure (II- 1) and a and b are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4-vinylbenzocyclobutene, where x is from about 40 wt. % to about 80 wt. % and y is from about 60 wt. % to about 20 wt. %, and the sum of x and y is 100 % of the weight of the number average molecular weight (Mn) of the block copolymer segment of structure (II- 1), and further where a is from about 94 mol. % to about 100 mol. % and b is from about 6 mol. % to 0 mol. %, where the sum of a and b is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4- vinylbenzocyclobutene, where x’ is the total wt. % of styrene and 4-vinylbenzocyclobutene repeat units, y’ is the wt. % of a styrene repeat unit substituted by Ri in structure (II-2) and a’ and b’ are the mol. %, respectively, of a repeat unit derived from styrene and a repeat unit derived from 4- vinylbenzocyclobutene, where x’ is from about 40 wt. % to about 80 wt. % and y’ is from about 60 wt. % to about 20 wt. %, and the sum of x’ and y’ is 100 % of the weight of the Mnof the random copolymer segment of structure (II-2), and further where a’ is from about 94 mol. % to about 100 mol. % and b’ is from about 6 mol. % to 0 mol. %, where the sum of a’ and b’ is 100 % of the total moles of the repeat unit derived from styrene and the repeat unit derived from 4-vinylbenzocyclobutene,New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC where said linking group Z, is an alkoxide comprising moiety of structure (III), (Illa) or (Illb) where Rz2, Rzs and Rz4, Rzs, Rze, are independently selected from H, a Ci-8 alkyl, and an aryl, Rz, Rzi, are either independently selected from H, a Ci-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1, and further where Rz? is H, a C1-8 alkyl, an aryl, a biphenyl moiety, and Rzs is H or a Ci-s alkyl, where said second block segment B is either a homopolymer segment, a di-block copolymer segment, or a random copolymer segment, when said block segment B is a homopolymer segment it has repeat units of structure (IV), when said block segment B is a di-block copolymer segment, it has structure (IV-2) which comprises a first block with repeat units of structures (IV) and a second block of structure (IV- 1), where structure (IV) and (IV- 1) have different structures, when said block segment B is a random copolymer segment, it has structure (IV-3) which comprises repeat units of structures (IV) and (IV- 1), where (IV) and (IV) are different structures, in structure (IV) X is oxy (-O-) or a direct valence bond, where nb is 1 or 0, nbl is 0 or 1, where when X is oxy, the sum of nb and nbl is 2, and where R2, R2a, R?b and R2c, are independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where Rs is a C1-4 linear alkylene moiety, in structure (IV-1) X’ is oxy (-O-) or a direct valence bond, where nb’ is 1 or 0, nb’ 1 is 0 or 1, and where when X’ is oxy the sum of nb’ and nb’ 1 is 2, and where R2’, R2’a, R2’b, and R2’care independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, or a -Rs-Aryl moiety, where R5 is a C1-4 alkylene, where in structure (IV-2), xa designates the wt. % of the repeat units of structure (IV) and ya designates the wt. % of repeat units of structure (IV-1), where xa is from about 40 wt. % to about 80 wt. % of the total weight of the Mnof said second block segment B, and ya is from about 60 wt. % to about 20 wt. %, where the sum of xa and ya equals 100 % of the weight of the Mnof said second block segment B of structure (IV-2), where in structure (IV-3), xa’ designates the wt. % of the repeat units of structure (IV) and ya’ designates the wt. % of repeat units of structure (IV-1), where xa‘ is from about 40 wt. % to about 80 wt. % of the total weight of said second block B, and ya’ is from about 60 wt. % to about 20 wt. % of said second block segment B, where the sum of xa’ and ya’ equals 100 % of the weight of the Mnof said second block segment B of structure (IV-3), and said first end group, Ei, is a Ci-is alkyl, or a C3-6 branched alkyl and said second end group, E2, is a carbonyl alkyl (-C(=O)-alkyl) moiety, where said alkyl is a C1-8 alkyl or aryl, and furtherNew PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC where the number average molecular (Mn) of the said block copolymer of structure (I) is from about 2000 g / mol to about 100,000 g / mol, and the ratio of the Mnof said first block segment A to the Mnof said second block segment B ranges from about 0.40 to about 0.75;(IV) (iv-1) (IV-3).

2. The block copolymer of claim 1, where structure (I), consist of a first block segment A and a second block segment B, a linking moiety Z between said first and second block segments A and B, and a first and second end group Ei and E2.

3. The block copolymer of claims 1 or 2, wherein the ratio of the Mnof block segment A to the Mnof block segment B is from about 0.47 to about 0.67.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC4. The block copolymer of claims 1 or 3, wherein said ratio of the Mnof block segment A to Block segment B is from about 0.40 to about 0.60.

5. The block copolymer of claims 1 or 3, wherein said ratio of the Mnof block segment A to block segment B is from about 0.61 to about 0.75.

6. The block copolymer of structure (I) of any one of claims 1 to 5, which has a number average molecular weight (Mn) from about 3,000 g / mol to about 90,000 g / mol.

7. The block copolymer of any one of claims 1 to 6, where said first block segment A has an Mn from about 2,000 g / mol to about 41,000 g / mol and were said second block segment B, has and Mnwhich is from about 2,250 g / mol to about 44,500 g / mol, excluding values of Mnof said first block segment A and second block segment B calculated from the ratio of the Mnof block segment A to Block segment B of about 0.40 to about 0.60 second block segment B which fall out of said ranges of Mn for first block segment A and second block segment B.

8. The block copolymer of any one of claims 1 to 7, where said polydispersity ranges from 1.00 to about 1.15.

9. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said block segment A has a volume % ranging from about 43 vol. % to about 71 vol. % and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.40 to about 0.60.

10. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said block segment Ahas a volume % ranging from about 43 vol. % to about 71 vol. % and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.61 to about 0.75.

11. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said block segment A, when Ri is a -Si(R3a)2-R3 moiety, has a vol. % from about 47 to about 53 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

12. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said block segment A, when Ri is a -Si(R3a)2-R3 moiety, has a vol. % from about 47 to about 53 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC13. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said non polar block segment A, when Ri is a - C1-15 linear alkyl or a C3-15 branched alkyl moiety, said non-polar block segment A has a volume % from about 44 vol. % to about 65 vol. % of the total volume of said non polar block segment A and said polar block segment B, and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.40 to about 0.60.

14. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said non polar block segment A, when Ri is a - C1-15 linear alkyl or a C3-15 branched alkyl moiety, said non-polar block segment A has a volume % from about 44 vol. % to about 65 vol. % of the total volume of said non polar block segment A and said polar block segment B, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

15. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said non polar block segment A, when Ri is -Si(R3b)2-R3c-[Si(R3b)2-O]ni-R3d-R4 moiety, said non-polar block segment A has a volume % from about 50 vol. % to about 62 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

16. The block copolymer of any one of claims 1 to 8, where said copolymer is one, where said non polar block segment A, when Ri is -Si(R3b)2-R3c[Si(R3b)2-O]ni-R3d-R4 moiety, said non-polar block segment A has a volume % from about 50 vol. % to about 62 vol. % of the total volume of said non polar block segment A and said polar block segment B and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

17. The block copolymer of any one of claims 1 to 16, wherein said first block segment A, has structure (II- 1).

18. The block copolymer of any one of claims 1 to 17, wherein said first block segment A, has structure (II- 1 ) and x is from about 45 wt. % to 75 wt. % and y is from 55 wt. % to 25 wt. %, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

19. The block copolymer of any one of claims 1 to 17, wherein said first block segment A, has structure (II- 1 ) and x is from about 45 wt. % to 75 wt. % and y is from 55 wt. % to 25 wt. %, and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.61 to about 0.75.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC20. The block copolymer of any one of claims 1 to 19, wherein said first block segment A, has structure (II- 1 ), and b is 0 mol. %.

21. The block copolymer of any one of claims 1 to 18, wherein said first block segment A, has structure (II- 1 ) and b ranges from about 0.5 mol. % to about 6 mol. %.

22. The block copolymer of any one of claims 1 to 16, wherein said first block segment A, has structure (II-2).

23. The block copolymer of any one of claims 1 to 16, and 22, where said first block segment A, has a structure (II-2) were x ranges from about 45 wt. % to about 75 wt. % and y ranges from about 55 wt. % to about 25 wt. %, and said ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

24. The block copolymer of any one of claims 1 to 16, and 22, where said first block segment A, has a structure (II-2) were x ranges from about 45 wt. % to about 75 wt. % and y ranges from about 55 wt. % to about 25 wt. % and said ratio of the Mnof block segment A to the Mnof block segment B is from about 0.61 to about 0.75.

25. The block copolymer of any one of claims 1 to 16, and 22 to 24, wherein said first block segment A, has structure (II-2) and b’ is 0 mol. %.

26. The block copolymer of any one of claims 1 to 12, and 22 to 24, wherein said first block segment A, has structure (II-2) and b’ ranges from about 0.5 mol. % to about 6 mol. %.

27. The block copolymer of any one of claims 1 to 26, where Ri is a C1-15 linear alkyl.

28. The block copolymer of claim 27, where Ri is a C1-10 linear alkyl.

29. The block copolymer of claim 27 or 28, where Ri is a C1-8 linear alkyl.

30. The block copolymer of any one of claims 27 to 29, where Ri is a C1-5 linear alkyl.

31. The block copolymer of any one of claims 27 to 30, where Ri is methyl or ethyl.

32. The block copolymer of any one of claims 27 to 31, where Ri is methyl.

33. The block copolymer of any one of claims 1 to 26, where Ri is a C3-15 branched alkyl.

34. The block copolymer of claim 33, where Ri is a C3-10 branched alkyl.

35. The block copolymer of claim 33 or 34, where Ri is a C3-5 branched alkyl.

36. The block copolymer of any one of claims 33 to 35, where Ri is tert-butyl.

37. The block copolymer of any one of claims 1 to 26, where Ri is a -Si(R3a)2-R3 moiety.

38. The block copolymer of claim 37, where R3 is C1-15 linear alkyl.

39. The block copolymer of claim 37, where R3 is C5-15 linear alkyl.

40. The block copolymer of claim 37, where R3 is C10-15 linear alkyl.

41. The block copolymer of claim 37, where R3 is C15 linear alkyl.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC42. The block copolymer of claim 37, where R3 is C1-10 linear alkyl.

43. The block copolymer of any one of claims 37 and 42, where R3 is C1-8 linear alkyl.

44. The block copolymer of any one of claims 37, 42 and 43, where R3 is C1-5 linear alkyl.

45. The block copolymer of any one of claims 37, 42 to 44, where R3 is C1-3 linear alkyl.

46. The block copolymer of any one of claims 37, 42 to 45, where R3 is ethyl or methyl.

47. The block copolymer of any one of claims 37, 42 to 45, where R3 is methyl.

48. The block copolymer of claim 37, where R3 is C3-15 branched alkyl.

49. The block copolymer of claim 37 or 48, where R3 is C3-10 branched alkyl.

50. The block copolymer of any one of claims 37, 48 and 49, where R3 is C3-8 branched alkyl.

51. The block copolymer of any one of claims 37, 48 to 50, where R3 is C3-5 branched alkyl.

52. The block copolymer of any one of claims 37, 48 to 51, where R3 is tert-butyl.

53. The block copolymer of any one of claims 37 to 52, where Rsais C1-15 linear alkyl.

54. The block copolymer of claim 37 and 53, where Rsais C1-10 linear alkyl.

55. The block copolymer of any one of claims 37 to 54, where Rsais C1-8 linear alkyl.

56. The block copolymer of any one of claims 37 to 55, where Rsais C1-5 linear alkyl.

57. The block copolymer of any one of claims 37 to 56, where Rsais C1-3 linear alkyl.

58. The block copolymer of any one of claims 37 to 57, where Rja is ethyl or methyl.

59. The block copolymer of any one of claims 37 to 58, where Rja is methyl.

60. The block copolymer of claim 59, where Rsais methyl and R3 is a C15 linear alkyl.

61. The block copolymer of claim 37, where Rsais C3-15 branched alkyl.

62. The block copolymer of claim 37 or 61, where Rsais C3-10 branched alkyl.

63. The block copolymer of any one of claims 37 and 61 to 62, where Rsais C3-8 branched alkyl.

64. The block copolymer of any one of claims 37 and 61 to 63, where Rsais C3-5 branched alkyl.

65. The block copolymer of any one of claims 37, 62 to 63, where Rsais tert-butyl.

66. The block copolymer of any one of claim 1 to 26, and 37, where Ri is -Si(CH3)3.

67. The block copolymer of any one of claims 1 to 26, where Ri is a -Si(R3b)2-R3c-[Si(R3b)2-O]nl-R3d-R4.

68. The block copolymer of claim 67, where Rsb is a C1-15 linear alkyl.

69. The block copolymer of any one of claims 67 and 68, where Rsb is a C1-10 linear alkyl.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC70. The block copolymer of any one of claims 67 to 69, where Rsb and R4 are individually selected from a C1-5 linear alkyl.

71. The block copolymer of any one of claims 67 to 70, where Rsb and R4 are individually selected from a C1-4 linear alkyl.

72. The block copolymer of any one of claim 67 to 71, where Rsb and R4 are individually selected from ethyl or methyl.

73. The block copolymer of any one of claims 67 to 72, where Rsb and R4 are methyl.

74. The block copolymer of any one of claims 1 to 73, where said linking group Z is an alkoxide moiety of structure (III), where nz is 0.

75. The block copolymer of any one of claims 1 to 73, where said linking group Z has structure (III-l),76. The block copolymer of claim 75, where Rz2 is an aryl and Rzi is H.

77. The block copolymer of claims 74 or 75, where said linking group Z, has structure (HI-2),78. The block copolymer of any one of claims 1 to 74, where said linking group Z has structure (III-3) where Rz2 is a H or a Ci to C4 alkyl,79. The block copolymer of any one of claims 1 to 74, and 78, where said linking group Z has structure (III-3a),H (— CH2- c— )-oH (III-3a).

80. The block copolymer of any one of claims 1 to 74 and 78, where said linking group Z has structure (III-3b),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC81. The block copolymer of any one of claims 1 to 74 and 78, where said linking group Z has structure (III-3c),82. The block copolymer of any one of claims 1 to 74 and 78, where said linking group Z has structure (III-3d),83. The block copolymer of any one of claims 1 to 74, where Rz, Rzi, form together a C3 to C4 alkylene moiety which forms a 5 to 6 membered ring, where said linking group Z has structure (III-4),84. The block copolymer of any one of claim 1 to 74, and 83, where said linking group Z has structure (III-4a),85. The block copolymer of any one of claims 1 to 73, where said linking group Z is an alkoxide moiety of structure (III), where nz is 1.

86. The block copolymer of any one of claims 1 to 73 and 85, where said linking group Z has structure (III- 5),87. The block copolymer of any one of claims 1, 73 and 84, where said linking group Z has structure (III-6),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC88. The block copolymer of any one of claims 1 to 73 and 85, where said linking group Z has structure (III-7),89. The block copolymer of any one of claims 1 to 73 and 85, where said structure (III), is one wherein Rz2 and Rz4 are H, and Rz, Rzi and Rzs are independently a C1-8 alkyl and nz is 1.

90. The block copolymer of any one of claim 1 to 73 and 85, where said linking group Z has structure (III-8),91. The block copolymer of any one of claims 1 to 73, where said structure (III), is one wherein Rz, Rzs and Rz4, are H, and Rzl is an aryl, and Rz2 is a C1-8 alkyl and nz is 1.

92. The block copolymer of any one of claims 1 to 72, and 89, where said linking group Z has structure (III-9),93. The block copolymer of any one of claims 1 to 73, and 92, where said linking group Z has structure (III- 10),94. The block copolymer of any one of claims 1 to 73, where said linking group Z is an alkoxide moiety of structure (Illa)New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC95. The block copolymer of claim 94, wherein in structure (Illa) Rzs and Rzb are individually selected from H or a Ci-8 alkyl.

96. The block copolymer of claim 94, wherein in structure (Illa) Rzs and Rzb are individually selected from H or an aryl.

97. The block copolymer of claim 94, wherein said linking group Z has structure (Illa- 1)98. The block copolymer of claim 94, wherein said linking group Z has structure (IIIa-2)99. The block copolymer of any one of claims 1 to 73, where said linking group Z is an alkoxide moiety of structure (Illb),100. The block copolymer of claim 99, where in structure (Illb) Rz? is H and Rzs is a Ci-8 alkyl.

101. The block copolymer of claim 99, where in structure (Illb) Rz? is a Ci-8 alkyl and Rzs is H.

102. The block copolymer of claim 99, where in structure (Illb) Rz? is a Ci-4 alkyl and Rzs is H.

103. The block copolymer of claim 99, where in structure (Illb) Rz? is a Ci-8 alkyl and Rzs is a Ci-8 alkyl.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC104. The block copolymer of any one of claims 1 to 73, and 99, where said linking group Z is an alkoxide moiety of structure105. The block copolymer of any one of claims 1 to 73, and 99, where said linking group Z is an alkoxide moiety of structure106. The block copolymer of claim 99, where in structure (Illb), Rz? is an aryl and Rzs is H.

107. The block copolymer of claim 99, where said linking group has structure (IIIc-1),108. The block copolymer of claim 99, where in structure (Illb), Rz? is a biphenyl moiety, and Rzs is H.

109. The block copolymer of claim 99, where said linking group has structure (IIIc-2),110. The block copolymer of any one of claims 1 to 109, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IV).

111. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC112. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-1),113. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-3), where R2, R.2a, and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a - Rs -Aryl moiety, where R5 is a C1-4 linear alkylene moiety, and R2c is selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,114. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-4), where R2, and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,115. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-5), where R2a and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,116. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-6), where R2, and R2a are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC117. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-7), where R2a is selected from a Ci-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where R5 is a Ci -4 linear alkylene moiety,118. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-8), where R?b is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a Ci -4 linear alkylene moiety,119. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-9), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a Ci -4 linear alkylene moiety,120. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-10), where R2a is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a Ci -4 linear alkylene moiety,121. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-11), where R2 is individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety, and where R2c is individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC122. The block copolymer of any one of claims 1 to 110, wherein said second block segment B is a homopolymer block which has a repeat unit of structure (IVa-12), where R2 and R2a are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,123. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-12a),124. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-13), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety, and R2c is selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety,125. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-14),126. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-14’),127. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVa-15),128. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC129. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb), where R2, R2a and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a - Rs -Aryl moiety, where R5 is a C1-4 linear alkylene moiety,130. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb’),131. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb’), where R2, R2a, R2b and R2C are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety,132. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-1),133. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-2), where R2, and R2b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,134. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-3), where R2, and R2a areNew PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,135. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-4), where R2a, and R?b are individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,136. The block copolymer of any one of claims 1 to 110, wherein said second block segment B, is a homopolymer block which has a repeat unit of structure (IVb-5), where R2a, is individually selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -R5- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,137. The block copolymer of any one of claims 1 to 110, wherein said second block segmentB, has structure (IV-2), where structure (IV) and (IV- 1) are different structures,(IV) (IV-1) (IV-2).

138. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV-2a), where structure (IVa) and (IVa-1) are different structures,(IVa) (wa-i) (IV-2a).

139. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV2b), where structures (IVb) and (IVb-1) are different structures,(IVb) (TVb-1) (IV-2b).New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC140. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV2b’), where structures (IVc-2) and (IVc-3) are different structures,(TVc-2) (TVc-3) (IV-2b’).

141. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV-2b”), where R2’ais selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where Rs is a C1-4 linear alkylene moiety,(IVc) (IVc-1) (IV-2b”).

142. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV-2c), where structures (IVa) and (IVb-1) are different structures,(IVa) OVb-D (IV-2c).

143. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, has structure (IV-2d),(IVb) (IVa-1) (IV-2d).

144. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2e), where R2, R2a, and R2c are independently either H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety,145. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2f), where R2, R.2a, and R2c are independently either a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC146. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2g), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where R5 is a Ci- 4 linear alkylene moiety, and R?cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and R2’cis selected from H, a Ci- 6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,147. The block copolymer of any one of claims 1 to 110, and 137, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-2h), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a Ci- 4 linear alkylene moiety, and R2c is selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,148. The block copolymer of any one of claims 1 to 110, wherein said second block segmentB, is said random copolymer segment of structure (IV-3),(IV) (IV-1) (IV-3).

149. The block copolymer of any one of claims 1 to 110, wherein said second block segmentB, has structure (IV-3 a), where structure (IVa) and (IVa-1) are different structures,150. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, has structure (IV3b), where structures (IVb) and (IVb-1) are different structures,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(IVb) c™-1) (IV-3b).

151. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, has structure (IV-3c), where structures (IVa) and (IVb-1) are different structures,(IVa) c™1) (IV-3c).

152. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, has structure (IV-3d),(IVb) (IVa-1) (IV-3d).

153. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, has structure (IV-3e), where R2, R2a, R2b, and R2c are independently either H, a Ci- 6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, where R5 is a C1-4 linear alkylene moiety,154. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3f), where R2, R2a, R2b, and R2c are independently either a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs- Aryl moiety, where R5 is a C1-4 linear alkylene moiety,155. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3g), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where R5 is a Ci- 4 linear alkylene moiety, and R?cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and R2’cis selected from H, a Ci- 6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC156. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3h), where R2 is selected from a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs -Aryl moiety, where R5 is a Cn 4 linear alkylene moiety, and R?cis selected from H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, and where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety, O R2C O[ / II I \ / II — rC — C - O-pco-f-CR2157. The block copolymer of any one of claims 1 to 110, and 149, wherein said second block segment B, is a di-block copolymer segment, of structure (IV-3i), where R2’ is selected from a H, a C1-6 linear alkyl, a C3-6 branched alkyl, an aryl moiety, and a -Rs-Aryl moiety,158. The block copolymer of any one of claims 1 to 157, where said second block segment B has an Mnbetween about 5,000 g / mol to about 17,000 g / mol.

159. The block copolymer of claims 137 to 147, where said block segment B, is a diblock copolymer segment where xa ranges from about 40 wt. % to about 80 wt. % and ya ranges from about 60 wt. % to about 20 wt. %, and the sum of xa and ya is 100 % of the weight of the Mnof said second block segment B.

160. The block copolymer of any one of claims 146, 147, and 159 where said block segment B, is a diblock copolymer segment where xa ranges from about 40 wt. % to about 80 wt. % and ya ranges from about 60 wt. % to about 20 wt. %, and the sum of xa and ya is 100 % of the weight of the Mnof said second block segment B.

161. The block copolymer of claims 148 to 157, where xa’ ranges from about 40 wt. % to about 80 wt. % and ya’ ranges from about 60 wt. % to about 20 wt. %, and the sum of xa’ and ya’ is 100 % of the weight of the Mnof said second block segment B.

162. The block copolymer of claims 155 to 157, and 161, where xa’ ranges from about 40 wt. % to about 80 wt. % and ya’ ranges from about 60 wt. % to about 20 wt. %, and the sum of xa’ and ya’ is 100 % of the weight of the the Mnof said second block segment B.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC163. The block copolymer of any one of claims 1 to 162, where said end group Ei is a C3-10 alkyl.

164. The block copolymer of any one of claims 1 to 163, where said end group Ei is a C3-10 alkyl which has structure (IV), where RE is a C1-4 alkyl and RE is a C1-5 alkyl,165. The block copolymer of any one of claims 1 to 164, where Ei is sec-butyl.

166. The block copolymer of any one of claims 1 to 165, where said end group E2 is a carbonyl alkyl (-C(=O)-alkyl) where said alkyl is a linear C1-8 alkyl.

167. The block copolymer of any one of claims 1 to 166, where said end group E2 is a carbonyl alkyl (-C(=O)-alkyl) where said alkyl is methyl.

168. The block copolymer of any one of claims 1 to 9, which has structure (Va), where Ri is selected from and C1-15 linear alkyl, and a C3-15 branched alkyl, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2c is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol,169. The block copolymer of any one of claims 1 to 9 and 168, wich has structure (Va-1),170. The block copolymer of any one of claims 1 to 9, 168 and 169, which has structure (Va-2) or structure (Va-2a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC171. The block copolymer of any one of claims 1 to 9 and 168 to 170, which has structure172. The block copolymer of any one of claims 1 to 9 and 168 to 169, which has structure(Va-4),(Va-4).

173. The block copolymer of any one of claims 1 to 9 and 168 to 169, which has structure(Va-5),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(Va-5).

174. The block copolymer of any one of claims 1 to 9, 168 and 169, which has structure(Va-6),175. The block copolymer of any one of claims 1 to 9 and 168 and 169, which has structure(Va-7),176. The block copolymer of any one of claims 1 to 9, 167 and 168, which has structure(Va-8),177. The block copolymer of any one of claims 1 to 9 and 168 to 169, which has structure(Va-9),New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC178. The block copolymer of any one of claims 1 to 9, 168 and 169, which has structure(Va-10),179. The block copolymer of any one of claims 1 to 9 and 168 to 169, which has structure(Va-11),180. The block copolymer of any one of claims 163 to 179, where y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A.

181. The block copolymer of any one of claims 163 to 179, where y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.

182. The block copolymer of any one of claims 1 to 10 which has structure (Vb), where Ri is selected from a Ci-is linear alkyl, a C3-15 branched alkyl, and a -Si(R3a)2-R3 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2c is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol, and b ranges from about 0.5 mol. % to about 6 mol. %, of the total moles of the repeat units derived from styrene and 4-vinylbenzocyclobutene,New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC183. The block copolymer of any one of claims 1 to 10, and 182, which has structure (Vb-184. The block copolymer of any one of claims 1 to 10 and 182 to 183, which has structure(Vb-2) or structure (Vb-2a),185. The block copolymer of any one of claims 1 to 10 and 182 to 184, which has structure(Vb-3) or structure (Vb-3a),186. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure(Vb-4),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC187. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure (Vb-5),(Vb-5).

188. The block copolymer of any one of claims 1 to 9, and 182 to 183, which has structure(Vb-6),189. The block copolymer of any one of claims 1 to 9 and 183 which has structure (Vb-7),190. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure (Vb-8),New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC191. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure(Vb-9),192. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure(Vb-10),193. The block copolymer of any one of claims 1 to 9 and 182 to 183, which has structure(Vb-11),(Vbl l).

194. The block copolymer of any one of claims 1 to 10 and 182 to 193, where y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC195. The block copolymer of any one of claims 1 to 10 and 182 to 193, where y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.

196. The block copolymer of any one of claims 1 to 10, which has structure (Vc), where Ri is selected from and Ci-is linear alkyl, and a C3-15 branched alkyl, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R?c is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol,197. The block copolymer of any one of claims 1 to 10 and 196 which has structure (Vc-1),198. The block copolymer of any one of claims 1 to 10, and 196 or 197 which has structure (Vc-2) or structure (Vc-2a),199. The block copolymer of any one of claims 1 to 10, and 196 to 198, which has structure(Vc-3) or structure (Vc-3a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC200. The block copolymer of any one of claims 1 to 10 and 196 or 197 which has structure(Vc-4),(Vc-4).

201. The block copolymer of any one of claims 1 to 10 and 196 or 197 which has structure(Vc-5),(Vc-5).

202. The block copolymer of any one of claims 1 to 10, and 196 or 197 which has structure(Vc-6),New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC203. The block copolymer of any one of claims 1 to 10 and 196 or 197 which has structure (Vc-7),204. The block copolymer of any one of claims 1 to 10, and 197, which has structure (Vc- 8),205. The block copolymer of any one of claims 1 to 10 and 196 or 197, which has structure (Vc-9),206. The block copolymer of any one of claims 1 to 10, and 196 or 197, which has structure(Vc-10),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC207. The block copolymer of any one of claims 1 to 10 and 196 or 197, which has structure (Vc-11),208. The block copolymer of any one of claims 196 to 207, where y’ is from about 18 wt. % to about 22 wt. %, of the total weight of the molecular weight of said first block segment A.

209. The block copolymer of any one of claims 197 to 207, where y’ is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.

210. The block copolymer of any one of claims 1 to 10, which has structure (Vd), where Ri is a -Si(R3a)2-R.3 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2c is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol,211. The block copolymer of any one of claims 1 to 10 and 210, which has structure (Vd-1),212. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure (Vd-2) or structure (Vd-2a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC213. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-3) or structure (Vd-3a),214. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-4),215. The block copolymer of any one of claims 1 to 10, 210 to 211, which has structure (Vd-5) or structure (Vd-5a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC216. The block copolymer of any one of claims 1 to 10, 210 to 211, which has structure (Vd-6) or structure (Vd-6a),217. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-7),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC(Vd-7).

218. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-8),(Vd-8).

219. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-9),220. The block copolymer of any one of claims 1 to 9 and 210 to 211, which has structure(Vd-10),221. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-11),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC222. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-12),223. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure (Vd-13),224. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure (Vd-14),225. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-15),226. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-16),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC227. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-17),228. The block copolymer of any one of claims 1 to 9 and 210 to 211, which has structure(Vd-18),229. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-19),230. The block copolymer of any one of claims 1 to 10 and 210 to 211, which has structure(Vd-20),New PCT application 21. August 2025Merck Patent GmbH Our ref.: AZ75319PC231. The block copolymer of any one of claims 210 to 230, where y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A.

232. The block copolymer of any one of 210 to 230, where y is from about 45 wt. % to about55 wt. %, of the total weight of the molecular weight of said first block segment A.

233. The block copolymer of any one of claims 1 to 10, which has structure (Ve), where Ri is a -Si(R3b)2-R3c-[Si(R3b)2-O]ni-R3d-R4 moiety, R2 is H, a C1-6 linear alkyl, or a C3-6 branched alkyl, and R2c is selected from H, a C1-6 linear alkyl, and a C3-6 branched alkyl, where the number average (Mn) of said block segment A ranges from about 5,000 g / mol to about 12,000 g / mol and said block segment B ranges from about 7,000 g / mol to about 14,000 g / mol,235. The block copolymer of any one of claims 1 to 10, 233 and 234 which has structure(Ve-2) or structure (Ve-2a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC236. The block copolymer of any one of claims 1 to 10, 233 to 235, which has structure (Ve-3) or structure (Ve-3a),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC237. The block copolymer of any one of claims 1 to 10 and 233 which has structure (Ve-4),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC238. The block copolymer of any one of claims 1 to 10 and 233 and 237, which has structure(Ve-5),239. The block copolymer of any one of claims 1 to 10 and 233 which has structure (Ve-6),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC240. The block copolymer of any one of claims 1 to 9 and 233 and 239, which has structure(Ve-7),241. The block copolymer of any one of claims 1 to 10 and 233, which has structure (Ve-8),New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC242. The block copolymer of any one of claims 1 to 10 and 233 and 241, which has structure (Ve-9),243. The block copolymer of any one of claims 1 to 10 and 233 which has structure (Ve-10),244. The block copolymer of any one of claims 1 to 10 and 233 and 243, which has structure(Ve-11),245. The block copolymer of any one of claims 233 to 245, where y is from about 27 wt. % to about 33 wt. %, of the total weight of the molecular weight of said first block segment A.New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC246. The block copolymer of any one of claims 233 to 244, where y is from about 45 wt. % to about 55 wt. %, of the total weight of the molecular weight of said first block segment A.

247. A composition comprising, the block copolymer of any one of claims 1 to 246 and an organic spin casting solvent.

248. A composition comprising, the block copolymer of any one of claims 1 to 4, 6, 7, 8, 9, 11, 13, 15, 17, 18, 20, 21, 22, 23, 25 to 246, wherein the ratio of the Mnof block segment A to the Mnof block segment B is from about 0.40 to about 0.60.

249. A composition comprising, the block copolymer of any one of claims 1 to 3, 5, 6, 7, 8, 10, 12, 14, 16, 17, 19, 20, 21, 22, 24, 25 to 246 wherein the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

250. A composition comprising, the block copolymer of any one of claims 1 to 4, 6 to 9, 11, 13, 15, 17, 18, 20, 21, 27 to 246, where said first block segment has structure (II- 1), and the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

251. A composition comprising, the block copolymer of any one of claims 1 to 4, 5, 6, 7, 8,9, 11, 13, 15, 22, 23, 25, to 246, where said first block segment has structure (II-2), and the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.40 to about 0.60.

252. A composition comprising, the block copolymer of any one of claims 1 to 4, 6 to 9, 11, 13, 15, 17, 18, 20, 21, 27 to 246, where said first block segment has structure (II- 1), and the ratio of the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

253. A composition comprising, the block copolymer of any one of claims 1 to 3, 5, 6 to 8,10, 12, 14, 16, 22 to 246, where said first block segment has structure (II-2), and the ratio the Mnof block segment Ato the Mnof block segment B is from about 0.61 to about 0.75.

254. The composition of any one of claim 247 to 253, where said block copolymer is present in a concentration from about 0.5 wt. % to about 3 wt. %.

255. A process of coating the composition of any one of claim 247 to 254 on a substrate.

256. A process of self-assembly comprising steps: i) forming a coating of a neutral layer on a substrate, ii) coating the composition of any one of claims 247 to 254 on to said neutral layer, to form a film of a block copolymer with polar and non-polar polymer segments,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC iii) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a self-assembled film pattern of the polar and nonpolar polymer segments of said film of said block copolymer, iv) using said self-assembled patterned film as a mask, etching said substrate with a plasma to pattern transfer this self-assembled patterned film into the substrate.

257. A process of chemoepitaxy directed self-assembly for pattern multiplication of L / S features comprising steps: ia) forming a coating of crosslinked pinning layer on a substrate, iia) forming a coating of a photoresist on said crosslinked pinning layer, iiia) imaging said coating of photoresist with radiation through a mask to form a L / S pattern of exposed areas to radiation, iva) developing said L / S pattern of exposed areas with a developer to form a L / S pattern imaged photoresist over said crosslinked layer, va) using a plasma and the L / S imaged photoresist as a mask to transfer said L / S pattern into said crosslinked pinning layer, forming a crosslinked pinning layer with a L / S pattern over said substrate, via) using said crosslinked pinning layer with a L / S pattern, depositing a brush neutral layer selectively on the areas in said crosslinked pinning layer with a L / S pattern which are open to the substrate, producing a chemoepitaxy L / S pattern of pinning and neutral areas over said substrate, viia) forming a film of block copolymer using the composition of any one of claims 248, 250, and 251 on said chemoepitaxy L / S pattern, viiia) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to induce in said film of block copolymer a multiplication of the L / S pattern by directed self-assembly induced by the underlying L / S pattern, ixa) using this film of block copolymer with a multiplication of the L / S pattern as a mask for etching into said substrate a multiplied L / S pattern with a plasma.

258. A process of chemoepitaxy directed self-assembly for pattern multiplication of CH features comprising steps: ib) forming a coating of crosslinked pinning layer on a substrate, iib) forming a coating of a photoresist on said crosslinked pinning layer, iiib) imaging said coating of photoresist with radiation through a mask to form a CH pattern of exposed areas to radiation,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC ivb) developing said CH pattern of exposed areas with a developer to form a CH pattern imaged photoresist over said crosslinked layer, vb) using a plasma and the CH imaged photoresist as a mask to transfer said CH pattern into said crosslinked pinning layer, forming a crosslinked pinning layer with a CH pattern over said substrate, vib) using said crosslinked pinning layer with a CH pattern, depositing a brush neutral layer selectively on the areas in said crosslinked pinning layer with a CH pattern which are open to the substrate, producing a chemoepitaxy CH pattern of pinning and neutral areas over said substrate, viib) forming a film of block copolymer using the composition of any one of claims 249, 252 and 253 on said chemoepitaxy CH pattern, viiib) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to induce in said film of block copolymer a multiplication of the L / S pattern by directed self-assembly induced by the underlying CH pattern, ixb) using this film of block copolymer with a multiplication of the CH pattern as a mask for etching into said substrate a multiplied CH pattern.

259. A process for forming a CH array into a substrate by self-assembly, comprising steps: iac) forming a coating of a grafted or crosslinked neutral layer on a substrate, iic) coating the composition of any one of claims 249, 252 and 253 onto said neutral layer, to form a film, iiic) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a self-assembled film contact hole pattern, and ivc) etching said substrate using said self-assembled film contact hole pattern as mask with a plasma to form a contact hole pattern in the substrate.

260. A process for pattern rectification of a EUV L / S pattern, comprising steps: id) forming a coating of a crosslinked pinning layer on a substrate, iid) coating said crosslinked pinning layer with EUV photoresist and imaging said photoresist to form an overlying L / S patterned EUV photoresist, iiid) using said overlying L / S array patterned photoresist as a mask, transferring this L / S array pattern into the neutral layer, forming a neutral layer with a L / S array pattern, ivd) coating the composition of any one of claims 248, 250, and 251 onto said neutral layer with a L / S array pattern, to form a film of block copolymer,New PCT application 21. August 2025 Merck Patent GmbH Our ref.: AZ75319PC vd) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a L / S array pattern in the block copolymer film by directed self-assembled chemoepitaxy, vid) etching said substrate using said L / S array pattern in the film formed by directed selfassembled chemoepitaxy as mask with a plasma to form a L / S array pattern in the substrate.

261. The process for pattern rectification of a EUV CH pattern, comprising steps: ie) forming a coating of a crosslinked pinning layer on a substrate, iie) coating said crosslinked pinning layer with EUV photoresist and imaging said photoresist to form an overlying CH array patterned EUV photoresist, iiie) using said overlying CH array patterned photoresist as a mask, transferring this CH array pattern into the neutral layer, forming a neutral layer with a CH array pattern, ive) coating the composition of any one of claims 249, 252 and 253, onto said neutral layer with a CH array pattern, to form a film of block copolymer, ve) baking said film, in an inert gas atmosphere, at a temperature selected from about 170°C to about 250°C for 15 min to 2 hrs, to form a CH array pattern in the block copolymer film by directed self-assembled chemoepitaxy, vie) etching said substrate using said CH array pattern in the film formed by directed selfassembled chemoepitaxy as mask with a plasma to form a CH array pattern in the substrate.

262. The use of the block copolymer of any one of claims 1 to 186 in the manufacture of integrated circuits.

263. The use of the composition of any one of claims 247 to 254 in the manufacture of integrated circuits.

264. The use of the process of any one of claims 255 to 261 in the manufacture of integrated circuits.

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