Block copolymer formulations for improving self-assembly topography in directed self-assembly applications

Abstract

A composition comprising components a), b) and c) wherein a) is a block copolymer component or a blend of at least two block copolymers, b) is at least one low Tg oligomer polystyrene additive, and c) is an organic spin casting organic solvent. Component b) (if more than one, alone) has a Tg in the range of about 68.0 DEG C to about 90.0 DEG C, a Mw in the range of about 2,500 g / mol to about 8,000 g / mol, a polydispersity in the range of about 1.20 to about 1.80, and is further selected from the group consisting of styrene homopolymers prepared by free radical polymerization, styrene random copolymers prepared by free radical polymerization, styrene random copolymers prepared by free radical polymerization, styrene random copolymers prepared by free radical polymerization, styrene random copolymers prepared by free radical polymerization, styrene random copolymers prepared by free radical polymerization, and styrene random copolymers prepared by free radical polymerization. The repeating units consist solely of styrene repeating units and wherein at least two styrene repeating units are present, and a mixture of the styrene homopolymer and at least one styrene random copolymer. A DSA treatment process using the composition is also described.

Description

Field of the Invention

[0001] The disclosed subject matter relates to a method for manufacturing a DSAIC containing a low T g Block copolymer compositions of additives. Background Art

[0002] Self-assembly of block copolymers is a method that can be used to generate increasingly smaller patterned features for manufacturing microelectronic devices in which critical dimensions (CDs) of nanoscale features can be achieved. Self-assembly methods are desirable for expanding the resolution capabilities of microlithography techniques for arrays of repeating features such as contact holes or pillars. In conventional photolithography methods, ultraviolet (UV) radiation can be used to expose a photoresist layer coated on a substrate or layered substrate through a mask. Positive or negative photoresists are available, and these can also contain refractory elements such as silicon to enable dry development for conventional integrated circuit (IC) plasma processing. In positive photoresists, UV radiation transmitted through the mask causes a photochemical reaction in the photoresist, allowing the exposed areas to be removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation transmitted through the mask causes the exposed areas to become less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features such as gates, vias, or interconnects are then etched into the substrate or layered substrate, and the remaining photoresist is removed. When conventional photolithography exposure processes are used, the size of integrated circuit features is limited. Due to limitations associated with aberrations, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture, further reductions in pattern size are difficult to achieve using radiation exposure. The demand for large-scale integration has led to a continuous reduction in circuit size and features in devices. In the past, the ultimate resolution of features depended on the wavelength of light used to expose the photoresist, which has its own limitations. Directed (also known as guided) self-assembly techniques, such as graphoepitaxy and chemical epitaxy using block copolymer imaging, which employ patterned areas on a substrate, are highly desirable techniques for enhancing resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography or to achieve even higher resolution and CD control in methods employing EUV, electron beam, deep UV, or immersion lithography. Directed self-assembling block copolymers comprise blocks of etch-resistant copolymer units and blocks of highly etchable copolymer units that, when coated, aligned, and etched on a substrate, produce areas of very high density patterns.

[0003] For the directional (guiding) or non-guiding self-assembly of the block copolymer film on patterned or non-patterned substrate area respectively, the self-assembly process of the block polymer layer typically occurs during the annealing of the film covering the neutral layer. The neutral layer on the semiconductor substrate can be a non-patterned neutral layer, or in chemical epitaxy or graphoepitaxy, the neutral layer can contain graphoepitaxy or chemical epitaxy guiding features (formed by above-mentioned UV lithography) respectively. During the annealing of the block copolymer film, the following neutral layer guides the nanophase separation of the block copolymer domain. An example is to form a phase-separated domain, which is a lamella or column perpendicular to the neutral layer surface below. The block copolymer domains of these nanophase separations form pre-patterns (for example, lines and intervals L / S), which can be transferred to substrates by etching processes (for example, plasma etching). In graphoepitaxy or chemical epitaxy, these guiding features can indicate both pattern rectification and pattern multiplication. In the case of a non-patterned neutral layer, this produces a repeating array such as L / S or CH. For example, in conventional block copolymers such as poly(styrene-b-methyl methacrylate) (P(Sb-MMA)), where the two 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 grafted or cross-linked at the polymer-substrate interface.

[0004] In the graphoepitaxy directed self-assembly method, block copolymers are self-organized around a substrate pre-patterned with conventional photolithography (ultraviolet, deep UV, electron beam, extreme UV (EUV) exposure source) to form repeating morphological features, such as line / space (L / S) or contact hole (CH) patterns. In the example of L / S directed self-assembly arrays, block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different spacings in the grooves between the pre-patterned lines, thereby enhancing pattern resolution by subdividing the intervals in the grooves between the morphological lines into finer patterns. For example, diblock copolymers or triblock copolymers, which can microphase separate and include carbon-rich blocks (such as styrene or containing certain other elements such as Si, Ge, Ti) and highly plasma-etchable or removable blocks that resist plasma etching, can provide high-resolution pattern clarity. The example of highly etchable blocks can include monomers that are rich in oxygen and do not contain refractory elements and can form highly etchable blocks, such as methyl methacrylate. The plasma etching gas used in the etching method for delimiting the self-assembly pattern is typically that used in the method for manufacturing integrated circuits (ICs). In this way, very fine patterns than those delimited by conventional photolithography can be created in typical IC substrates, thereby realizing pattern multiplication. Similarly, features such as contact holes can be made denser by using graphoepitaxy, in which suitable block copolymers are arranged by self-directed self-assembly around the array of contact holes or posts delimited by conventional photolithography, thereby forming a denser array of the region of etchable and etch-resistant domains, which produces a denser array of contact holes when etching. Therefore, graphoepitaxy has the potential to provide both pattern rectification and pattern multiplication.

[0005] In chemical epitaxy or pinning chemical epitaxy, the self-assembly of block copolymers is formed on the surface of the region where its guiding feature is different chemical affinities, without or without significant morphology (also known as non-guided morphology), which means a directed self-assembly process. For example, conventional photolithography (UV, deep UV, electron beam, EUV) can be used to pattern the surface of substrate to create different chemical affinities in line and space (L / S) patterns, where the exposed areas where its surface chemistry is changed by radiation alternate with unexposed areas, and no chemical changes are shown. These areas do not present morphological differences, but do have surface chemistry differences or pinning to directed self-assemble block copolymer segments. Specifically, the directed self-assembly of the block copolymers whose block segments contain anti-etching (such as styrene repeating units) and fast etching repeating units (such as methyl methacrylate repeating units) will allow for accurate arrangement of anti-etching block segments and highly etchable block segments on the pattern. This technology allows for accurate arrangement of these block copolymers, and after plasma or wet etching processing, pattern is subsequently patterned into substrate. Chemical epitaxy has the advantage that it can be fine-tuned by varying the chemical differential to help improve line edge roughness and CD control, thereby allowing pattern rectification. Other types of patterns such as repeating contact hole (CH) arrays can also be pattern rectified using chemical epitaxy.

[0006] A neutral layer is a layer on the surface of a substrate or treated substrate that has no affinity for any of the block segments of the block copolymer employed in directed self-assembly. In graphoepitaxy methods for directed self-assembly of block copolymers, neutral layers are useful because they allow for proper placement or orientation of the block polymer segments for directed self-assembly, which results in proper placement of etch-resistant block polymer segments and highly etchable block polymer segments relative to the substrate. For example, in a surface containing line and space features already defined by conventional radiation lithography, the neutral layer allows the block segments to be oriented so that the block segments are oriented perpendicular to the surface of the substrate, an orientation that 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 lines defined by conventional photolithography. If the substrate interacts too strongly with one of the block segments, it will be caused to lie flat on the surface to maximize the surface contact between the segment and the substrate; such a surface will disrupt the desired vertical alignment, which can be used to achieve pattern rectification or pattern multiplication based on features created by conventional photolithography. Modifying selected small areas or pinning the substrate so that it interacts strongly with one block of the block copolymer and leaving the rest of the surface coated with a neutral layer can be used to force the domains of the block copolymer to align in the desired direction and is the basis of pinned chemical epitaxy or graphoepitaxy for pattern multiplication.

[0007] Although self-assembly using polystyrene-b-polymethyl methacrylate (PS-b-PMMA) is widely used as a next-generation patterning material in photolithography, where the nanophase separation assembly method generates well-aligned domain arrays, this is accompanied by a large number of defect formations if the film thickness exceeds 50 nm. These defects are significant in contact holes and line / space multiplication processes and need to be significantly reduced to improve the device yield in any commercially viable IC-manufacturing using directed self-assembly. One of the origins of defects is insufficient diffusion of block segments, which generates defects such as dislocations, bridging, networks, and line or column collapse. Therefore, new materials and methods are needed that can achieve self-assembly of block copolymer domains with a greatly reduced number of these defects even in films with a thickness exceeding 50 nm. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 SEM images of annealed and plasma-etched block copolymer (BCP) formulations containing the free-radically polymerized h-PS oligomer additives 1, 2, 3, 5, 6, or 7 of the present invention taken at 2 and 4 or 50 FOV show good defect-free contact hole (CH) self-assembly.

[0009] Figure 2 SEM images of annealed and plasma-etched block copolymer (BCP) formulations containing comparative free-radically polymerized h-PS oligomer additive 4 or anionically polymerized h-PS oligomer additives 1 or 2 taken at 2 and 4 FOVs show poor contact hole (CH) self-assembly with defects. SUMMARY OF THE INVENTION

[0011] We have discovered a number of low T g Low polystyrene additives, which can be used as additives with block copolymers (BCPs) to form novel block copolymer compositions that can be used to adjust the low T g wt.% of styrene additives showed improved performance. Surprisingly, when formulated with BCP, low T g The styrene additive showed very poor morphology during self-assembly annealing. In contrast and surprisingly, when used as a BCP additive, low T g Oligostyrene additives are used in these M w This interesting phenomenon suggests that the BCP formulation dynamics are unexpectedly strongly influenced by the mobility of smaller-sized and chemically random-structured oligomeric additives by strongly promoting better dynamics of the BCP formulation.

[0012] In particular, the present invention relates to a composition comprising components a), b) and c), wherein a) is a block copolymer component or a blend of at least two block copolymers;

[0013] b) is at least one low T g Oligomeric polystyrene additives, wherein each additive individually has a T ranging from about 68.0°C to about 90.0°C g and having an M ranging from about 2,500 g / mole to about 8,000 g / mole w , having a polydispersity of 1.20 to about 1.80, and further wherein the styrene additive is selected from the group consisting of: at least one styrene homopolymer prepared by free radical polymerization, at least one styrene random copolymer prepared by free radical polymerization, the repeating units of which consist solely of styrene repeating units and wherein at least two styrene repeating units are present, a mixture of at least one said styrene homopolymer and at least one said styrene random copolymer; and c) is an organic spin casting solvent.

[0014] Another aspect of the present invention is a method of using the above-described composition in a self-assembly process and subsequently pattern-transferring the self-assembled pattern into a substrate. Detailed Description of the Invention

[0016] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not limitations on the claimed subject matter. In this application, unless otherwise specifically stated, the use of the singular includes the plural, the word "a / an" means "at least one", and the use of "or" means "and / or". In addition, the use of the term "including" and other forms such as "includes" and "included" is not restrictive. In addition, unless otherwise specifically stated, terms such as "element" or "component" include elements and components comprising one unit and elements or components comprising more than one unit. As used herein, unless otherwise stated, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0017] The term C-1 to C-4 alkyl includes methyl and C-2 to C-4 straight chain alkyl and C-3 to C-4 branched chain alkyl moieties, such as the following: 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 C-1 to C-8 alkyl includes methyl, C-2 to C-8 straight chain, C-3 to C-8 branched chain alkyl, C-4 to C-8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) or C-5-C-8 alkylenecycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0018] The term C-2 to C-5 alkylene includes C-2 to C-5 straight chain alkylene moieties (e.g., ethylene, propylene, etc.) and C-3 to C-5 branched chain alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0019] Diblock and triblock copolymers of styrene and acrylic acid moieties useful as components in the inventive compositions described herein can be prepared by a variety of methods, such as anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, living radical polymerization, and the like (Macromolecules 2019, 52, 2987-2994; Macromol. Rapid Commun. 2018, 39, 1800479; A. Deiter Shluter et al. Synthesis of Polymers, 2014, Vol. 1, p. 315; Encyclopedia of Polymer Science and Technology, 2014, Vol. 7, p. 625.)

[0020] The random copolymer poly(styrene-co-methyl methacrylate) is abbreviated as "P(S-co-MMA)", and the oligomeric form of this material is abbreviated as oligo(S-co-MMA). Similarly, the block copolymer poly(styrene-block-methyl methacrylate) is abbreviated as P(Sb-MMA).

[0021] The term "g / mole" is an abbreviation for grams per mole.

[0022] The term “CH” is an abbreviation for contact hole lithographic feature, and the term “L / S” is an abbreviation for line and space lithographic feature.

[0023] In the following description, the term "Synth." is an abbreviation of synthesis; the term "Comp." is an abbreviation of comparison; and the term "Ex." is an abbreviation of example.

[0024] As used herein, the terms oligomer, oligo, and oligomeric polymer refer to low T g Additive and refers to low molecular weight polymers whose molecular weight range is specific to the type of additive as indicated herein.

[0025] As used herein, the term acrylic includes repeating units derived from acrylate derivatives, for example, repeating units derived from acrylate derivatives having the following structure, wherein the alkyl moiety can be a C-1 to C-8 alkyl, and Xacryl is H or a C-1 to C-4 alkyl:

[0026]

[0027] The term styrenic as used herein includes repeating units derived from styrenic derivatives, for example, repeating units derived from styrenic derivatives having the following structure, wherein the Xsty moiety is H or a C-1 to C-4 alkyl group, and the Rsty moiety is H or a C-1 to C-8 moiety:

[0028]

[0029] Composition

[0030] One aspect of the present invention is a composition comprising components a), b) and c), wherein,

[0031] a) is a block copolymer component or a blend of at least two block copolymers.

[0032] b) is at least one low T g Oligomeric polystyrene additives, wherein each additive individually has a T ranging from about 68.0°C to about 90.0°C g and having an M ranging from about 2,500 g / mole to about 8,000 g / mole w , having a polydispersity of from 1.20 to about 1.80, and further wherein the styrene additive is selected from the group consisting of,

[0033] at least one styrene homopolymer prepared by free radical polymerization,

[0034] At least one styrene random copolymer prepared by free-radical polymerization, the repeating units of which consist exclusively of styrene repeating units and in which at least two styrene repeating units are present, and mixtures of at least one such styrene homopolymer and at least one such styrene random copolymer.

[0035] c) is an organic spin-casting solvent.

[0036] In one aspect of the composition of the present invention described above, it consists essentially of components a), b), and c). In one aspect of this embodiment, the term "consisting essentially of" requires that other components may be present that do not affect the properties of the material and are only present in a total concentration of about 10 wt.% of the composition. In another aspect of this embodiment, these other components are only present in a total concentration of about 5 wt.% of the composition. In another aspect of this embodiment, these other components are only present in a total concentration of about 1 wt.%. In another aspect of this embodiment, these other components are present in a total concentration of about 0.5 wt.%.

[0037] In another aspect of the above composition of the present invention, it consists of components a), b) and c).

[0038] 1) Component b) Low T g Oligomeric polystyrene additives

[0039] In another aspect of the above composition of the present invention, it is wherein each component b) additive individually has a T in the range of about 68.0°C to about 90.0°C. gIn another aspect of this embodiment, the range is from about 68.5°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.6°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.7°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.7°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.8°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.8°C to about 90.0°C. In another aspect of this embodiment, the range is from about 68.9°C to about 90.0°C. In another aspect of this embodiment, the range is from about 69.0°C to about 90.0°C. In another aspect of this embodiment, the range is from about 69.1°C to about 90.0°C. In another aspect of this embodiment, the range is from about 69.2°C to about 90.0°C. In another aspect of this embodiment, the range is from about 69.3°C to about 90.0°C. In another aspect of this embodiment, the range is from about 69.3°C to about 89.9°C. In another aspect of this embodiment, the range is from about 69.3°C to about 89.8°C. In another aspect of this embodiment, the range is from about 69.0°C to about 89.7°C. In another aspect of this embodiment, the range is from about 69.3°C to about 89.7°C.

[0040] In another aspect of this embodiment, it ranges from about 68.0°C to about 90.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 89.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 88.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 87.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 86.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 85.0°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 84.9°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 84.8°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 84.7°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 84.6°C. In another aspect of this embodiment, it ranges from about 68.0°C to about 84.5°C. In another aspect of this embodiment, the range is from about 68.0°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.1°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.2°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.3°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.3°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.4°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.5°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.6°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.7°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.8°C to about 84.4°C. In another aspect of this embodiment, the range is from about 68.9°C to about 84.4°C. In another aspect of this embodiment, the range is from about 69.0° C. to about 84.4° C. In another aspect of this embodiment, the range is from about 69.1° C. to about 84.4° C. In another aspect of this embodiment, the range is from about 69.2° C. to about 84.4° C. In another aspect of this embodiment, the range is from about 69.3° C. to about 84.4° C.

[0041] In another aspect of the above-described composition of the present invention, it is a composition wherein each component b) additive individually has a polydispersity ranging from about 1.30 to about 1.80. In another aspect of this embodiment, it ranges from about 1.35 to about 1.80. In another aspect of this embodiment, it ranges from about 1.36 to about 1.80. In another aspect of this embodiment, it ranges from about 1.37 to about 1.80. In another aspect of this embodiment, it ranges from about 1.38 to about 1.80. In another aspect of this embodiment, it ranges from about 1.39 to about 1.80. In another aspect of this embodiment, it ranges from about 1.40 to about 1.80. In another aspect of this embodiment, it ranges from about 1.40 to about 1.75. In another aspect of this embodiment, it ranges from about 1.40 to about 1.74. In another aspect of this embodiment, it ranges from about 1.40 to about 1.73. In another aspect of this embodiment, it ranges from about 1.40 to about 1.72. In another aspect of this embodiment, it ranges from about 1.40 to about 1.71. In another aspect of this embodiment, it ranges from about 1.40 to about 1.71. In another aspect of this embodiment, it ranges from about 1.40 to about 1.70. In another aspect of this embodiment, it ranges from about 1.40 to about 1.69.

[0042] In another aspect of the above composition of the present invention, wherein each of said at least one low T g The oligomeric polystyrene additives individually have an M ranging from about 2,700 g / mole to about 8,000 g / mole. w. In another aspect of this embodiment, it ranges from about 2,800 g / mole to about 8,000 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,900 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,800 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,700 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,600 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,500 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,400 g / mole. In another aspect of this embodiment, it ranges from about 2,900 g / mole to about 7,300 g / mole. In another aspect of this embodiment, the range is from about 2,900 g / mole to about 7,200 g / mole. In another aspect of this embodiment, the range is from about 2,900 g / mole to about 7,100 g / mole. In another aspect of this embodiment, the range is from about 2,900 g / mole to about 7,000 g / mole. In another aspect of this embodiment, the range is from about 2,900 g / mole to about 6,900 g / mole. In another aspect of this embodiment, the range is from about 2,900 g / mole to about 6,800 g / mole.

[0043] In another aspect of the composition, the component b) additive is at least one of the styrene homopolymers or the styrene random copolymers prepared by free radical polymerization. In one aspect of this embodiment, it consists of one of the styrene homopolymers prepared by free radical polymerization.

[0044] In another aspect of the compositions described herein, the component b) additive is at least one of the styrene homopolymers described herein and further has structure (A) whose repeating units consist of repeating units having structure (I). In structure (I), n1 is the number of repeating units and specifies that this is a repeating unit, R A1 、R A2 、R A3 、R A4 、R A5 independently selected from H or C-1 to C-8 alkyl, R m1is H or methyl, and the styrene homopolymer has two terminal groups as shown in structure (A), one of which is H and the other is a methyl moiety substituted with Rr, Rr1 and Rr2, wherein Rr1 is C-1 to C-8 alkyl, Rr2 is selected from C-1 to C-8 alkyl, Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl or aryl moiety. In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 、R A5 In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 、R A5 is H. In another aspect of this embodiment, Rm1 is H. In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 、R A5 is H and R m1 is H. In another aspect of this embodiment, Rr is a cyano moiety (-CN). In another aspect of this embodiment, the component b) additive consists of one of the styrene homopolymers of structure (A). In another aspect of this embodiment, the component b) additive is at least two different styrene homopolymers of structure (A).

[0045]

[0046] In another aspect of the composition, the component b) additive is at least two of the styrene homopolymers or at least two of the styrene random copolymers, both prepared by free radical polymerization. In one aspect of this embodiment, it is two of the styrene homopolymers prepared by free radical polymerization.

[0047] In another aspect of the composition, the component b) additive is at least one of the styrene random copolymers having structure (B), wherein its repeating units consist of two different repeating units of structures (II) and (III), wherein n2 and n3 are the number of these repeating units and specify that these are repeating units, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and RB10 are independently selected from H or C-1 to C-8 alkyl, R m2 、R m3 independently selected from H or methyl; and the styrene random copolymer has two end groups as shown in structure (B), one of which is H and the other is a methyl moiety substituted by Rr3, Rr4 and Rr5, wherein Rr4 is C-1 to C-8 alkyl, Rr5 is selected from C-1 to C-8 alkyl, Rr3 is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl or aryl moiety. In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 , and R B6 、R B7 、R B8 、R B9 and R B10 In one aspect of this embodiment, at least one of R is C-1 to C-4 alkyl, which is methyl. In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 Both H and R B6 、R B7 、R B8 、R B9 and R B10 In one aspect of this embodiment, at least one of R is C-1 to C-4 alkyl; in one aspect of this embodiment, it is methyl. In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 are H. In another aspect of these embodiments, R m2 and R m3are all H. In another aspect of this embodiment, Rr3 is a cyano moiety (-CN). In another aspect of this embodiment, the component b) additive consists of one of the styrene random copolymers of structure (B). In another aspect of this embodiment, the component b) consists of at least two different of the styrene random copolymers of structure (B).

[0048]

[0049] In another aspect of the composition, the component b) additive is a mixture of at least one of the styrene homopolymers and at least one of the styrene random copolymers prepared by free radical polymerization. In another aspect of this embodiment, it consists of one of the styrene homopolymers and one of the random copolymers prepared by free radical polymerization.

[0050] In another aspect of the composition, the component b) additive is a mixture of at least one styrene homopolymer of structure (A) and at least one styrene random copolymer of structure (B). In this aspect, the styrene homopolymer has structure (A) having repeating units of structure (I) and two end groups as shown in structure (A). In the repeating units of structure (I), n1 is the number of repeating units and specifies that this is a repeating unit, R A1 、R A2 、R A3 、R A4 、R A5 independently selected from H or C-1 to C-8 alkyl, R m1 is H or methyl. In addition, as shown in structure (A), one of the terminal groups is H and the other is a methyl moiety substituted with Rr, Rr1 and Rr2, wherein Rr1 is C-1 to C-8 alkyl, Rr2 is selected from C-1 to C-8 alkyl, and Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl or aryl moiety. In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 、R A5 In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 and R A5 In another aspect of this embodiment, Rm1 is H. In another aspect of this embodiment, R A1 、R A2 、R A3 、R A4 、RA5 is H and R m1 is H. In another aspect of this embodiment, Rr is a cyano moiety (—CN).

[0051] Furthermore, in this embodiment of the present invention, wherein the component b) additive is a mixture of at least one styrene homopolymer of structure (A) and at least one styrene random copolymer of structure (B), in which the repeating units of the styrene random copolymer of structure (B) consist of two repeating units of structures (II) and (III) and the styrene random copolymer has two end groups, wherein, in structures (II) and (III), n2 and n3 are the number of these repeating units, respectively, and specify that these are repeating units, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 are independently selected from H or C-1 to C-8 alkyl, R m2 、R m3 Independently selected from H or methyl. These two terminal groups are shown in structure (B), where one is H and the other is a methyl moiety substituted by Rr3, Rr4, and Rr5, where Rr4 is C-1 to C-8 alkyl, Rr5 is selected from C-1 to C-8 alkyl, Rr3 is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C-1 to C-8 alkyl or aryl moiety. In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 In another aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 Both H and R B6 、R B7 、R B8 、R B9 and R B10 In one aspect of this embodiment, at least one of R is C-1 to C-4 alkyl; in one aspect of this embodiment, it is methyl. In another aspect of this embodiment, RB1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 are H. In another aspect of these embodiments, R m2 and R m3 Both are H. In another aspect of this embodiment, Rr3 is a cyano moiety (-CN).

[0052]

[0053] 2) Component a) Block copolymer component

[0054] In another aspect of the composition, component a) is selected from a single triblock copolymer and a blend of at least two different triblock copolymers, or a single diblock copolymer and a blend of at least two different diblock copolymers.

[0055] In another aspect of the composition, component a) is an ABA triblock copolymer component selected from the group consisting of an ABA triblock copolymer a-1t), an ABA triblock copolymer a-2t), and a blend of two ABA triblock copolymers a-1t) and ABA triblock copolymers a-2t) of different compositions, wherein a-1t) is an ABA triblock copolymer comprising an intermediate B) styrene block segment having repeating units of styrene structure (I') and two terminal acrylic block A) segments of equal length having structure (II'), wherein R1 and R3 are independently selected from H and C-1 to C-4 alkyl, R2 is H or C-1 to C-8 alkyl, and R4 is C-1 to C-8 alkyl, and based on the total moles of repeating units of structures (I') and (II'), the mole % value of the styrene repeating units of structure (I') is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating units of structure (II') is from about 20 mole % to about 60 mole %, wherein the individual mole % values ​​of the repeating units of structures (I') and (II') are selected from their respective ranges to add up to 100 mole % of the total moles of repeating units of structures (I') and (II'), and the triblock copolymer a-it) has a polydispersity of from about 1.0 to about 1.1 and has an M of from about 70,000 g / mole to about 350,000 g / mole. n .

[0056]

[0057] Furthermore, in this aspect, the ABA triblock copolymer a-2t) is an ABA triblock copolymer comprising a middle B) block segment having repeating units of a styrene structure (Ia) and two end block A) segments of equal length having an acrylic structure (IIa), wherein R 1a and R 3a are independently selected from H and C-1 to C-4 alkyl, R 2a is H or C-1 to C-8 alkyl, R 4a It is a C-1 to C-8 alkyl group.

[0058] Furthermore, also in this aspect, the mole % value of the styrene repeating units of structure (Ia) is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating units of structure (IIa) is from about 20 mole % to about 60 mole %, based on the total moles of repeating units of structures (Ia) and (IIa), and

[0059] wherein the individual mole % values ​​of the repeating units of structures (Ia) and (IIa) are selected from their respective ranges to add up to a total mole of 100 mole % of the repeating units of structures (Ia) and (IIa). Finally, in this aspect, the triblock copolymer a-2t) has a polydispersity of from about 1.0 to about 1.1 and also has an M of from about 70,000 g / mole to about 350,000 g / mole. n .

[0060]

[0061] In another aspect of the composition, wherein the component a) is an ABA triblock copolymer component selected from the group consisting of ABA triblock copolymers a-1t), ABA triblock copolymers a-2t), and blends of ABA triblock copolymers a-1t) and ABA triblock copolymers a-2t), more specifically, R1, R 1a , R2 and R 2a is H and R3, R 3a , R4 and R 4a In another aspect of the composition, wherein the component a) is a triblock copolymer as described above, in one embodiment, the component a) is selected from the group consisting of a triblock copolymer of structure (ABA-1), a triblock copolymer of structure (ABA-2), and a mixture of these two block copolymers, wherein mt, mta, nt, and nta are the number of repeating units, and R 1s 、R 1sa 、R 2s and R 2sa independently selected from hydrogen, C-1 to C-8 alkyl, -N(R 3s )2、-OR 4s and Si(R 5s)3, where R 3s 、R 4s and R 5s R1 and R3 are independently selected from C-1 to C-4 alkyl, and R2 is H or C-1 to C-8 alkyl, and R4 is C-1 to C-8 alkyl. In addition, in this embodiment, based on the total moles of both styrene and acrylic acid repeating units in Structure (ABA-1), the mole % value of styrene repeating units is from about 40 mole % to about 80 mole %, and the mole % value of acrylic acid is from about 20 mole % to about 60 mole %, wherein the individual mole % values ​​of the repeating units of Structures (I') and (II') are selected from their respective ranges to add up to 100 mole % of the total moles of the repeating units of Structures (I') and (II'), and the triblock copolymer of Structure (ABA-1) has a polydispersity of from about 1.0 to about 1.1 and has an M of from about 70,000 g / mole to about 350,000 g / mole. n , and the triblock copolymer of structure (ABA-2) has a polydispersity of about 1.0 to about 1.1 and also has an M of about 70,000 g / mole to about 350,000 g / mole n In another aspect of this embodiment, R1, R 1a , R2, R 2a 、R 1s 、R 1sa 、R 2s 、R 2sa is H and R3, R 3a , R4 and R 4a is methyl. In one aspect of this embodiment, component a) consists solely of the ABA triblock copolymer of structure (ABA-1); in another aspect of this embodiment, component a) consists solely of the ABA triblock copolymer of structure (ABA-2); and in another aspect of this embodiment, component a) consists of a mixture of the triblock copolymers of structures (ABA-1) and (ABA-2). In another aspect of this embodiment of the blend of a-1t) and a-2t), it is a blend and component wherein the total mole % of styrene repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole % and wherein the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %.

[0062]

[0063] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2).

[0064] In this aspect, a-1) is a diblock copolymer comprising block A) of styrene repeating units having a styrene structure (I') and block B) of an acrylic structure (II'), wherein R1 and R3 are independently selected from H and C-1 to C-4 alkyl, R2 is H or C-1 to C-8 alkyl, and R4 is C-1 to C-8 alkyl. In addition, in this aspect, based on the total moles of repeating units of structures (I') and (II'), the mole % value of repeating units of structure (I') is from about 40 mole % to about 80 mole %, and the mole % value of repeating units of structure (II') is from about 20 mole % to about 60 mole %. In addition, in this aspect, the individual mole % values ​​of repeating units of structures (I') and (II') are selected from their respective ranges to add up to 100 mole % of the total moles of repeating units of structures (I') and (II'). Furthermore, in this aspect, the diblock copolymer a-1) has a polydispersity of from about 1.0 to about 1.1 and an M of from about 50,000 g / mole to about 150,000 g / mole. n .

[0065]

[0066] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), a-2) is a diblock copolymer comprising blocks Aa) having repeating units of styrene structure (Ia) and blocks Ba) having repeating units of acrylic acid structure (IIa), wherein R 1a and R 3a are independently selected from H or C-1 to C-4 alkyl, R 2a is H or C-1 to C-8 alkyl, R 4a Is a C-1 to C-8 alkyl group. In addition, in this aspect, based on the total moles of the repeating units of structures (Ia) and (IIa), the mol% value of the repeating units of structure (Ia) is about 40 mol% to about 80 mol%, and the mol% value of the repeating units of structure (IIa) is about 20 mol% to about 60 mol%. In addition, also in this aspect, the individual mol% values ​​of the repeating units of structures (Ia) and (IIa) are selected from their respective ranges to add up to a total mole of 100 mol% of the repeating units of structures (Ia) and (IIa). In addition, also in this aspect, the diblock copolymer a-2) has a polydispersity of about 1.0 to about 1.1 and also has an M of about 30,000 g / mole to about 90,000 g / mole. n .

[0067]

[0068] In another aspect of the composition, wherein the component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), R1, R 1a , R2 and R 2a is H and R3, R 3a , R4 and R 4a It's methyl.

[0069] In another aspect of the embodiment, wherein component a) is a diblock copolymer a-1) and a-2), these have structure (IS) and structure (ISa), respectively, wherein R 1s 、R 1sa 、R 2s and R 2sa independently selected from hydrogen, C-1 to C-8 alkyl, -N(R 3s )2、-OR 4s and Si(R 5s )3, where R 3s 、R 4s and R 5s In one aspect of this embodiment, R 1s 、R 2s 、R 1sa and R 2sa It's hydrogen.

[0070]

[0071] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1) and blends of a-1) and a-2). In this embodiment, diblock copolymer component a-1) and / or diblock copolymer component a-2) independently have a polydispersity ranging from 1.00 to about 1.03. In another aspect of this embodiment, diblock copolymer component a-1) has an M of about 93,000 g / mole to about 105,300 g / mole. n .

[0072] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1) and blends of a-1) and a-2), the mole % value for repeating units of structure (I') for diblock copolymer component a-1) is from about 40 mole % to about 60 mole %, and the mole % value for repeating units of structure (II') is from about 40 mole % to about 60 mole %.

[0073] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1) and blends of a-1) and a-2), the mole % value for repeating units of structure (I') for diblock copolymer component a-1) is from about 60 mole % to about 75 mole %, and the mole % value for repeating units of structure (II') is from about 25 mole % to about 40 mole %.

[0074] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1) and blends of a-1) and a-2), the mole % value for repeating units of structure (I') for diblock copolymer component a-1) is from about 40 mole % to about 80 mole %, and the mole % value for repeating units of structure (II') is from about 20 mole % to about 60 mole %.

[0075] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1) and blends of a-1) and a-2), the mole % value for repeating units of structure (I') for diblock copolymer component a-1) is from about 40 mole % to about 60 mole %, and the mole % value for repeating units of structure (II') is from about 40 mole % to about 60 mole %.

[0076] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-2) and a blend of a-1) and a-2), the two different diblock copolymers independently having a polydispersity ranging from 1.00 to about 1.03.

[0077] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-2) and blends of a-1) and a-2), the diblock copolymer component a-2) having an M of about 40,800 g / mole to about 61,200 g / mole. n .

[0078] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % value of repeating units of structures (I') and (Ia) is from about 40 mole % to about 60 mole % for a single block copolymer a-1) or a-2) or in a blend of a-1) and a-2), and the total mole % value of repeating units of structures (II') and (IIa) is from about 40 mole % to about 60 mole %.

[0079] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % value of repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole % for a single block copolymer a-1) or a-2) or in a blend of a-1) and a-2), and the total mole % value of repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %.

[0080] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), component a) is a blend of a-1) and a-2).

[0081] In another aspect of the composition, wherein the component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the component a) is a-1) or a-2).

[0082] In another aspect of the composition, component a) comprises from about 0.5 wt.% to about 2.0 wt.% of the total composition.

[0083] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), component a) comprises from about 0.5 wt.% to about 2.0 wt.% of the total composition.

[0084] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % of styrene repeating units of structures (I') and (Ia) is from about 40 mole % to about 60 mole %, and the total mole % of acrylic repeating units of structures (II) and (IIa) is from about 40 mole % to about 60 mole %.

[0085] In another aspect of the composition, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % of styrene repeating units of structures (I') and (Ia) is from about 65 mole % to about 70 mole %, and further wherein the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 30 mole % to about 35 mole %.

[0086] In another aspect of the composition, wherein the component a) is selected from the group consisting of a triblock copolymer component a-1t), a triblock copolymer a-2t), and a blend of a-1t) and a-2t), the total mole % of styrene repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole % and the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %.

[0087] In another aspect of the composition, wherein the component a) is selected from the group consisting of a triblock copolymer component a-1t), a triblock copolymer a-2t), and a blend of a-1t) and a-2t), the total mole % of styrene repeating units of structures (I') and (Ia) being from about 40 mole % to about 60 mole %, and further wherein the total mole % of acrylic repeating units of structures (II') and (IIa) being from about 40 mole % to about 60 mole %, and component b) an additive, the low T g The oligomeric polystyrene additive is the at least one styrene homopolymer prepared by free radical polymerization.

[0088] In any one of the above embodiments, component b) accounts for about 0.05wt.% to about 2.0wt.% of the total composition (including solvent). In another aspect of this embodiment of component b) additive, this component can account for about 0.05wt.% to about 0.5wt.% of the total weight of the composition (including the spin-cast organic solvent). In another aspect of this embodiment, it ranges from about 0.08wt.% to about 0.4wt.%. In another aspect of this embodiment, it ranges from about 0.1wt.% to about 0.4wt.%. In another aspect of this embodiment, it ranges from about 0.15wt.% to about 0.4wt.%. In yet another aspect of this embodiment, it ranges from about 0.2wt.% to about 0.3wt.%.

[0089] 3) Component c) Spin-cast organic solvent

[0090] For component c), spin-casting organic solvents, suitable solvents for dissolving the above-mentioned composition of the present invention include glycol ether derivatives 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; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylic acid esters such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylic acid esters of dibasic acids such as diethyl oxalate and diethyl malonate; dicarboxylic acid esters of glycols such as ethylene glycol diacetate and propylene glycol dimethyl ether; diol diacetates; and hydroxycarboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl-3-hydroxypropionate; ketoesters such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketoether derivatives such as diacetone alcohol methyl ether; ketoalcohol derivatives such as acetol or diacetone alcohol; ketals or acetals such as 1,3 dioxolane and diethoxypropane; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0091] In addition, the compositions of the present invention described above may further comprise an additive selected from the group consisting of: surfactants, inorganic-containing polymers; additives including small molecules, inorganic-containing molecules, surfactants, photoacid generators, thermal acid generators, quenchers, hardeners, cross-linkers, chain extenders, and the like; and a combination comprising at least one of the foregoing, wherein one or more of the additional components and / or additives are co-assembled with the block copolymer to form a block copolymer assembly.

[0092] method

[0093] Another aspect of the present invention is a method comprising the steps of:

[0094] i) forming a coating of a neutral layer on a substrate,

[0095] ii) applying a composition of any of the compositions of the present invention described herein onto the neutral layer to form a film

[0096] iii) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and

[0097] iv) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

[0098] Another aspect of the present invention is a method for forming a line and space array comprising the steps of:

[0099] ia) forming a coating of a neutral layer on a substrate,

[0100] iia) applying a composition onto the neutral layer to form a film, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % of styrene repeating units of structures (I') and (Ia) of which is from about 40 mole % to about 60 mole %, and the total mole % of acrylic repeating units of structures (II') and (IIa) of which is from about 40 mole % to about 60 mole %.

[0101] iiia) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and

[0102] iva) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

[0103] Another aspect of the present invention is a method for forming a contact hole array, comprising the steps of:

[0104] ib) forming a coating of a neutral layer on a substrate,

[0105] iib) applying a composition onto the neutral layer to form a film, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), the total mole % of styrene repeating units of structures (I') and (Ia) being from about 60 mole % to about 75 mole %, and further wherein the total mole % of acrylic repeating units of structures (II') and (IIa) being from about 25 mole % to about 40 mole %,

[0106] iiib) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and

[0107] ivb) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

[0108] Another aspect of the present invention is a method for forming a line and space array comprising the steps of:

[0109] ic) forming a coating of a neutral layer on a substrate,

[0110] iic) applying a composition onto the neutral layer to form a film, wherein component a) is selected from the group consisting of triblock copolymer component a-1t), triblock copolymer a-2t), and blends of a-1t) and a-2t), the total mole % of styrene repeating units of structures (I') and (Ia) being from about 60 mole % to about 75 mole % and the total mole % of acrylic repeating units of structures (II') and (IIa) being from about 25 mole % to about 40 mole %,

[0111] iiic) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and

[0112] ivc) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

[0113] Another aspect of the present invention is a method for forming a contact hole array, comprising the steps of:

[0114] id) forming a coating of a neutral layer on a substrate,

[0115] iid) applying a composition onto the neutral layer to form a film, wherein component a) is selected from the group consisting of triblock copolymer component a-1t), triblock copolymer a-2t), and blends of a-1t) and a-2t), the total mole % of styrene repeating units of structures (I') and (Ia) being from about 60 mole % to about 75 mole % and the total mole % of acrylic repeating units of structures (II') and (IIa) being from about 25 mole % to about 40 mole %,

[0116] iiid) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and

[0117] ivd) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate. Example

[0118] Chemicals and characterization

[0119] Unless otherwise stated, all chemicals 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., David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization” and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0120] All synthesis experiments were performed under N2 atmosphere. Photolithography experiments were performed as described in the paper.

[0121] The photolithography experiments were performed using a TEL Clean ACT8 track. SEM images were taken using an Applied Materials NanoSEM_3D scanning electron microscope at 2 FOV magnification or 4 FOV magnification (field of view (FOV) = 5 μm).

[0122] Etching experiments were performed on a self-assembled monolayer block copolymer of methyl methacrylate and styrene using standard isotropic oxygen etching conditions.

[0123] Unless otherwise stated, molecular weight measurements (also known as M w M n Polydispersity) is determined by and Gel permeation chromatography (PSS Inc., Germany) using a μ-ultrastyragel column was performed using THF as the eluent. Polystyrene polymer standards were used for calibration. In these measurements, the term "K" is synonymous with 1000 g / mole or 1000 Daltons.

[0124] DSC measurements of glass transition temperature were performed using a TA Instruments DSC Q1000 under nitrogen at a heating rate of 10°C / min. g ) is measured in the first heating scan from 0° C. to 120° C. The midpoint of the endothermic transition is considered.

[0125] TGA analyses reported herein were performed under nitrogen at a heating rate of 10°C / min using a TA Instruments TGA 550. The temperatures at 1% and 5% weight loss were recorded.

[0126] Recorded in CD2Cl2 using a Bruker Advanced III 400 MHz spectrometer 1 HNMR spectrum.

[0127] Synthesis of neutral layer and block copolymers

[0128] Synthesis Example 1: Synthesis of P(S-co-VBCB-co-MMA)-Bz-OH Neutral Layer Material

[0129] The synthesis of azo initiator is described in US9574104B1 and is used in this polymerization. In a 2L 4-neck round-bottom flask equipped with a stirring rod, reflux condenser, temperature controller and nitrogen bubbling tube, styrene (143.8g, 1.38 moles), methyl methacrylate (184.9g, 1.84 moles), 4-vinylbenzocyclobutene (180.0g, 1.38 moles) and 2-butanone (620g) are added. The reaction mixture is stirred while nitrogen is bubbled in for 20min. The mixture is heated in a heating mantle and the temperature controller is set to 80°C. At 80°C, over 1 minute, a solution of azo initiator (3.05g, 5.07mmol) in 2-butanone (12.2g) is added. The mixture is heated at 80°C for 20 hours. Over 1 minute, an additional solution of azo initiator (1.22g) in 2-butanone (4.88g) is added. Heating of the mixture was continued at 80°C for 24 hours. The mixture was cooled, diluted with 2-butanone (900 g) and then slowly precipitated in IPA (15 L). The precipitate was collected by vacuum filtration and oven dried. The residue was redissolved in THF (15% solids) and precipitated in MeOH (15 L). The precipitate was collected by vacuum filtration and oven dried. The solid was redissolved in 2-butanone (1900 g), filtered through a 0.2 μm nylon filter and slowly precipitated into IPA (15 L). The precipitate was collected by vacuum filtration and oven dried. The polymer was an off-white solid, 290 g (57.0%). GPC: 38,842 g / molM n , 90,053g / molM w , 2.30PDI.

[0130] Synthesis Example 2: Synthesis of P(Sb-MMA)(78K-b-39K)

[0131] Styrene and methyl methacrylate monomers are distilled into calibrated ampules in the presence of a dehydrating agent and stored under N2. The liquid is transferred to the reactor via an ampoule or using a stainless steel cannula under N2. 700 mL of dry tetrahydrofuran is added to a dry 1 L round-bottom reactor equipped with a side arm, a magnetic stirring bar, and a nitrogen / vacuum three-way septum adapter for connecting the ampoule. The temperature of the reactor is reduced to -78 ° C using a dry ice-acetone bath. Then, after titrating the impurities, 0.2 mL (1.4 M solution) of sec-butyl lithium is added to the reactor. Then, 20 g (0.192 mole) of styrene is added to the reactor from its ampoule under rapid stirring. The reaction solution becomes yellow-orange and reacts by stirring for 30 minutes. Subsequently, 0.06 g (0.0003 mole) of 1,1'-diphenylethylene (DPE) in 2.5 mL of dry toluene is added to the reactor via an ampoule. The orange color of the reaction mixture turned into a deep brick red, indicating that the styryllithium active center was converted into a delocalized DPE adduct carbon anion. After stirring for 2 minutes, a small amount (2 mL) of the reaction mixture was extracted for PS block molecular weight analysis. Methyl methacrylate (9.98 g, 0.0998 mole) was then added via an ampoule. After 30 minutes, the reaction was terminated with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (5 times the polymer solution) containing 10% water, filtered, and dried under vacuum at 55°C for 12 hours to obtain 28 g of P(Sb-MMA) consisting of 66 mol.% polystyrene blocks and 34 mol.% polymethyl methacrylate blocks (94% yield).

[0132] Equipped with and Gel permeation chromatography on a μ-ultrastyragel column showed that the first P (SDPE) block had M n (GPC) = 64,622 g / mol and M w / M n =1.02. The molecular weight of the diblock copolymer obtained from GPC is M n,PS-b-PMMA =107,150 g / mol and M w / M n =1.01.

[0133] Synthesis Example 3: Synthesis of P(Sb-MMA)(34K-b-17K)

[0134] PS-PMMA (34-17K) was synthesized using the same procedure described in Example 2. In order to achieve the target M of PS block and PMMA block n , add 0.42 mL of 1.4 M sec-butyllithium solution while keeping the amounts of styrene and MMA the same as in Example 2. and Gel permeation chromatography on a μ-ultrastyragel column showed that the first P (SDPE) block had M n (GPC) = 34,872 g / mol and M w / M n =1.03. The molecular weight of the diblock copolymer obtained from GPC is M n,PS-b-PMMA =49,240 g / mol and M w / M n =1.02. 1 H NMR showed 66.1 mol.% polystyrene blocks and 33.9 mol.% polymethyl methacrylate blocks.

[0135] Synthesis Example 4 Synthesis of P(Sb-MMA)(45k-b-51k)

[0136] P(Sb-MMA)(45K-b-51K) was synthesized using the same procedure as described in Example 2. In order to achieve the target M n The composition of the PS and PMMA blocks was varied, and the amounts of initiator and monomer were changed. Briefly, 20 g (0.192 mol) of styrene was polymerized with 0.32 mL (1.4 M solution) of sec-butyllithium. 0.095 g (0.0005 mol) of 1,1'-diphenylethylene (DPE) in 2.5 ml of dry toluene was then added to the reactor via an ampoule. The orange color of the reaction mixture turned dark brick red, indicating that the styryllithium active center was converted into a delocalized DPE adduct carbon anion. After stirring for 2 min, a small amount (2 mL) of the reaction mixture was withdrawn for PS block molecular weight analysis. Methyl methacrylate (22.85 g, 0.23 mol) was then added via an ampoule. The reaction was terminated after 30 min with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (5 times the polymer solution) containing 10% water, filtered, and dried under vacuum at 55° C. for 12 h to obtain 40 g of P(Sb-MMA) composed of 46.9 mol.% polystyrene blocks and 53.1 mol.% polymethyl methacrylate blocks (94% yield).

[0137] Equipped with and Gel permeation chromatography on a μ-ultrastyragel column showed that the first P (SDPE) block had M n (GPC) = 45,048 g / mol and M w / M n =1.04. The molecular weight of the diblock copolymer obtained from GPC is Mn,PS-b-PMMA =88,348 g / mol and M w / M n =1.02.

[0138] Synthesis of Inventive and Comparative h-PS Oligomer Additives

[0139] Synthesis Example 5: Synthesis of h-PS Additive 1

[0140] Styrene (59.1 g, 568 mmol), 1-dodecanethiol (4.15 g, 20.5 mmol), AIBN (3.37 g, 20.5 mmol) and 2-butanone (62.5 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected and dried under vacuum at 50°C overnight. 36.7 g (60%) white powder, GPC: 3,436 g / mol Mn, 5,455 g / mol Mn w , 1.59PDI

[0141] Synthesis Example 6: Synthesis of h-PS Additive 2

[0142] Styrene (381.3 g, 3.66 mol), 1-dodecanethiol (23.03 g, 114 mmol), AIBN (18.7 g, 114 mmol) and 2-butanone (400 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected and dried under vacuum at 50°C overnight. 263 g (67%) white powder, GPC: 4,267 g / mol M n , 6,814 g / mole M w , 1.60PDI

[0143] Synthesis Example 7: Synthesis of h-PS Additive 3

[0144] Styrene (47.9 g, 459 mmol), 1-dodecanethiol (2.65 g, 13 mmol), AIBN (2.15 g, 13 mmol) and 2-butanone (50 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected and dried in vacuo at 50°C overnight. 33.9 g (69%) white powder, GPC: 4,729 g / molM n , 7,698 g / mole M w , 1.63PDI

[0145] Synthesis Example 8: Synthesis of h-PS Comparative Additive 4

[0146] Styrene (59.8 g, 574 mmol), 1-dodecanethiol (3.32 g, 16 mmol), AIBN (2.69 g, 16 mmol) and 2-butanone (62.5 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected by filtration and dried under vacuum at 50°C overnight. 44 g (72%) white powder, GPC: 9,301 g / molM n , 15,538 g / mole M w , 1.67PDI

[0147] Synthesis Example 9: Synthesis of h-PS Additive 5

[0148] Styrene (53.2 g, 511 mmol), 1-dodecanethiol (11.48 g, 6 mmol), AIBN (9.32 g, 29 mmol) and 2-butanone (62.5 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected and dried in vacuo at 50°C overnight. 16.2 g (28%) white powder, GPC: 1,952 g / molM n , 2,898 g / mole M w , 1.48PDI

[0149] Synthesis Example 10: Synthesis of h-PS Additive 6

[0150] Styrene (55.4 g, 532 mmol), 1-dodecanethiol (8.73 g, 43 mmol), AIBN (7.08 g, 43 mmol) and 2-butanone (62.5 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected by filtration and dried under vacuum at 50°C overnight. 26.7 g (45%) white powder, GPC: 2,425 g / mol M n , 3,386 g / mole M w , 1.40PDI

[0151] Synthesis Example 11: Synthesis of h-PS Additive 7

[0152] Styrene (57.7 g, 554 mmol), 1-dodecanethiol (5.90 g, 29 mmol), AIBN (4.79 g, 29 mmol) and 2-butanone (62.5 g) were added to a flask and bubbled with nitrogen for 30 minutes. The mixture was heated in an 80°C oil bath for 16 hours. The mixture was cooled to room temperature, diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected by filtration and dried under vacuum at 50°C overnight. 39.1 g (65%) white powder, GPC: 2,323 g / mol M n , 3,934 g / mole M w , 1.69PDI.

[0153] Synthesis Example 12: Synthesis of h-PS Comparative Additive 1

[0154] Styrene (27.3 g, 262 mmol) and cyclohexane (181 g) were added to a Schlenk flask and degassed three times using a freeze-thaw technique. The mixture was titrated with sec-BuLi until a yellow color persisted. Sec-BuLi (2.79 mL, 1.4 M in cyclohexane, 4 mmol) was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. The mixture was diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected and dried under vacuum at 50°C overnight. 19 g (70%) white powder, GPC: 5475 g / mol M n , 5937g / mole M w , 1.08PDI

[0155] Synthesis Example 13: Synthesis of h-PS Comparative Additive 2

[0156] Styrene (31.2 g, 300 mmol) and cyclohexane (207 g) were added to a Schlenk flask and degassed three times using the freeze-thaw technique. The mixture was titrated with sec-BuLi until a yellow color persisted. sec-BuLi (2.79 mL, 1.4 M in cyclohexane, 4 mmol) was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. The mixture was diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved in ethyl acetate as a 15% solid solution, washed three times with DI water and precipitated in isopropanol. The polymer was collected by filtration and dried under vacuum at 50°C overnight. 24 g (76%) white powder, GPC: 6700 g / molM n , 7300g / mole M w , 1.09PDI

[0157] The following describes experiments conducted on annealable block copolymer formulations that affect the observed morphology and LCDU as well as the observed torsional dependence (which describes the quality of the contact holes and the multiplicity of contact holes for perfect alignment on the pre-pattern) by adjusting the wt.% amount of specific oligomeric styrene additives. It was unexpectedly found that higher wt.% contents of oligomeric polystyrene additives impart improved properties, but only in the case of certain types of these oligomers. Specifically, in studying homooligomeric polystyrene of 100 mol% homopolystyrene (h-PS), it was unexpectedly found that such materials prepared by controlled synthesis methods (such as anionic polymerization) showed very poor morphology for the block copolymers in which these were used during the DSA treatment; while those prepared by free radical polymerization in the claimed M wh-PS oligomeric additives within the range of 100-150 nm showed good morphology during the same DSA treatment of block copolymers, and furthermore there was a strong correlation with the molecular weight of these additives and their effectiveness in imparting good morphology to the block copolymer formulations during self-assembly annealing. In fact, surprisingly, when blended with block copolymers during self-assembly, the molecular weights exceeding the claimed M w h-PS of the range also showed poor morphology. While not being bound by theory, it is believed that this phenomenon indicates that in BCP formulations, the annealing kinetics during self-assembly are unexpectedly strongly influenced by some complex mobility coefficients imparted by the oligomeric additives, which simultaneously have smaller sizes and chemically random oligomeric structures, which contribute to the better kinetics of these BCP formulations.

[0158] Synthesis and properties of h-PS oligomers

[0159] Synthesis Examples 5 to 13 show how inventive and comparative h-PS oligomeric materials were synthesized, and Tables 1 and 2 summarize the characteristics of these materials and also give a summary of the performance of these when used as additives to block copolymers during annealing on neutral layer coated substrates.

[0160] The h-PS oligomers of the present invention in Table 1 and the comparative formulations in Table 2 were prepared, containing 20 wt.% of the total solids of these h-PS oligomers and 80 wt.% of the total solids of the block copolymer (BCP). Synthesis Example 2: Synthesis of P(Sb-MMA) (78K-b-39K) was diluted to 1.2 wt.% solids in the spin-casting solvent PGMEA. The solution was filtered using a 0.2 μm PTFE filter.

[0161] All additives shown in the following treatment results and Tables 1 and 2 were blended at 20 wt.% with the block copolymer, where the block copolymer constituted 80 wt.% of the total of the additives and block polymer. Specifically, this was done using 0.8 g of PS-b-PMMA, 0.2 g of the additive to be tested, and 82.3 g of PGMEA.

[0162] Processing conditions:

[0163] Example 1: Synthesis of P(S-co-VBCB-co-MMA)-Bz-OH Neutral Layer Material: A 1.2 wt.% solution in PGMEA was spin-coated onto a Si wafer and baked at 250°C for 2 minutes to form a 7 nm thick cross-linked neutral layer. Formulations containing h-PS oligomer additives 1 to 3 and 5 to 7, as well as comparative additives 1, 2, and 4, were then spin-coated separately onto the cross-linked neutral layer to form a 47 nm thick coating of a block copolymer formulation containing h-PS oligomer additives 1 to 3 and 5 to 7, as well as comparative additives 1, 2, and 4. These coatings were baked at 110°C for 1 minute and then annealed at 260°C under N2 for 15 minutes. The annealed coatings were then etched using O2 plasma etching to create contact holes.

[0164] Table 1 shows a summary of the characteristics of different types of h-PS oligomers of the present invention prepared by free radical polymerization and their annealing properties. Figure 1 As shown in , these materials show good performance when blended with block copolymers, and when the composition is coated on a neutral layer and annealed, the self-assembled column morphology of the block copolymer does not collapse during the rapid annealing process achieved by the h-PS oligomers of the present invention.

[0165] A summary of the properties of the different types of comparative h-PS oligomers studied, prepared by free radical or anionic polymerization, is shown in Table 2. When coated on neutral layer coated substrates and annealed, these materials showed poor performance with collapse of the self-assembled pillar morphology during the rapid annealing process.

[0166] Table 1 Additive characterization and thermal properties

[0167]

[0168]

[0169] Table 2. Additive Characterization and Thermal Properties of Comparative Examples

[0170]

[0171] Figure 1 SEM images with a field of view (FOV) of 2, 4, or 50 of each of the BCP formulations (Table 1) containing h-PS oligomers of the present invention prepared by free radical polymerization are shown after these formulations were coated on a neutral layer-coated substrate and annealed and etched with O plasma, wherein these formulations gave good self-assembly of the contact holes, which showed defect-free vertical contact hole morphology.

[0172] Figure 2SEM images at a field of view (FOV) of 2 or 4 of each of the BCP formulations (Table 2) containing comparative h-PS oligomers prepared by free radical polymerization or anionic polymerization are shown after these formulations were coated on a neutral layer coated substrate and annealed and etched with O plasma. w range (Comparative Additive 4) or deviate from the claimed polydispersity range (Comparative Additives 1 and 2), it unexpectedly shows that poor self-assembly of contact holes occurs with defects, which are observed as dark spots, which are indicative of defects caused by collapsed vertical pillar morphology due to reduced self-assembly kinetics. Table 1 shows that the thermogravimetric temperatures of the anionically polymerized comparative additives 1 and 2 are much higher than their respective free radical polymerized additives 1 and 3. It is expected that with additives 2 and 3 (having similar M w ) all showed defect-free vertical contact hole morphology as in the case of the formulation with Additive 2 (Table 1).

[0173] While the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is to be understood that this disclosure is made by way of example only and that those skilled in the art may resort to numerous variations in the conditions and sequence of steps without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A composition comprising components a), b) and c), wherein: a) is a block copolymer component or a blend of at least two block copolymers, b) is at least one low T g Oligomeric polystyrene additives, wherein each additive individually has a T ranging from about 68.0°C to about 90.0°C g and having an M ranging from about 2,500 g / mole to about 8,000 g / mole w , having a polydispersity of 1.20 to about 1.80, and further wherein the styrene additive is selected from the group consisting of at least one styrene homopolymer prepared by free radical polymerization, at least one random styrene copolymer prepared by free-radical polymerization, the repeating units of which consist exclusively of styrene repeating units and in which at least two styrene repeating units are present, a mixture of at least one of said styrene homopolymers and at least one of said styrene random copolymers, c) is an organic spin-casting solvent.

2. The composition according to claim 1, wherein The composition consists of components a), b) and c).

3. The composition according to claim 1 or 2, wherein In said component b), each additive individually has a T ranging from about 69.0°C to about 89.7°C. g .

4. The composition according to any one of claims 1 to 3, wherein Each additive individually has a polydispersity of about 1.30 to about 1.

80.

5. The composition according to any one of claims 1 to 4, wherein The component b) is at least one of the styrene homopolymers or at least one of the styrene random copolymers.

6. The composition according to any one of claims 1 to 5, wherein The component b) is at least one of the styrene homopolymers and furthermore has structure (A), the repeating units of which consist of repeating units having structure (I), wherein n1 is the number of repeating units and specifies that this is a repeating unit, R A1 、R A2 、R A3 、R A4 、R A5 independently selected from H or C-1 to C-8 alkyl, R m1 is H or methyl, and the styrene homopolymer has two terminal groups as shown in structure (A), one of which is H and the other is a methyl moiety substituted with Rr, Rr1 and Rr2, wherein Rr1 is a C-1 to C-8 alkyl group, Rr2 is selected from C-1 to C-8 alkyl groups, Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl group or an aryl moiety; 7. The composition according to claims 1 to 5, wherein The component b) is at least one random copolymer of styrene having structure (B), wherein its repeating units consist of two different repeating units of structures (II') and (III), wherein n2 and n3 are the number of these repeating units and specify that these are repeating units, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 are independently selected from H or C-1 to C-8 alkyl, R m2 、R m3 are independently selected from H or methyl, and The styrene random copolymer has two end groups as shown in structure (B), one of which is H and the other is a methyl moiety substituted with Rr3, Rr4 and Rr5, wherein Rr4 is a C-1 to C-8 alkyl group, Rr5 is selected from C-1 to C-8 alkyl groups, Rr3 is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl group or an aryl moiety; 8. The composition according to any one of claims 1 to 5, wherein The component b) is a mixture of at least one of the styrene homopolymers and at least one of the styrene random copolymers.

9. The composition according to claim 1 or 6, wherein The component b) is a mixture of at least one styrene homopolymer and at least one styrene random copolymer, wherein: The styrene homopolymer has structure (A), the repeating units of which consist of repeating units having structure (I), wherein n1 is the number of repeating units and specifies that this is a repeating unit, R A1 、R A2 、R A3 、R A4 、R A5 independently selected from H or C-1 to C-8 alkyl, R m1 is H or methyl, and the styrene homopolymer has two terminal groups as shown in structure (A), one of which is H and the other is a methyl moiety substituted with Rr, Rr1 and Rr2, wherein Rr1 is C-1 to C-8 alkyl, Rr2 is selected from C-1 to C-8 alkyl, Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl or aryl moiety; and Furthermore, the styrene random copolymer has structure (B), wherein its repeating units consist of two repeating units of structures (II') and (III), wherein n2 and n3 are the numbers of these repeating units, respectively, specifying that these are repeating units, R B1 、R B2 、R B3 、R B4 、R B5 、R B6 、R B7 、R B8 、R B9 and R B10 are independently selected from H or C-1 to C-8 alkyl, R m2 、R m3 are independently selected from H or methyl, and the styrene random copolymer has two end groups as shown in structure (B), one of which is H and the other is a methyl moiety substituted by Rr2, Rr3 and Rr4, wherein Rr4 is a C-1 to C-8 alkyl, Rr5 is selected from C-1 to C-8 alkyl, Rr3 is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C-1 to C-8 alkyl or aryl moiety; 10. The composition according to any one of claims 1 to 9, wherein The component b) is at least one low T g oligomeric polystyrene additives, wherein each additive individually has an M ranging from about 2,900 g / mole to about 7,700 g / mole w .

11. The composition according to any one of claims 1 to 10, wherein The component a) is selected from a single triblock copolymer and a blend of at least two triblock copolymers, or a single diblock copolymer and a blend of at least two diblock copolymers.

12. The composition according to any one of claims 1 to 11, wherein The component a) is an ABA triblock copolymer component selected from the group consisting of an ABA triblock copolymer a-1t), an ABA triblock copolymer a-2t), and a blend of two different ABA triblock copolymers a-1t) and an ABA triblock copolymer a-2t), wherein a-1t) is an ABA triblock copolymer comprising an intermediate B) styrene block segment having repeating units of styrene structure (I') and two terminal acrylic block A) segments of equal length having structure (II'), wherein R1 and R3 are independently selected from H and C-1 to C-4 alkyl, R2 is H or C-1 to C-8 alkyl, R4 is C-1 to C-8 alkyl, and The mole % value of the styrene repeating unit of structure (I') is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating unit of structure (I') is from about 20 mole % to about 60 mole %, based on the total moles of the repeating units of structures (I') and (II'), wherein the individual mole % values ​​of the repeating units of structures (I') and (II') are selected from their respective ranges to add up to 100 mole % of the total moles of the repeating units of structures (I') and (II'), and The triblock copolymer a-1t) has a polydispersity of about 1.0 to about 1.1, and With an M of about 70,000 g / mole to about 350,000 g / mole n , a-2t) is an ABA triblock copolymer comprising a middle B) block segment having repeating units of styrene structure (Ia) and two end block A) segments of equal length having acrylic structure (IIa), wherein R 1a and R 3a are independently selected from H and C-1 to C-4 alkyl, R 2a is H or C-1 to C-8 alkyl, R 4a is a C-1 to C-8 alkyl group, The mole % value of the styrene repeating units of structure (Ia) is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating units of structure (IIa) is from about 20 mole % to about 60 mole %, based on the total moles of the repeating units of structures (Ia) and (IIa), and wherein the individual mole % values ​​of the repeating units of structures (Ia) and (IIa) are selected from their respective ranges to add up to 100 mole % of the total moles of the repeating units of structures (Ia) and (IIa), and The triblock copolymer a-2t) has a polydispersity of about 1.0 to about 1.1, and having an M of about 70,000 g / mol to about 350,000 g / mol n 13. The composition of claim 12, wherein R1, R 1a , R2 and R 2a is H and R3, R 3a , R4 and R 4a It's methyl.

14. The composition according to any one of claims 1 to 13, wherein Component a) is a triblock copolymer selected from the group consisting of a triblock copolymer of structure (ABA-1), a triblock copolymer of structure (ABA-2), and a mixture of these two block copolymers, wherein mt, mta, nt, and nta are the number of repeating units, R 1s 、R 1sa 、R 2s and R 2sa independently selected from hydrogen, C-1 to C-8 alkyl, -N(R 3s )2、-OR 4s and Si(R 5s )3, where R 3s 、R 4s and R 5s are independently selected from C-1 to C-4 alkyl, and R1, R 1a , R2, R 2a , R3, R 3a , R4 and R 4a As defined in claim 12, 15. The composition of claim 14, wherein R1, R 1a , R2, R 2a and R 1s 、R 1sa 、R 2s and R 2sa is H and R3, R 3a , R4 and R 4a It's methyl.

16. The composition according to any one of claims 1 to 11, wherein a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), wherein a-1) is a diblock copolymer comprising a block A) of styrene repeating units having a styrene structure (I') and a block B) having an acrylic structure (II'), wherein R1 and R3 are independently selected from H and C-1 to C-4 alkyl, R2 is H or C-1 to C-8 alkyl, R4 is C-1 to C-8 alkyl, and The mole % value of the styrene repeating unit of structure (I') is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating unit of structure (II') is from about 20 mole % to about 60 mole %, based on the total moles of the repeating units of structures (I') and (II'), wherein the individual mole % values ​​of the repeating units of structures (I') and (II') are selected from their respective ranges to add up to 100 mole % of the total moles of the repeating units of structures (I') and (II'), and The diblock copolymer a-1) has a polydispersity of from about 1.0 to about 1.1 Having an M of about 50,000 g / mole to about 150,000 g / mole n , a-2) is a diblock copolymer comprising a block Aa) having a repeating unit of a styrene structure (Ia) and a block Ba) having a repeating unit of an acrylic acid structure (IIa), wherein R 1a and R 3a are independently selected from H or C-1 to C-4 alkyl, R 2a is H or C-1 to C-8 alkyl, R 4a is a C-1 to C-8 alkyl group, and The mole % value of the styrene repeating units of structure (Ia) is from about 40 mole % to about 80 mole %, and the mole % value of the acrylic repeating units of structure (IIa) is from about 20 mole % to about 60 mole %, based on the total moles of the repeating units of structures (Ia) and (IIa), and wherein the individual mole % values ​​of the repeating units of structures (Ia) and (IIa) are selected from their respective ranges to add up to 100 mole % of the total moles of the repeating units of structures (Ia) and (IIa), and The diblock copolymer a-2) has a polydispersity of from about 1.0 to about 1.1, Having an M of about 30,000 g / mole to about 90,000 g / mole n , 17. The composition of claim 16, wherein Component a) is wherein R1, R 1a , R2 and R 2a is H and R3, R 3a , R4 and R 4a It is a component of methyl.

18. The composition according to claim 16 or 17, wherein The diblock copolymers a-1) and a-2) have structures (IS) and (ISa), respectively, wherein R 1s 、R 1sa 、R 2s and R 2sa independently selected from hydrogen, C-1 to C-8 alkyl, -N(R 3s )2、-OR 4s and Si(R 5s )3, where R 3s 、R 4s and R 5s independently selected from C-1 to C-4 alkyl, 19. The composition of claim 18, wherein R 1s 、R 2s 、R 1sa and R 2sa It's hydrogen.

20. The composition of any one of claims 16 to 19, wherein For component a), the diblock copolymer component a-1) has a polydispersity of 1.00 to about 1.

03.

21. The composition of any one of claims 16 to 20, wherein For component a), the diblock copolymer component a-1) has an M of about 93,000 g / mole to about 105,300 g / mole. n .

22. The composition of any one of claims 16 to 21, wherein For the diblock copolymer component a-1), the mole % value of repeating units of structure (I') is from about 40 mole % to about 60 mole %, and the mole % value of repeating units of structure (II') is from about 40 mole % to about 60 mole %.

23. The composition of any one of claims 16 to 21, wherein For the diblock copolymer component a-1), the mole % value of repeating units of structure (I') is from about 60 mole % to about 75 mole %, and the mole % value of repeating units of structure (II') is from about 25 mole % to about 40 mole %.

24. The composition of any one of claims 16 to 23, wherein For component a), the diblock copolymer component a-2) has a polydispersity of 1.00 to about 1.

03.

25. The composition of any one of claims 15 to 24, wherein For component a), the AB diblock copolymer component a-2) has an M of about 40,800 g / mole to about 61,200 g / mole. n .

26. The composition of any one of claims 16 to 25, wherein For component a), for a single block copolymer a-1) or a-2) or in a blend of a-1) and a-2), the total mole % value of repeating units of structures (I') and (Ia) is from about 40 mole % to about 60 mole %, and the total mole % value of repeating units of structures (II') and (IIa) is from about 40 mole % to about 60 mole %.

27. The composition of any one of claims 16 to 25, wherein For component a), for a single block copolymer a-1) or a-2) or in a blend of a-1) and a-2), the total mole % value of repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole %, and the total mole % value of repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %.

28. The composition of any one of claims 16 to 27, wherein Component a) is a blend of a-1) and a-2).

29. The composition of any one of claims 16 to 27, wherein Component a) is a-1) or a-2).

30. The composition of any one of claims 1 to 29, wherein Component a) comprises from about 0.5 wt.% to about 2.0 wt.% of the total composition.

31. The composition of any one of claims 16 to 21, 24, 25, 28, and 30, wherein component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), having a total mole % of styrene repeating units of structures (I') and (Ia) of from about 40 mole % to about 80 mole % and a total mole % of acrylic repeating units of structures (II') and (IIa) of from about 20 mole % to about 60 mole %.

32. The composition of any one of claims 16 to 21, 24, 25, 28 and 30, wherein Component a) is a diblock copolymer component selected from the group consisting of diblock copolymers a-1), diblock copolymers a-2), and blends of a-1) and a-2), wherein the total mole % of styrene repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole %, and further wherein the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %.

33. The composition of any one of claims 12 to 15, wherein Component a) is selected from the group consisting of triblock copolymer components a-1t), triblock copolymers a-2t), and blends of a-1t) and a-2t), wherein the total mole % of styrene repeating units of structures (I') and (Ia) is from about 40 mole % to about 80 mole %, and the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 20 mole % to about 60 mole %.

34. The composition of any one of claims 12 to 15, wherein Component a) is selected from the group consisting of a triblock copolymer component a-1t), a triblock copolymer a-2t), and a blend of a-1t) and a-2t), wherein the total mole % of styrene repeating units of structures (I') and (Ia) is from about 60 mole % to about 75 mole %, and further wherein the total mole % of acrylic repeating units of structures (II') and (IIa) is from about 25 mole % to about 40 mole %, and component b) wherein the low T g The oligomeric polystyrene additive is the at least one styrene homopolymer prepared by free radical polymerization.

35. A method comprising the steps of: i) forming a coating of a neutral layer on a substrate, ii) applying the composition according to any one of claims 1 to 34 onto the neutral layer to form a film, iii) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and iv) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

36. A method for forming a line and space array comprising the steps of: ia) forming a coating of a neutral layer on a substrate, iia) applying the composition according to claim 31 onto the neutral layer to form a film, iiia) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and iva) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

37. A method for forming a contact hole array, comprising the steps of: ib) forming a coating of a neutral layer on a substrate, iib) applying the composition according to claim 32 onto the neutral layer to form a film, iiib) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and ivb) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

38. A method for forming a line and space array comprising the steps of: ic) forming a coating of a neutral layer on a substrate, iic) applying the composition according to claim 33 onto the neutral layer to form a film, iiic) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and ivc) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

39. A method for forming a contact hole array, comprising the following steps: id) forming a coating of a neutral layer on a substrate, iid) applying the composition according to claim 34 onto the neutral layer to form a film, iiid) baking the film at a temperature selected from about 240° C. to about 280° C. in an inert gas atmosphere to form a self-assembled film, and ivd) etching the substrate with plasma to transfer the self-assembled film pattern into the substrate.

40. Use of a composition as claimed in any one of claims 1 to 34 in a self-assembly process followed by pattern transfer of the self-assembled pattern into a substrate.

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