Block copolymer formulations for improving self-assembling shapes in induced 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, and b) is at least one low T g A composition comprising an oligomeric polystyrene additive, and c) an organic solvent for organic spin casting. Component b) individually, if there are two or more, has a Tg in the range of approximately 68.0°C to approximately 90.0°C and a M in the range of approximately 2,500 g / mol to approximately 8,000 g / mol. w The composition is selected from the group consisting of a styrene homopolymer produced by radical polymerization, a styrene random copolymer produced by radical polymerization (whose repeating units consist solely of styrene repeating units, and which have at least two types of styrene repeating units), and a mixture of the styrene homopolymer and at least one of the styrene random copolymers. A DSA processing method using this composition is also disclosed.

Description

[Technical Field]

[0001] The disclosed invention is a low-T for use in a DSA IC manufacturing process. g This relates to block copolymer compositions containing additives. [Background technology]

[0002] Self-assembly of block copolymers is a useful method for generating even smaller patterned shapes for the fabrication of microelectronic devices, achieving limiting dimensions (CD) of nanoscale shapes. Self-assembly methods are desirable to extend the resolving capabilities of microlithography techniques for repeating shapes such as arrays of contact holes or posts. Conventional lithography methods may use ultraviolet (UV) light to expose a photoresist layer coated on a substrate or layered substrate through a mask. Positive or negative photoresists are useful, and these may also contain heat-resistant elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive photoresists, UV radiation passing through the mask triggers a photochemical reaction in the photoresist, causing the exposed area to be removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through the mask makes the radiation-exposed area difficult to remove with a developer solution or by conventional IC plasma processing. Next, integrated circuit patterns, such as gates, vias, or interconnects, are etched into the substrate or layered substrate, and residual photoresist is removed. When using conventional lithography exposure processes, there are limitations to the geometric dimensions of integrated circuit patterns. Further reduction of pattern dimensions is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Due to the need for large-scale integration, the circuit dimensions and patterns of devices have been continuously reduced. In the past, the final resolution of the pattern depended on the wavelength of light used to expose the photoresist, which itself has limitations. Guided (or induced) self-assembly techniques such as graphoepitaxy and chemoepitaxy using block copolymer imaging with patterned regions on the substrate are highly desirable techniques used to improve resolution while reducing CD variation.These technologies can be used to enhance conventional UV lithography techniques or to enable even higher resolution and CD control in strategies using EUV, electron beam, deep UV, or immersion lithography. The inductively self-assembling block copolymer comprises blocks of etching-resistant copolymer units and blocks of highly etchable copolymer units, which, when coated, aligned, and etched on a substrate, provide areas of very high-density patterns.

[0003] In the guided or unguided self-assembly of block copolymer films on patterned or unpatterned substrate regions, the self-assembly process of this block polymer layer typically occurs during the annealing of this film covering a neutral layer. This neutral layer on a semiconductor substrate may be an unpatterned neutral layer, or, in the case of chemoepitaxy or graphoepitaxy, this neutral layer may contain graphoepitaxy or chemoepitaxy guide patterns (formed via the UV lithography techniques described above), respectively. During the annealing of the block copolymer film, the underlying neutral layer induces nanophase separation of block copolymer domains. One example is the formation of phase-separated domains that are lamellae or cylinders perpendicular to the surface of the underlying neutral layer. These nanophase-separated block copolymer domains form pre-patterns (e.g., line-and-space L / S), which can be transferred into the substrate via an etching process (e.g., plasma etching). In graphoepitaxy or chemoepitaxy, these guide figures can induce both pattern modification and pattern multiplication. In the case of an unpatterned neutral layer, this generates, for example, a repeating array of L / S or CH. For example, in conventional block copolymers such as poly(styrene-β-methyl methacrylate) (P(Sb-MMA)) where both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermal annealing the block copolymer onto a layer of non-preferential or neutral material that is grafted or crosslinked at the polymer-substrate interface.

[0004] In graphoepitaxy-induced self-assembly, block copolymers self-assemble on a substrate that has been pre-patterned using conventional lithography (ultraviolet, deep UV, electron beam, or extreme ultraviolet (EUV) exposure sources) to form repeating topographic patterns such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-induced self-assembly array, the block copolymers can enhance pattern resolution by dividing the space in the trenches between topographic lines into finer patterns, by forming self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the pre-patterned lines. For example, diblock copolymers or triblock copolymers containing carbon-rich blocks (e.g., styrene, or some other element such as Si, Ge, or Ti) that can undergo microphase separation and are resistant to plasma etching, and blocks that are highly plasma-etchable or removeable, can provide high-resolution pattern definition. Examples of highly etchable blocks may include monomers that are oxygen-rich, free of heat-resistant elements, and capable of forming highly etchable blocks, such as methyl methacrylate. The plasma etching gas used in the etching process to define the self-assembling pattern is typically the same gas used in processes for manufacturing integrated circuits (ICs). In this way, patterns much finer than those defined by conventional lithography techniques can be generated on typical IC substrates, thereby achieving pattern multiplication. Similarly, graphoepitaxy can be used in which suitable block copolymers align themselves by induced self-assembly around an array of contact holes or posts defined by conventional lithography, thereby creating a denser array of etchable and etch-resistant domains, which gives a denser array of contact holes when etched, and thus generating denser patterns such as contact holes. As a result, graphoepitaxy has the potential to provide both pattern modification and pattern multiplication.

[0005] In chemical epitaxy, or pinned chemical epitaxy, the self-assembly of block copolymers is formed on a surface that has no or very little topography (i.e., non-guided topography) that underlies the induced self-assembly process, but has guide figures that are regions of different chemistry. For example, the surface of a substrate can be patterned using conventional lithography (UV, deep UV, electron beam, EUV) to create a line-and-space (L / S) pattern of surfaces with different chemistry, where exposed areas where the surface chemistry has been alternated by radiation are alternating with unexposed areas that do not show chemical changes. These areas do not provide topographic differences but provide surface chemical differences or pinning that induce the self-assembly of block copolymer segments. Specifically, the induced self-assembly of block copolymers with block segments containing etch-resistant repeating units (e.g., styrene repeating units) and fast-etchable repeating units (e.g., methyl methacrylate repeating units) would allow for the precise placement of etch-resistant and fast-etchable block segments on the pattern. This technique allows for the precise placement of these block copolymers and subsequent pattern transfer to the substrate after plasma or wet etching. Chemical epitaxy has the advantage of allowing for pattern modification by fine-tuning this through changes in chemical differences, which helps improve line edge roughness and CD control. Other types of patterns, such as repeating contact hole (CH) arrays, can also be modified using chemoepitaxy.

[0006] The neutral layer is a layer on the substrate or the surface of the treated substrate that has no affinity for any of the block segments of the block copolymer used in induced self-assembly. The neutral layer is useful in the graphoepitaxy method of induced self-assembly of block copolymers because it allows for the proper placement or orientation of the block polymer segments for induced self-assembly, resulting in the proper placement of etch-resistant and highly etchable block polymer segments on the substrate. For example, on a surface containing line-and-space patterns defined by conventional radiolithography, the neutral layer allows the block segments to be oriented so that they are perpendicular to the surface of the substrate, an orientation that is ideal for both pattern modification and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, this segment will lie flat on its surface, maximizing the contact area between the segment and the substrate; such a surface will disrupt the desired vertical alignment, which can be used to achieve either pattern modification or pattern multiplication based on the figure generated by conventional lithography. Modifying or pinning selected small areas of the substrate to strongly interact with one block of the block copolymer, while leaving the rest of the surface coated with a neutral layer, can be useful for aligning the domains of the block copolymer in a desired direction, and this forms the basis for pinned chemoepitaxy or graphoepitaxy used for pattern multiplication.

[0007] Self-assembly using polystyrene-β-polymethyl methacrylate (PS-β-PMMA), along with nanophase separation assembly processes that produce well-aligned arrays of domains, is widely used as a next-generation patterning material in lithography. However, this process is accompanied by the formation of a significant number of defects when the film thickness exceeds 50 nm. These defects are critical in contact hole and line / space doubling processes and need to be significantly reduced to improve device yield in any commercially viable IC manufacturing using induced self-assembly. One cause of defects is insufficient diffusion of block segments, resulting in defects such as misalignment, bridging, network structures, and line or cylinder collapse. Therefore, there is a demand for new materials and processes that can result in self-assembly of block copolymer domains with a significantly reduced number of these defects, even in films with thicknesses exceeding 50 mm. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 shows SEM images taken at 2 and 4 or 50 FOV of annealed and plasma-etched block copolymer (BCP) formulations containing radical-polymerized h-PS oligomer type additives 1, 2, 3, 5, 6, or 7 according to the present invention, exhibiting good self-assembly of defect-free contact holes (CH). [Figure 2] Figure 2 shows SEM images taken at 2 and 4 FOV of annealed and plasma-etched block copolymer (BCP) formulations containing a comparative radical-polymerized h-PS oligomer type additive 4 or anionic-polymerized h-PS oligomer type additive 1 or 2, exhibiting defective contact hole (CH) self-assembly. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] US9574104B1 (Patent Document 1) [Non-patent literature]

[0010] [Non-Patent Document 1] Macromolecules 2019,52,2987-2994 [Non-Patent Document 2] Macromol.Rapid Commun.2018,39,1800479 [Non-Patent Document 3] A.Deiter Shluter et al Synthesis of Polymers,2014,Volume 1,p.315 [Non-Patent Document 4] Encyclopedia of Polymer Science and Technology,2014,Vol 7,p.625 [Non-Patent Document 5] David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization”, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005) [Overview of the Initiative]

[0011] The inventors have identified a series of T polymers produced by standard radical polymerization that can be used as additives with block copolymers (BCPs) to form novel block copolymer compositions. g An oligomer-type styrene-based additive was discovered. The novel block copolymer composition is this low T g The performance is improved by adjusting the weight percentage of styrene-based additives. Surprisingly, low T is produced by controlled synthesis methods such as anionic polymerization. g Styrene-based additives exhibited very poor morphology during self-assembly annealing when combined with BCP. In contrast, surprisingly, low T produced by standard radical polymerization performed better. g Oligomer-type styrene additives are specific Mw When adjusted to the polydispersity range and used as a BCP additive, it gave a good self-assembled shape during this self-assembly annealing. This interesting phenomenon indicates that the BCP formulation dynamics are surprisingly strongly affected by the mobility of oligomeric additives of relatively small size and chemically random structure that strongly contribute to the better dynamics of the BCP formulation.

[0012] Specifically, the present invention is a composition comprising components a), b) and c), 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-based additive, each additive individually having a T in the range from about 68.0 °C to about 90.0 °C g and an M in the range from about 2,500 g / mol to about 8,000 g / mol, having a polydispersity from 1.20 to about 1.80, and further, the styrene-based additive is at least one styrene-based homopolymer produced by radical polymerization, at least one styrene-based random copolymer produced by radical polymerization, the repeating units of which consist only of styrene-based units and at least two styrene-based repeating units are present, the at least one styrene-based random copolymer, and at least one mixture of the at least one styrene-based homopolymer and the at least one styrene-based random copolymer, and c) is an organic spin-cast solvent, relating to the composition.

[0013] Another aspect of the present invention is a method of using the composition in a self-assembly process and then pattern transferring its self-assembled pattern into a substrate.

Embodiments for Carrying Out the Invention

[0014] ​​Both the general description above and the detailed description below are illustrative and explanatory, and should be understood not to limit the invention described in the claims. In this application, unless otherwise specifically stated, the use of the singular form includes the plural, the singular form means "at least one (or one kind)", and the use of "or" means "and / or". Furthermore, the use of "includes" and other verb forms such as "includes" is not limiting. Also, unless otherwise specifically stated, descriptions such as "element" or "component" include both elements and components containing one constituent unit, and elements or components containing more than one constituent unit. Unless otherwise indicated, the conjunction "and" used herein is intended to be compatible, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. The use of "and / or" used herein refers to any combination of the aforementioned elements, including the use of a single element.

[0015] The term C1-C4 alkyl includes methyl, C2-C4 linear alkyl, and C3-C4 branched alkyl moieties, such as 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), and 2-butyl (-CH(CH3)CH2-CH3). Similarly, the term C1-C8 alkyl includes methyl, C2-C8 linear alkyl, C3-C8 branched alkyl, C4-C8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) or C5-C8 alkylene cycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0016] The term C2-C5 alkylene encompasses both C2-C5 linear alkylene moieties (e.g., ethylene, propylene, etc.) and C3-C5 branched alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0017] Diblock and triblock copolymers of styrene-based and acrylic-based portions, useful as components in the compositions according to the present invention described herein, can be produced by various methods, such as anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-cleavage-chain transfer (RAFT) polymerization, living radical polymerization, and similar methods (Macromolecules 2019, 52, 2987-2994 (Non-Patent Literature 1); Macromol. Rapid Commun. 2018, 39, 1800479 (Non-Patent Literature 2); A. Deiter Shluter et al Synthesis of Polymers, 2014, Volume 1, p.315 (Non-Patent Literature 3); Encyclopedia of Polymer Science and Technology, 2014, Vol 7, p.625 (Non-Patent Literature 4)).

[0018] 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).

[0019] The notation "g / mol (or mol)" is an abbreviation for the number of grams per mole.

[0020] The term "CH" is an abbreviation for contact-hole lithography, and the term "L / S" is an abbreviation for line-and-space lithography.

[0021] In the following descriptions, "Synth." is an abbreviation for "synthesis," "Comp." is an abbreviation for "comparative," and "Ex." is an abbreviation for "Example."

[0022] The terms oligomer, oligo, and oligomeric polymer used herein refer to low Tg This refers to additives, and specifically to low molecular weight polymers having a molecular weight range specific to the additive types shown here.

[0023] The term "acrylic" as used herein includes repeating units derived from acrylate derivatives, such as repeating units derived from acrylate derivatives having the following structure: In the following formula, the Alkyl portion may be a C1-C8 alkyl group, and Xacryl is either H or a C1-C4 alkyl group:

[0024] [ka] The term "styrene-based" as used herein includes repeating units derived from styrene derivatives, such as repeating units derived from styrene derivatives having the following structure: In the following formula, the Xsty portion is H or a C1-C4 alkyl group, and the Rsty portion is H or a C1-C8 portion:

[0025] [ka] composition One aspect of the present invention is a composition comprising the following components a), b), and c): a) is one type of block copolymer component, or a blend of at least two types of block copolymers. b) is at least one kind of low T g These are oligomeric polystyrene-based additives, and each additive is individually controlled in the temperature range of approximately 68.0°C to approximately 90.0°C. g It has and M in the range of approximately 2,500 g / mol to approximately 8,000 g / mol w It has polydispersity from 1.20 to about 1.80, and furthermore, the styrene-based additive is • At least one styrene-based homopolymer produced by radical polymerization, - At least one styrene-based random copolymer produced by radical polymerization, wherein the repeating units consist only of styrene-based repeating units and contain at least two types of styrene-based repeating units, and A mixture of at least one styrene-based homopolymer and at least one styrene-based random copolymer, Selected from the group consisting of, c) is an organic spin-casting solvent.

[0026] In one aspect of the composition according to the present invention described above, it comprises essentially components a), b) and c). In one aspect of this embodiment, the statement “complies essentially with” means that there may be other components that do not affect the performance of the material, and such other components are present in total at a concentration of no more than about 10% by weight of the composition. In another aspect of this embodiment, these other components are present in total at a concentration of no more than about 5% by weight of the composition. In yet another aspect of this embodiment, these other components are present in total at a concentration of no more than about 1% by weight. In yet another aspect of this embodiment, these other components are present in total at a concentration of no more than about 0.5% by weight.

[0027] In another aspect of the composition according to the present invention described above, it comprises components a), b), and c).

[0028] 1) Component b) Low T g Oligomer-type polystyrene additives In another aspect of the composition according to the present invention described above, this means that each component b) additive is individually heated in the range of about 68.0°C to about 90.0°C. gThis has the following characteristics. In one other aspect of this embodiment, this is a range from about 68.5°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.6°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.7°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.7°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.8°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.8°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.9°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 69.0°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 69.1°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 69.2°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 69.3°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 69.3°C to about 89.9°C. In one other aspect of this embodiment, this is a range from about 69.3°C to about 89.8°C. In one other aspect of this embodiment, this is a range from about 69.0°C to about 89.7°C. In one other aspect of this embodiment, this is a range from about 69.3°C to about 89.7°C.

[0029] In one other aspect of this embodiment, this is a range from about 68.0°C to about 90.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 89.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 88.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 87.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 86.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 85.0°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 84.9°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 84.8°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 84.7°C. In one other aspect of this embodiment, this is a range from about 68.0°C to about 84.6°C. In another aspect of this embodiment, this is a range from about 68.0°C to about 84.5°C. In another aspect of this embodiment, this is a range from about 68.0°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.1°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.2°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.3°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.3°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.4°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.5°C to about 84.4°C. In one other aspect of this embodiment, this is a range from about 68.6°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.7°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.8°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 68.9°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 69.0°C to about 84.4°C. In another aspect of this embodiment, this is a range from about 69.1°C to about 84.4°C.In one other aspect of this embodiment, this ranges from approximately 69.2°C to approximately 84.4°C. In another other aspect of this embodiment, this ranges from approximately 69.3°C to approximately 84.4°C.

[0030] In one aspect of the composition according to the present invention described above, this is the case in which each component b) additive individually has polydispersity in the range of about 1.30 to about 1.80. In one aspect of this embodiment, this is the range of about 1.35 to about 1.80. In one aspect of this embodiment, this is the range of about 1.36 to about 1.80. In one aspect of this embodiment, this is the range of about 1.37 to about 1.80. In one aspect of this embodiment, this is the range of about 1.38 to about 1.80. In one aspect of this embodiment, this is the range of about 1.39 to about 1.80. In one aspect of this embodiment, this is the range of about 1.40 to about 1.80. In one aspect of this embodiment, this is the range of about 1.40 to about 1.75. In one aspect of this embodiment, this is the range of about 1.40 to about 1.74. In one other aspect of this embodiment, this ranges from about 1.40 to about 1.73. In another aspect of this embodiment, this ranges from about 1.40 to about 1.72. In another aspect of this embodiment, this ranges from about 1.40 to about 1.71. In another aspect of this embodiment, this ranges from about 1.40 to about 1.71. In another aspect of this embodiment, this ranges from about 1.40 to about 1.70. In another aspect of this embodiment, this ranges from about 1.40 to about 1.69.

[0031] In another aspect of the composition according to the present invention, this is the at least one low T of component b). g Each oligomeric polystyrene additive is individually available in a range of approximately 2,700 g / mol to approximately 8,000 g / mol. wThis has the following characteristics: In one other aspect of this embodiment, this is in the range of about 2,800 g / mol to about 8,000 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,900 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,800 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,700 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,600 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,500 g / mol. In one other aspect of this embodiment, this is in the range of about 2,900 g / mol to about 7,400 g / mol. In one other aspect of this embodiment, this ranges from about 2,900 g / mol to about 7,300 g / mol. In another aspect of this embodiment, this ranges from about 2,900 g / mol to about 7,200 g / mol. In another aspect of this embodiment, this ranges from about 2,900 g / mol to about 7,100 g / mol. In another aspect of this embodiment, this ranges from about 2,900 g / mol to about 7,000 g / mol. In another aspect of this embodiment, this ranges from about 2,900 g / mol to about 6,900 g / mol. In another aspect of this embodiment, this ranges from about 2,900 g / mol to about 6,800 g / mol.

[0032] In one other aspect of the composition, component b) additive is either at least one of the styrene homopolymers or at least one of the styrene random copolymers produced by radical polymerization. In one aspect of this embodiment, this consists of one of the styrene homopolymers produced by radical polymerization.

[0033] In another aspect of the compositions described herein, component b) additive is at least one of the styrene homopolymers, further comprising structure (A) having repeating units having structure (I). In structure (I), n1 is the number of repeating units, indicating that these are repeating units, R A1 , R A2 , R A3 , R A4 , R A5 Each is individually selected from H or C1-C8 alkyl, and R m1 is H or methyl, and the styrene-based 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, where Rr1 is a C1-C8 alkyl and Rr2 is selected from C1-C8 alkyl, and Rr is a cyano moiety (-CN) or a carbonyl alkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety. In one other aspect of this embodiment, R A1 , R A2 , R A3 , R A4 , R A5 R is individually selected from H or C1-C4 alkyl groups. In one other aspect of this embodiment, R A1 , R A2 , R A3 , R A4 , R A5 is H. In one other aspect of this embodiment, Rm1 is H. In one other aspect of this embodiment, R A1 , R A2 , R A3 , R A4 , R A5 H is and R m1 is H. In one other aspect of this embodiment, Rr is the cyano moiety (-CN). In one other aspect of this embodiment, the component b) additive consists of one of the styrene homopolymers of structure (A). In one other aspect of this embodiment, the component b) additive is at least two different styrene homopolymers of structure (A).

[0034] [ka] In one aspect of the composition, the component b) additive is either at least two of the styrene homopolymers or at least two of the styrene random copolymers, both produced by radical polymerization. In one aspect of this embodiment, this is two of the styrene homopolymers, produced by radical polymerization.

[0035] In another aspect of the composition, component b) additive is at least one of the styrene-based random copolymers having structure (B), wherein the repeating units consist of two different repeating units of structure (II) and (III), where n2 and n3 are the number of these repeating units, indicating that they are repeating units, and R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B8 , R B9 , and R B10 R is independently selected from H or C1-C8 alkyl groups. m2 , R m3 R is independently selected from H or methyl; and the styrene-based random copolymer has two terminal groups as shown in structure (B), one of which is H and the other is a methyl moiety substituted with Rr3, Rr4 and Rr5, where Rr4 is a C1-C8 alkyl, Rr5 is selected from C1-C8 alkyl, and Rr3 is a cyano moiety (-CN) or a carbonyl alkyl moiety (-C(C=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety. In one other aspect of this embodiment, R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B8 , R B9 , and R B10is independently selected from H or C1-C4 alkyl. In one other aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 and R B6 、R B7 、R B8 、R B9 、and at least one of R B10 is C1-C4 alkyl, and in one aspect of this embodiment, this is methyl. In one other aspect of this embodiment, R B1 、R B2 、R B3 、R B4 、R B5 are all H, and at least one of R B6 、R B7 、R B8 、R B9 、and R B10 is C1-C4 alkyl; in one aspect of this embodiment, this is methyl. In one other 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 all H. In one other aspect of these embodiments, R m2 and R m3 are both H. In one other aspect of this embodiment, Rr3 is a cyano moiety (-CN). In one other aspect of this embodiment, the component b) additive consists of one of the styrene random copolymers of structure (B). In one other aspect of this embodiment, the component b) consists of at least two different said random styrene copolymers of structure (B).

[0036]

Chemical formula

[0037] In another aspect of the composition, the component b) additive is a mixture of at least one of the styrene-based homopolymers of structure (A) and at least one of the styrene-based random copolymers of structure (B). In this aspect, the styrene-based homopolymer has structure (A), which has a repeating unit of structure (I) and two end groups shown in structure (A). In the repeating unit of structure (I), n1 is the number of repeating units, indicating that this is a repeating unit, and R A1 , R A2 , R A3 , R A4 , R A5 is individually selected from H or C1-C8 alkyl, and R m1 is H or methyl. Further, as shown in structure (A), one of the end groups is H, and the other is a methyl moiety substituted by Rr, Rr1, and Rr2, where Rr1 is C1-C8 alkyl, Rr2 is selected from C1-C8 alkyl, and Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is C1-C8 alkyl or an aryl moiety. In another aspect of this embodiment, R A1 , R A2 , R A3 , R A4 , R A5 is individually selected from H or C1-C4 alkyl. In another aspect of this embodiment, R A1 , R A2 , R A3 , R A4 , and R A5 are all H. In another aspect of this embodiment, Rm1 is H. In another aspect of this embodiment, R A1 , RA2 , R A3 , R A4 , R A5 H is and R m1 is H. In one other aspect of this embodiment, Rr is the cyano moiety (-CN).

[0038] Furthermore, in this embodiment of the present invention, 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 the styrene random copolymer of structure (B), the repeating unit consists of two repeating units of structure (II) and (III), and the styrene random copolymer has two terminal groups, where in structures (II) and (III), n2 and n3 are the number of these repeating units, indicating that these are repeating units, and R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B8 , R B9 , and R B10 R is independently selected from H or C1-C8 alkyl groups. m2 , R m3 R is independently selected from H or methyl. Two terminal groups are shown in structure (B), one of which is H and the other is a methyl moiety substituted by Rr3, Rr4 and Rr5, where Rr4 is a C1-C8 alkyl, Rr5 is selected from C1-C8 alkyls, and Rr3 is a cyano moiety (-CN) or a carbonyl alkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety. In one other aspect of this embodiment, R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B8 , R B9 , and R B10R is independently selected from H or C1-C4 alkyl groups. In one other aspect of this embodiment, R B1 , R B2 , R B3 , R B4 , R B5 All are H, and R B6 , R B7 , R B8 , R B9 , and R B10 At least one of them is a C1-C4 alkyl group; in one aspect of this embodiment, this is methyl. In one 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 All of these are H. In one of the other aspects of these embodiments, R m2 and R m3 Both are H. In another aspect of this embodiment, Rr3 is the cyano moiety (-CN).

[0039] [ka]

[0040] 2) Component a) Block copolymer component 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.

[0041] In another aspect of the composition, component a) is an ABA-type triblock copolymer component selected from the group consisting of ABA-type triblock copolymer a-1t), ABA-type triblock copolymer a-2t), and a blend of two ABA-type triblocks of different compositions, wherein a-1t) is an ABA-type triblock copolymer comprising an intermediate B) styrene-based block segment of repeating units having a styrene-based structure (I') and two terminal acrylic-based block A) segments of the same length having a structure (II'), wherein R1 and R3 are independently selected from H and C1-C4 alkyl, and R2 is H or C1 The triblock copolymer a-1t) has polydispersity from about 1.0 to about 1.1 and a molecular weight from about 70,000 g / mol to about 350,000 g / mol. n It holds.

[0042] [ka] Furthermore, from this perspective, the ABA-type triblock copolymer a-2t) is an ABA-type triblock copolymer comprising an intermediate B) block segment of repeating units having a styrene-based structure (Ia) and two terminal A) segments of the same length having an acrylic-based structure (IIa), where R 1a and R 3a R is independently selected from H and C1-C4 alkyl groups. 2a is H or C1-C8 alkyl, R 4a These are C1-C8 alkyl groups.

[0043] Furthermore, from this perspective, the mole percentage values ​​based on the total number of moles of repeating units of structures (Ia) and (IIa) are approximately 40 mol% to approximately 80 mol% for styrene-based repeating units of structure (Ia), and approximately 20 mol% to approximately 60 mol% for acrylic-based repeating units of structure (IIa), and The respective values ​​of the mole percent of the repeating units of structures (Ia) and (IIa) are selected from their respective ranges such that the total number of moles of the repeating units of structures (Ia) and (IIa) sums up to 100 mol%. Finally, in this respect, the triblock copolymer a-2t) has polydispersity from about 1.0 to about 1.1 and M from about 70,000 g / mol to about 350,000 g / mol. n It holds.

[0044] [ka] In another aspect of the composition, more specifically, R1, R 1a , R2 and R 2a H is H, and R3, R 3a , R4 and R 4a is methyl. In one aspect of the composition in which component a) is the previously described triblock copolymer, in one embodiment, component a) is selected from a triblock copolymer of structure (ABA-1), a triblock copolymer of structure (ABA-2), and a mixture of these two types of block copolymers, where mt, mta, nt and nta are the number of repeating units, and R 1s , R 1sa , R 2s , and R 2sa These are independently hydrogen, C1-C8 alkyl, and -N(R 3s )2, -OR 4s , and Si(R 5s) Selected from 3, here R 3s , R 4s and R 5s R1 is independently selected from C1-C4 alkyl groups, and R1 and R3 are independently selected from H and C1-C4 alkyl groups, R2 is H or C1-C8 alkyl group, and R4 is C1-C8 alkyl group. Furthermore, in this embodiment, the mol% values ​​based on the total number of moles of both styrene-based and acrylic repeating units in structure (ABA-1) are approximately 40 mol% to approximately 80 mol% for the styrene-based repeating units and approximately 20 mol% to approximately 60 mol% for the acrylic repeating units, where the respective mol% values ​​of the repeating units in structures (I') and (II') are selected from their respective ranges such that the total number of moles of the repeating units in structures (I') and (II') sum to 100 mol%, and the triblock copolymer of structure (ABA-1) has a polydispersity of approximately 1.0 to approximately 1.1, and a molecular weight of approximately 70,000 g / mol to approximately 350,000 g / mol. n The triblock copolymer having and structure (ABA-2) exhibits polydispersity from about 1.0 to about 1.1, and a molecular weight from about 70,000 g / mol to about 350,000 g / mol. n It has. In one other aspect of this embodiment, R1, R 1a , R2, R 2a , R 1s , R 1sa , R 2s , R 2sa H is H, and R3, R 3a , R4, and R 4ais methyl. In one aspect of this embodiment, component a) consists solely of the ABA-type triblock copolymer of structure (ABA-1), in another aspect of this embodiment, component a) consists solely of the ABA-type 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, the blend of a-1t) and a-2t) has a total mol% of styrene repeating units of structures (I') and (Ia) ranging from about 60 mol% to about 75 mol%, and a total mol% of acrylic repeating units of structures (II') and (IIa) ranging from about 25 mol% to about 40 mol%.

[0045] [ka] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2).

[0046] In this view, a-1) is a diblock copolymer of block A) having styrene repeating units having a styrene structure (I') and block B) having an acrylic structure (II'), where R1 and R3 are independently selected from H and C1-C4 alkyl, R2 is H or C1-C8 alkyl, and R4 is C1-C8 alkyl. Furthermore in this view, the molar percentage values ​​based on the total number of moles of the repeating units of structures (I') and (II') are approximately 40 mol% to approximately 80 mol% for the repeating units of structure (I') and approximately 20 mol% to approximately 60 mol% for the repeating units of structure (II'). Furthermore in this view, the respective molar percentage values ​​for the repeating units of structures (I') and (II') are selected from their respective ranges such that the total number of moles of the repeating units of structures (I') and (II') sum to 100 mol%. Furthermore, from this perspective, the diblock copolymer a-1) has polydispersity from about 1.0 to about 1.1, and M from about 50,000 g / mol to about 150,000 g / mol. n It holds.

[0047] [ka] Furthermore, in another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), where a-2) is a diblock copolymer of block Aa) having repeating units having a styrene structure (Ia) and block Ba) having repeating units having an acrylic structure (IIa), where R 1a and R 3a R is independently selected from H or C1-C4 alkyl groups, 2a is H or C1-C8 alkyl, R 4aThe C1-C8 alkyl group is also included. Furthermore, from this perspective, the mole percentage values ​​based on the total number of moles of the repeating units of structure (Ia) and (IIa) are approximately 40 mol% to 80 mol% for the repeating units of structure (Ia) and approximately 20 mol% to 60 mol% for the repeating units of structure (IIa). Furthermore, from this perspective, the respective mole percentage values ​​for the repeating units of structure (Ia) and (IIa) are selected from their respective ranges such that the total number of moles of the repeating units of structure (Ia) and structure (IIa) sum to 100 mol%. Furthermore, from this perspective, the diblock copolymer a-2) has polydispersity from approximately 1.0 to approximately 1.1 and M from approximately 30,000 g / mol to approximately 90,000 g / mol. n It holds.

[0048] [ka] Furthermore, in another aspect of the composition, component a) is selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), R1, R 1a , R2 and R 2a H is H, and R3, R 3a , R4 and R 4a It is methyl.

[0049] In another aspect of the embodiment in which component a) is diblock copolymer a-1) and a-2), these have structure (IS) and structure (ISa), respectively, where R 1s , R 1sa , R 2s , and R 2sa These are independently hydrogen, C1-C8 alkyl, and -N(R 3s )2, -OR 4s , and Si(R 5s ) Selected from 3, here R 3s , R 4s and R 5s R is independently selected from C1-C4 alkyl groups. In one aspect of this embodiment, 1s , R 2s , R 1sa , and R2sa It is hydrogen.

[0050] [ka] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1) and a blend of a-1) and a-2). In this embodiment, diblock copolymer component a-1) and / or diblock copolymer component a-2) independently have polydispersity in the range of 1.00 to about 1.03. In another aspect of this embodiment, diblock copolymer component a-1) has polydispersity in the range of about 93,000 g / mol to about 105,300 g / mol n It holds.

[0051] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1) and a blend of a-1) and a-2), with respect to diblock copolymer component a-1), the molar percentage values ​​are such that the repeating units of structure (I') are from about 40 mol% to about 60 mol%, and the repeating units of structure (II') are from about 40 mol% to about 60 mol%.

[0052] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1) and a blend of a-1) and a-2), with respect to diblock copolymer component a-1), the molar percentage values ​​are such that the repeating units of structure (I') are from about 60 mol% to about 75 mol%, and the repeating units of structure (II') are from about 25 mol% to about 40 mol%.

[0053] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1) and a blend of a-1) and a-2), with respect to diblock copolymer component a-1), the molar percentage values ​​are such that the repeating units of structure (I') range from about 40 mol% to about 80 mol%, and the repeating units of structure (II') range from about 20 mol% to about 60 mol%.

[0054] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1) and a blend of a-1) and a-2), with respect to diblock copolymer component a-1), the molar percentage values ​​are such that the repeating units of structure (I') are from about 40 mol% to about 60 mol%, and the repeating units of structure (II') are from about 40 mol% to about 60 mol%.

[0055] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-2) and a blend of a-1) and a-2), the two different diblock copolymer components a-2) independently have polydispersity in the range of 1.00 to about 1.03.

[0056] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-2) and a blend of a-1) and a-2), wherein the diblock copolymer component a-2) is M from about 40,800 g / mol to about 61,200 g / mol n It holds.

[0057] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), in the case of a single block copolymer a-1) or a-2) or a blend of a-1) and a-2), the total molar percentage of repeating units of structure (I') and (Ia) is from about 40 mol% to about 60 mol%, and the total molar percentage of repeating units of structure (II') and (IIa) is from about 40 mol% to about 60 mol%.

[0058] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), in the case of a single block copolymer a-1) or a-2) or a blend of a-1) and a-2), the total molar percentage of repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and the total molar percentage of repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%.

[0059] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), where component a) is a blend of a-1) and a-2).

[0060] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), component a) is either a-1) or a-2).

[0061] In another aspect of the composition, component a) is present in an amount ranging from about 0.5% to about 2.0% by weight of the whole composition.

[0062] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), the amount of component a) is from about 0.5% by weight to about 2.0% by weight of the whole composition.

[0063] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), the total mol% of the styrene repeating units of structures (I') and (Ia) is from about 40 mol% to about 60 mol%, and the total mol% of the acrylic repeating units of structures (II) and (IIa) is from about 40 mol% to about 60 mol%.

[0064] In another aspect of the composition, component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), the total mol% of styrene repeating units of structures (I') and (Ia) is from about 65 mol% to about 70 mol%, and furthermore, the total mol% of acrylic repeating units of structures (II') and (IIa) is from about 30 mol% to about 35 mol%.

[0065] In another aspect of the composition, component a) is selected from the group consisting of triblock copolymer a-1t), triblock copolymer a-2t), and a blend of a-1t) and a-2t), the total mol% of styrene repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and the total mol% of acrylic repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%.

[0066] In another aspect of the composition, component a) is selected from the group consisting of triblock copolymer component a-1t), triblock copolymer a-2t), and a blend of a-1t) and a-2t), wherein the total mol% of the styrene repeating units of structures (I') and (Ia) is from about 40 mol% to about 60 mol%, and further, the total mol% of the acrylic repeating units of structures (II') and (IIa) is from about 40 mol% to about 60 mol%, and component b) is the low T additive g The oligomeric polystyrene additive is at least one of the styrene homopolymers produced by radical polymerization.

[0067] In any of the above embodiments, component b) is in an amount of about 0.05% to about 2.0% by weight of the whole composition including the solvent. In one other aspect of this embodiment, component b) as an additive may be in an amount of about 0.05% to about 0.5% by weight of the total weight of the composition including the organic solvent for spin casting. In one other aspect of this embodiment, this is in an amount of about 0.08% to about 0.4% by weight. In one other aspect of this embodiment, this is in an amount of about 0.1% to about 0.4% by weight. In one other aspect of this embodiment, this is in an amount of about 0.15% to about 0.4% by weight. In yet another aspect of this embodiment, this is in an amount of about 0.2% to about 0.3% by weight.

[0068] 3) Component c) Organic solvent for spin casting With respect to component c), suitable organic solvents for spin casting that dissolve the compositions according to 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); carboxylates, such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, such as diethyl oxilate and dimethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; Examples include ketone esters, such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, 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; ketone ether derivatives, such as methyl diacetone alcohol; ketone alcohol derivatives, such as acetol or diacetone alcohol; ketals or acetals, such as 1,3-dioxalane and diethoxypropane; lactones, such as butyrolactone; and amide derivatives, such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0069] In addition, the compositions of the present invention may further include surfactants, inorganic polymers; additives comprising small molecules, inorganic molecules, surfactants, photoacid generators, thermoacid generators, quenchers, curing agents, crosslinking agents, chain extenders, and the like; and additives selected from the group comprising combinations of at least one of the above, wherein one or more of the additional components and / or additives co-assemble with the block copolymer to form a block copolymer assembly.

[0070] processing Another aspect of the present invention is a method comprising the following steps: i) A step of forming a neutral layer coating on a substrate, ii) A step of coating the neutral layer with any one of the compositions according to the present invention described herein to form a film, iii) The step of baking the film in an inert gas atmosphere at a temperature of about 240°C to about 280°C to form a self-assembling film, and iv) Etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern.

[0071] Another aspect of this invention is a method for forming a line-and-space array, ia) A step of forming a neutral layer coating on a substrate, iia) a composition in which component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), and the total mol% of styrene repeating units of structure (I') and (Ia) is from about 40 mol% to about 60 mol%, and the total mol% of acrylic repeating units of structure (II') and (IIa) is from about 40 mol% to about 60 mol%, is coated onto the neutral layer to form a film. iiia) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and iva) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method includes the above.

[0072] Another aspect of this invention is a method for forming a contact hole array, ib) A step of forming a neutral layer coating on a substrate, iib) A step of forming a film by coating the neutral layer with a composition in which component a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), and the total mol% of styrene repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and furthermore, the total mol% of acrylic repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%, iiib) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and ivb) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method includes the above.

[0073] Another aspect of this invention is a method for forming a line-and-space array, ic) A step of forming a neutral layer coating on a substrate, iic) component a) is selected from the group consisting of triblock copolymer component a-1t), triblock copolymer a-2t), and a blend of a-1t) and a-2t), and the total mol% of styrene repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and the total mol% of acrylic repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%, and the composition is coated onto the neutral layer to form a film. ii) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and IVC) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method includes the above.

[0074] Another aspect of this invention is a method for forming a contact hole array, id) Step of forming a neutral layer coating on a substrate, The step of coating the neutral layer with a composition in which component a) is selected from the group consisting of triblock copolymer component a-1t), triblock copolymer a-2t), and a blend of a-1t) and a-2t), and the total mol% of styrene repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and the total mol% of acrylic repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%, thereby forming a film. iiid) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and ivd) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method includes the above. [Examples]

[0075] Chemicals and Characterization Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich Ltd. (3050 Spruce Street, St. Louis, Missouri 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”, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005) (Non-Patent Literature 5)).

[0076] All synthesis experiments were performed in an N2 atmosphere. Lithography experiments were performed as described herein.

[0077] Lithography experiments were performed using the TEL Clean ACT8 track. SEM images were taken using the NanoSEM 3D from Applied Materials. Scanning electron microscope images are shown at either 2FOV magnification or 4FOV magnification (field of view (FOV) = 5 μm).

[0078] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembling film block copolymers of methyl methacrylate and styrene.

[0079] Unless otherwise specified, molecular weight measurement (or, to put it another way, M w M n (Polydispersible) 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 The measurements were performed using gel permeation chromatography (PSS Inc., Germany) equipped with an Åμ-Ultrillagel column, with THF solvent as the eluent. Polystyrene polymer standards were used for calibration. In these measurements, the notation "K" is synonymous with 1000 g / mol or 1000 Daltons.

[0080] The glass transition temperature was measured using DSC (Digital Spectroscopy) with a heating rate of 10°C / min under nitrogen using a TA Instruments DSC Q1000. g The temperature was measured from 0 to 120°C in the first heating scan. The midpoint of the endothermic transition was taken into consideration.

[0081] The TGA analysis reported here was performed using a TA Instruments TGA 550 under nitrogen at a heating rate of 10°C / min. Temperatures were recorded at weight losses of 1% and 5%.

[0082] 1 The 1H NMR spectrum was recorded in CDCl2 using a Bruker Advanced III 400 MHz spectrometer.

[0083] Synthesis of neutral layer and block copolymer Synthesis Example 1: Synthesis of P(S-co-VBCB-co-MMA)-Bz-OH neutral layer material The synthesis of the azo initiator is described in US9574104B1 (Patent Document 1), and this was used in this polymerization. Styrene (143.8 g, 1.38 mol), methyl methacrylate (184.9 g, 1.84 mol), 4-vinylbenzocyclobutene (180.0 g, 1.38 mol), and 2-butanone (620 g) were added to a 2 L volume four-neck round-bottom flask equipped with a stirrer bar, reflux condenser, temperature controller, and nitrogen sparging tube. This reaction mixture was stirred for 20 minutes while spraying nitrogen. This mixture was heated in a heated mantle using a temperature controller set to 80°C. At 80°C, a solution of the azo initiator (3.05 g, 5.07 mmol) in 2-butanone (12.2 g) was added over 1 minute. This mixture was heated at 80°C for 20 hours. An additional solution of azo initiator (1.22 g) in 2-butanone (4.88 g) was added over 1 minute. The mixture was heated 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 dried in an oven. The residue was redissolved in THF (15% solids) and precipitated in MeOH (15 L). The precipitate was collected by vacuum filtration and dried in an oven. The solids were redissolved in 2-butanone (1900 g), filtered through a 0.2 μm nylon filter, and slowly precipitated in IPA (15 L). The precipitate was collected by vacuum filtration and dried in an oven. The polymer is 290 g (57.0%) of off-white solids. GPC: 38,842 g / mol M n , 90,053 g / mol M w 2.30 PDI.

[0084] Synthesis Example 2: Synthesis of P(Sb-MMA)(78K-b-39K) Styrene and methyl methacrylate monomers were distilled into ampoules calibrated in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using a stainless steel cannula. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of this reactor was reduced to -78°C using a dry ice-acetone bath. After titrating for impurities, 0.2 mL (1.4 M solution) of sec-butyllithium was added to the reactor. Then, 20 g (0.192 mol) of styrene was added to the reactor from its ampoule with rapid stirring. The reaction solution changed color to yellow-orange, and the reaction was stirred for 30 minutes. Next, 0.06 g (0.0003 mol) of 1,1'-diphenylethylene (DPE) in 2.5 mL of anhydrous toluene was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark reddish-brick color. This suggests that the styryllithium active center was converted to a delocalized DPE-added carbanion. After stirring for 2 minutes, a small amount (2 mL) of the reaction mixture was taken for PS block molecular weight analysis. Methyl methacrylate (9.98 g, 0.0998 mol) was then added via an ampoule. This reaction was stopped after 30 minutes with 1 mL of degassed methanol. The polymer was precipitated in excess isopropanol (5 times the volume of the polymer solution) containing 10% water, filtered, and dried under vacuum at 55°C for 12 hours to recover the block copolymer, yielding 28 g of P(Sb-MMA) (94% yield) consisting of 66 mol% polystyrene block and 34 mol% polymethyl methacrylate block.

[0085] 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column is performed with the first P(SDPE) block being M relative to the PS calibration standard. n (GPC) = 64,622 g / mol and M w / Mn It was shown that it has = 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.

[0086] Synthesis Example 3: Synthesis of P(Sb-MMA)(34K-b-17K) PS-PMMA(34-17K) was synthesized using the same procedure as described in Example 2. The target M of the PS block and PMMA block n To achieve this, 0.42 mL of a 1.4 M solution of sec-butyllithium was added while maintaining the same amounts of styrene and MMA as in Example 2. 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column is performed with the first P(SDPE) block being M relative to the PS calibration standard. n (GPC) = 34,872 g / mol and M w / M n It was shown that it has = 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 ¹H NMR showed a 66.1 mol% polystyrene block and a 33.9 mol% polymethyl methacrylate block.

[0087] Synthesis Example 4: Synthesis of P(Sb-MMA)(45k-b-51k) P(Sb-MMA)(45K-b-51K) was synthesized using the same procedure as described in Example 2. The amounts of initiator and monomer were varied to achieve the desired Mn and composition of the PS and PMMA blocks. Briefly, 20 g (0.192 mol) of styrene was polymerized with 0.32 mL (1.4 M solution) of sec-butyllithium. Then, 0.095 g (0.0005 mol) of 1,1'-diphenylethylene (DPE) in 2.5 ml of anhydrous toluene was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark reddish-brick color. This suggests that the styryllithium active center was converted to a delocalized DPE-added carbanion. After stirring for 2 minutes, a small amount (2 mL) of the reaction mixture was taken for molecular weight analysis of the PS block. Then, methyl methacrylate (22.85 g, 0.23 mol) was added via an ampoule. This reaction was stopped after 30 minutes using 1 mL of degassed methanol. The product was precipitated in excess isopropanol (5 times the volume of the polymer solution) containing 10% water, filtered, and dried under vacuum at 55°C for 12 hours to recover the block copolymer, yielding 40 g of P(Sb-MMA) (94% yield) consisting of 46.9 mol% polystyrene block and 53.1 mol% polymethyl methacrylate block.

[0088] 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column is performed with the first P(SDPE) block being M relative to the PS calibration standard. n (GPC) = 45,048 g / mol and M w / M n It was shown that it has = 1.04. The molecular weight of the diblock copolymer obtained from GPC is M n,PS-b-PMMA = 88,348 g / mol and M w / M n = 1.02.

[0089] Synthesis of the present invention and comparative h-PS oligomer type additives Synthesis Example 5: Synthesis of h-PS Additive 1 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected, redissolved as a 15% solid solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected and dried overnight in a vacuum at 50°C. 36.7 g (60%) of white polymer, GPC: 3,436 g / mol Mn, 5,455 g / mol M w 1.59 PDI.

[0090] Synthesis Example 6: Synthesis of h-PS Additive 2 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected, redissolved as a 15% solid solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected and dried overnight in a vacuum at 50°C. 263 g (67%) of white polymer, GPC: 4,267 g / mol Mn, 6,814 g / mol M w 1.60 PDI.

[0091] Synthesis Example 7: Synthesis of h-PS Additive 3 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected, redissolved as a 15% solid solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected and dried overnight in a vacuum at 50°C. 33.9 g (69%) of white polymer, GPC: 4,729 g / mol Mn, 7,698 g / mol M w 1.63 PDI.

[0092] Synthesis Example 8: Synthesis of h-PS comparative additive 4 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected by filtration, redissolved as a 15% solids solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected by filtration and dried overnight in a vacuum at 50°C. 44 g (72%) of white polymer, GPC: 9,301 g / mol Mn, 15,538 g / mol M w 1.67 PDI.

[0093] Synthesis Example 9: Synthesis of h-PS additive 5 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 nitrogen was sprayed for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected, redissolved as a 15% solid solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected and dried overnight in a vacuum at 50°C. 16.2 g (28%) of white polymer, GPC: 1,952 g / mol M n , 2,898 g / mol M w 1.48 PDI.

[0094] Synthesis Example 10: Synthesis of h-PS additive 6 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected by filtration, redissolved as a 15% solids solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected by filtration and dried overnight in a vacuum at 50°C. 26.7 g (45%) of white polymer, GPC: 2,425 g / mol Mn, 3,386 g / mol M w 1.40 PDI.

[0095] Synthesis Example 11: Synthesis of h-PS additive 7 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 sprayed with nitrogen for 30 minutes. This mixture was heated in an oil bath at 80°C for 16 hours. The mixture was cooled to room temperature, diluted with acetone, and precipitated in methanol. The polymer was collected by filtration, redissolved as a 15% solids solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected by filtration and dried overnight in a vacuum at 50°C. 39.1 g (65%) of white polymer, GPC: 2,323 g / mol Mn, 3,934 g / mol M w 1.69 PDI.

[0096] Synthesis Example 12: Synthesis of h-PS comparative additive 1 Styrene (27.3 g, 262 mmol) and cyclohexane (181 g) were added to a Schlenk flask and degassed three times using freeze-thaw technique. This mixture was titrated with sec-BuLi until it remained yellow. Sec-BuLi (2.79 mL, 1.4 M, 4 mmol in cyclohexane) was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. This mixture was diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved as a 15% solids solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected and dried overnight in vacuum at 50°C. 19 g (70%) of white polymer, GPC: 5475 g / mol Mn, 5937 g / mol M w 1.08 PDI.

[0097] Synthesis Example 13: Synthesis of h-PS comparative additive 2 Styrene (31.2 g, 300 mmol) and cyclohexane (207 g) were added to a Schlenk flask and degassed three times using freeze-thaw technique. This mixture was titrated with sec-BuLi until it remained yellow. Sec-BuLi (2.79 mL, 1.4 M, 4 mmol in cyclohexane) was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. This mixture was diluted with acetone and precipitated in methanol. The polymer was collected by filtration, redissolved as a 15% solids solution in ethyl acetate, washed three times with DI water, and precipitated in isopropanol. The polymer was collected by filtration and dried overnight in vacuum at 50°C. 24 g (76%) of white polymer, GPC: 6700 g / mol Mn, 7300 g / mol M w 1.09 PDI.

[0098] The experiments described below were carried out by adjusting the weight percentage of specific oligomeric styrene additives to affect the observed morphology and LCDU and twist dependence (which represent the quality of contact holes and the degree of overlap of contact holes when perfectly aligned on the pre-pattern) of annealable block copolymer formulations. Surprisingly, it was found that increasing the weight percentage content of oligomeric polystyrene additives provided improved performance only when certain types of these oligomers were used. Specifically, in the verification of homo-oligomeric polystyrene, which is 100 mol% homopolymerized styrene (h-PS), such materials produced by controlled synthesis methods such as anionic polymerization, for example, imparted very poor morphology to the block copolymer when used in DSA processing, while the M defined in the claims w It was unexpectedly discovered that h-PS oligomer-type additives produced by radical polymerization, having a range, exhibit good shape during the same DSA processing of block copolymers, and furthermore, there is a strong correlation between the molecular weight of these additives and their effect in giving good shape to the block copolymer formulation during self-assembly annealing. In fact, surprisingly, the M defined in the claims wEven h-PS outside the specified range exhibited poor morphology during self-assembly when blended with block copolymers. While not theoretically constrained, this phenomenon suggests that, in BCP formulations, the dynamics of annealing during self-assembly were unexpectedly strongly influenced by several complex mobility factors imparted by oligomeric additives, which have relatively small sizes and chemically random oligomeric structures that contribute to the better dynamics of these BCP formulations.

[0099] Synthesis and properties of h-PS oligomers Synthesis Examples 5-13 illustrate how the present and comparative h-PS oligomer materials were synthesized, and Tables 1 and 2 summarize the properties of these materials, as well as their performance when used as additives for block copolymers during annealing on a substrate coated with a neutral layer.

[0100] The h-PS oligomers according to the present invention shown in Table 1 and the comparative formulations shown in Table 2 were prepared. These formulations contained the h-PS oligomers in a proportion of 20% by weight of the total solids and the block copolymer (BCP) of Synthesis Example 2 (synthesis of P(Sb-MMA)(78K-b-39K)) in a proportion of 80% by weight of the total solids, and were diluted to a solids content of 1.2% by weight in PGMEA as a spin-casting solvent. These solutions were filtered using a 0.2 micron PTFE filter.

[0101] The following processing results and all additives listed in Tables 1 and 2 were blended with the block copolymer at a ratio of 20% by weight. The block copolymer accounted for 80% by weight of the total additives and block copolymer. Specifically, this was done using 0.8 grams of PS-b-PMMA, 0.2 grams of the test additive, and 82.3 grams of PGMEA.

[0102] Processing conditions: Example 1: Synthesis of P(S-co-VBCB-co-MMA)-Bz-OH A neutral layer material was spin-coated onto a Si wafer from a 1.2 wt% solution in PGMEA, and then baked at 250°C for 2 minutes to form a 7 nm thick crosslinked neutral layer. Each formulation containing h-PS oligomer-type additives 1-3 and 5-7, and comparative additives 1, 2, and 4, was individually spin-coated onto this crosslinked neutral layer to form a 47 nm thick coating of block copolymer formulations containing h-PS oligomer-type additives 1-3 and 5-7, and comparative additives 1, 2, and 4. These coatings were baked at 110°C for 1 minute, and then annealed under N2 at 260°C for 15 minutes. The annealed coatings were then etched using O2 plasma etching to create contact holes.

[0103] Table 1 summarizes the properties of various types of the h-PS oligomers of the present invention produced by radical polymerization, whose annealing performance was verified. As shown in Table 1 and Figure 1, when blended with block copolymers, these materials exhibited good performance during the high-speed annealing process enabled by the h-PS oligomers of the present invention, without causing the self-assembly of the block copolymer's cylindrical shape to collapse during the coating and annealing of the composition on a neutral layer.

[0104] Table 2 summarizes the properties of different types of comparative h-PS oligomers produced by either radical or anionic polymerization, which were the subject of evaluation. These materials exhibited poor performance when coated and annealed on substrates coated with a neutral layer, resulting in the collapse of the self-assembled cylindrical shape during the high-speed annealing process.

[0105] [Table 1]

[0106] [Table 2]

[0107] Figure 1 shows SEM images of each BCP formulation containing the h-PS oligomer according to the present invention (Table 1), produced by radical polymerization, at 2, 4, or 50 field of view (FOV) after coating and annealing on a substrate coated with a neutral layer, and then plasma etching with an O2 plasma. These formulations exhibited good self-assembly of contact holes, showing defect-free, vertical contact hole shapes.

[0108] Figure 2 shows SEM images of comparative h-PS oligomers (Table 2) produced by radical polymerization or anionic polymerization, in 2 or 4 field of view (FOV) after coating and annealing their formulations on a substrate coated with a neutral layer, and then plasma etching them with O2 plasma. Surprisingly, this shows that in the case of radically polymerized h-PS, the M specified in the claims is w In the case of these comparative oligomers, which fall outside the range (comparative additive 4) or outside the range of polydispersity defined in the claims (comparative additives 1 and 2), poor self-assembly of contact holes occurred, resulting in defects observed as dark spots. These dark spots suggest defects caused by a collapsed vertical syringe shape as a result of reduced self-assembly dynamics. Table 1 shows that the thermogravimetric analysis temperatures of the anionically polymerized comparative additives 1 and 2 are considerably higher than their corresponding radically polymerized additives 1 and 3, respectively. Similar M w BCP formulations containing additives 2 and 3 are both expected to exhibit defect-free vertical contact hole shapes, as in the case of the formulation containing additive 2 (Table 1).

[0109] While the disclosed and claimed inventions have been described and explained with a certain degree of detail, it should be understood that this disclosure is merely illustrative, and that a person skilled in the art may rely on numerous variations in the conditions and order of each step without departing from the spirit and scope of the disclosed and claimed inventions.

Claims

1. A composition comprising the following components a), b), and c): a) is one type of block copolymer component, or a blend of at least two types of block copolymers; b) is at least one kind of low T ｇ These are oligomeric polystyrene-based additives, and each additive is individually controlled in the temperature range of approximately 68.0°C to approximately 90.0°C. ｇ It has and M in the range of about 2,500 g / mol to about 8,000 g / mol ｗ It has a polydispersity of 1.20 to about 1.80, and furthermore, the styrene-based additive is - At least one styrene-based homopolymer produced by radical polymerization, - At least one styrene-based random copolymer produced by radical polymerization, wherein the repeating units consist only of styrene-based repeating units and contain at least two types of styrene-based repeating units, - A mixture of at least one styrene-based homopolymer and at least one styrene-based random copolymer, Selected from the group consisting of; c) is an organic spin-casting solvent.

2. The composition according to claim 1, comprising components a), b), and c).

3. In component b), each additive individually has a temperature range of approximately 69.0°C to approximately 89.7°C. ｇ A composition according to claim 1 or 2, having the following characteristics.

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 component b) is at least one of the styrene-based homopolymers or at least one of the styrene-based random copolymers.

6. Component b) is at least one of the styrene-based homopolymers, and further this has structure (A), and its repeating unit consists of those having structure (I), where n1 is the number of repeating units, which represents that this is a repeating unit, R Ａ１ , R Ａ２ , R Ａ３ , R Ａ４ , R Ａ５ is individually selected from H or C1-C8 alkyl, R ｍ１ is H or methyl, and the styrene-based homopolymer has two end groups shown in structure (A), one of which is H, and the other is a methyl moiety substituted with Rr, Rr １ and Rr ２ , where Rr １ is C1-C8 alkyl, Rr ２ is selected from C1-C8 alkyl, Rr is a cyano moiety (—CN) or a carbonylalkyl moiety (—C(═O)—Ri), Ri is C1-C8 alkyl or an aryl moiety, The composition according to any one of claims 1 to 5. 【Chemistry 1】

7. The component b) is at least one of the styrene-based random copolymers having structure (B), wherein the repeating units consist of two different repeating units of structure (II') and (III), where n2 and n3 are the number of these repeating units, and these represent that they are repeating units, R Ｂ１ , R Ｂ２ , R Ｂ３ , R Ｂ４ , R Ｂ５ , R Ｂ６ , R Ｂ７ , R Ｂ８ , R Ｂ９ , and R Ｂ１０ R is independently selected from H or C1-C8 alkyl groups. ｍ２ , R ｍ３ is independently selected from H or methyl, and The styrene-based random copolymer has two terminal groups as shown in structure (B), one of which is H and the other is Rr ３ , Rr ４ and Rr ５ This is a methyl moiety substituted by, where Rr ４ It is a C1-C8 alkyl group, and Rr ５ Rr is selected from C1 to C8 alkyl groups. ３ The composition according to any one of claims 1 to 5, wherein is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), and Ri is a C1-C8 alkyl or aryl moiety. 【Chemistry 2】

8. The composition according to any one of claims 1 to 5, wherein component b) is a mixture of at least one styrene-based homopolymer and at least one styrene-based random copolymer.

9. The component b) is a mixture of at least one styrene-based homopolymer and at least one styrene-based random copolymer, and The styrene-based homopolymer has structure (A), and its repeating units consist of those having structure (I), where n1 is the number of repeating units, and R represents that these are repeating units. Ａ１ , R Ａ２ , R Ａ３ , R Ａ４ , R Ａ５ Each is individually selected from H or C1-C8 alkyl, R ｍ１ is H or methyl, and the styrene-based homopolymer has two terminal groups as shown in structure (A), one of which is H and the other is Rr, Rr １ and Rr ２ This is a methyl moiety substituted with Rr １ It is a C1-C8 alkyl group, and Rr ２ Rr is selected from C1-C8 alkyl groups, Rr is a cyano moiety (-CN) or a carbonyl alkyl moiety (-C(=O)-Ri), Ri is a C1-C8 alkyl group or an aryl moiety, and Furthermore, the styrene-based random copolymer has structure (B), and its repeating units consist of two repeating units, structure (II') and (III), where n2 and n3 are the number of these repeating units, respectively, and these represent repeating units, R Ｂ１ , R Ｂ２ , R Ｂ３ , R Ｂ４ , R Ｂ５ , R Ｂ６ , R Ｂ７ , R Ｂ８ , R Ｂ９ , and R Ｂ１０ R is independently selected from H or C1-C8 alkyl groups. ｍ２ , R ｍ３ The styrene-based random copolymer is independently selected from H or methyl, and the styrene-based random copolymer has two terminal groups as shown in structure (B), one of which is H and the other is Rr ２ , Rr ３ and Rr ４ This is a methyl moiety substituted with Rr ４ It is a C1-C8 alkyl group, and Rr ５ Rr is selected from C1 to C8 alkyl groups. ３ The composition according to claim 1 or 6, wherein is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), and Ri is a C1-C8 alkyl or aryl moiety. 【Transformation 3】

10. The above component b) is at least one low T ｇ These are oligomeric polystyrene-based additives, and each additive is individually available in a range of approximately 2,900 g / mol to approximately 7,700 g / mol. ｗ A composition according to any one of claims 1 to 9, having the following characteristics.

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

12. The above component a) is an ABA-type triblock copolymer component selected from the group consisting of ABA-type triblock copolymer a-1t), ABA-type triblock copolymer a-2t), and a blend of two different ABA-type triblock copolymers a-1t) and ABA-type triblock copolymer a-2t), however, a-1t) is an ABA-type triblock copolymer comprising an intermediate B) styrene-based block segment having a styrene-based structure (I') and two terminal acrylic-based block A) segments of equal length having a structure (II'), where R １ and R ３ R is independently selected from H and C1-C4 alkyl groups. ２ is H or C1-C8 alkyl, R ４ is C1-C8 alkyl, and The mole percentage values ​​based on the total number of moles of repeating units of structures (I') and (II') range from approximately 40 mol% to approximately 80 mol% for the styrene-based repeating units of structure (I'), and from approximately 20 mol% to approximately 60 mol% for the acrylic-based repeating units of structure (I'). The individual values ​​of the mole percent of the repeating units of structures (I') and (II') are selected from their respective ranges such that the total number of moles of the repeating units of structures (I') and (II') sums up to 100 mol%; and The aforementioned triblock copolymer a-1t) has polydispersity from about 1.0 to about 1.1, and M from about 70,000 g / mol to about 350,000 g / mol. ｎ It has, 【Chemistry 4】 a-2t) is an ABA-type triblock copolymer comprising an intermediate B) block segment of a repeating unit having a styrene-based structure (Ia) and two terminal A) segments of equal length having an acrylic-based structure (IIa), where R １ａ and R ３ａ R is independently selected from H and C1-C4 alkyl groups. ２ａ is H or C1-C8 alkyl, R ４ａ These are C1-C8 alkyl groups, The mole percentage values ​​based on the total number of moles of the repeating units of structures (Ia) and (IIa) range from approximately 40 mol% to approximately 80 mol% for the styrene-based repeating units of structure (Ia), and from approximately 20 mol% to approximately 60 mol% for the acrylic-based repeating units of structure (IIa). The individual mole percentage values ​​for the repeating units of structures (Ia) and (IIa) are selected from their respective ranges such that the total number of moles of the repeating units of structures (Ia) and (IIa) sum to 100 mol%; and The aforementioned triblock copolymer a-2t) has polydispersity from about 1.0 to about 1.1, and M from about 70,000 g / mol to about 350,000 g / mol. ｎ Having, 【Transformation 5】 The composition according to any one of claims 1 to 11.

13. R １ , R １ａ , R ２ and R ２ａ H is H, and R ３ , R ３ａ , R ４ , and R ４ａ The composition according to claim 12, wherein is methyl.

14. Component (a) is a triblock copolymer selected from triblock copolymers of structure (ABA-1), triblock copolymers of structure (ABA-2), and mixtures of these two block copolymers, where mt, mta, nt, and nta are the number of repeating units, R １ｓ , R １ｓａ , R ２ｓ , and R ２ｓａ are independently selected from hydrogen, C1-C8 alkyl, -N(R ３ｓ ), -OR ４ｓ , and Si(R ５ｓ ), where R ３ｓ , R ４ｓ and R ５ｓ are independently selected from C1-C4 alkyl, and R １ , R １ａ , R ２ , R ２ａ , R ３ , R ３ａ , R ４ and R ４ａ are as defined in claim 12, a composition according to any one of claims 1 to 13.​​​​ 【Transformation 6】

15. R １ , R １ａ , R ２ , R ２ａ and R １ｓ , R １ｓａ , R ２ｓ and R ２ｓａ H is H, and R ３ , R ３ａ , R ４ , and R ４ａ The composition according to claim 14, wherein is methyl.

16. a) is a diblock copolymer component selected from the group consisting of diblock copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), however a-1) is a diblock copolymer of block A) containing styrene repeating units having a styrene structure (I') and block B) having an acrylic structure (II'), however, R １ and R ３ R is independently selected from H and C1-C4 alkyl groups. ２ is H or C1-C8 alkyl, R ４ is C1-C8 alkyl, and The mole percentage values ​​based on the total number of moles of repeating units in structures (I') and (II') range from approximately 40 mol% to approximately 80 mol% for the styrene-based repeating units of structure (I'), and from approximately 20 mol% to approximately 60 mol% for the acrylic-based repeating units of structure (II'). The individual values ​​of the mole percent of the repeating units of structures (I') and (II') are selected from their respective ranges such that the total number of moles of the repeating units of structures (I') and (II') sums up to 100 mol%; and The diblock copolymer a-1) has polydispersity from about 1.0 to about 1.1, and M from about 50,000 g / mol to about 150,000 g / mol. ｎ It has, 【Transformation 7】 a-2) is a diblock copolymer of block A-a) containing repeating units having a styrene-based structure (Ia) and block B-a) containing repeating units having an acrylic-based structure (IIa), however, R １ａ and R ３ａ R is independently selected from H or C1-C4 alkyl groups. ２ａ is H or C1-C8 alkyl, R ４ａ is C1-C8 alkyl, and The mole percentage values ​​based on the total number of moles of the repeating units of structures (Ia) and (IIa) range from approximately 40 mol% to approximately 80 mol% for the styrene-based repeating units of structure (Ia), and from approximately 20 mol% to approximately 60 mol% for the acrylic-based repeating units of structure (IIa). The individual mole percentage values ​​for the repeating units of structures (Ia) and (IIa) are selected from their respective ranges such that the total number of moles of the repeating units of structures (Ia) and (IIa) sum to 100 mol%; and The diblock copolymer a-2) has polydispersity from about 1.0 to about 1.1, and M from about 30,000 g / mol to about 90,000 g / mol. ｎ Having, 【Transformation 8】 The composition according to any one of claims 1 to 11.

17. Component a) is R １ , R １ａ , R ２ and R ２ａ H is H, and R ３ , R ３ａ , R ４ and R ４ａ The composition according to claim 16, wherein is methyl.

18. Diblock copolymers a-1) and a-2) each have structure (I-S) and structure (I-S-a), provided that R １ｓ , R １ｓａ , R ２ｓ , and R ２ｓａ These are independently hydrogen, C1-C8 alkyl, -N(R) ３ｓ ) ２ , -OR ４ｓ , and Si(R ５ｓ ) ３ Selected from, here R ３ｓ , R ４ｓ and R ５ｓ The composition according to claim 16 or 17, wherein is independently selected from C1 to C4 alkyl groups. 【Chemistry 9】

19. R １ｓ , R ２ｓ , R １ｓａ and R ２ｓａ The composition according to claim 18, wherein is hydrogen.

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

03.

21. Regarding component a), the diblock copolymer component a-1) ranges from approximately 93,000 g / mol to approximately 105,300 g / mol. ｎ A composition according to any one of claims 16 to 20, having the following characteristics.

22. The composition according to any one of claims 16 to 21, wherein, with respect to diblock copolymer component a-1), the molar percentage of the repeating units of structure (I') is from about 40 mol% to about 60 mol%, and the molar percentage of the repeating units of structure (II') is from about 40 mol% to about 60 mol%.

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

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

03.

25. Regarding component a), component a-2) of type AB diblock copolymer is M from approximately 40,800 g / mol to approximately 61,200 g / mol. ｎ A composition according to any one of claims 15 to 24, having the following characteristics:

26. The composition according to any one of claims 16 to 25, wherein with respect to component a), in either a single block copolymer a-1) or a-2) or a blend of a-1) and a-2), the total molar percentage of repeating units of structure (I') and (Ia) is from about 40 mol% to about 60 mol%, and the total molar percentage of repeating units of structure (II') and (IIa) is from about 40 mol% to about 60 mol%.

27. The composition according to any one of claims 16 to 25, wherein with respect to component a), in either a single block copolymer a-1) or a-2) or a blend of a-1) and a-2), the total molar percentage of repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and the total molar percentage of repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%.

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

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

30. The composition according to any one of claims 1 to 29, wherein component a) is in an amount of about 0.5% by weight to about 2.0% by weight of the total composition.

31. The composition according to 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 copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), the total mol% of the styrene repeating units of structure (I') and (Ia) is about 40 mol% to about 80 mol%, and the total mol% of the acrylic repeating units of structure (II') and (IIa) is about 20 mol% to about 60 mol%.

32. The composition according to 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 copolymer a-1), diblock copolymer a-2), and a blend of a-1) and a-2), the total mol% of the styrene repeating units of structure (I') and (Ia) is from about 60 mol% to about 75 mol%, and further, the total mol% of the acrylic repeating units of structure (II') and (IIa) is from about 25 mol% to about 40 mol%.

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

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

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

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

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

38. A method for forming a line-and-space array, the following steps: Steps include forming a neutral layer coating on a substrate, iic) A step of coating the neutral layer with the composition according to claim 33 to form a film, iii) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and ivc) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method, including the method described above.

39. A method for forming a contact hole array, the following steps: id) A step of forming a neutral layer coating on a substrate, i) A step of coating the neutral layer with the composition according to claim 34 to form a film, iii) The step of baking the film in an inert gas atmosphere at a temperature selected from about 240°C to about 280°C to form a self-assembling film, and ivd) A step of etching the substrate with plasma to transfer the self-assembling film into the substrate in a pattern, The method, including the method described above.

40. Use of the composition according to any one of claims 1 to 34 in a self-assembly process in which the pattern transfer of the self-assembled pattern to a substrate is performed.

Images