Photocurable composition containing reactive polymer

Abstract

The photocurable composition may include a polymerizable material and a photoinitiator, and the polymerizable material may include at least one polymerizable monomer and at least one reactive polymer. The reactive polymer may have a carbon content of at least 75% based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer may be at least 400 g / mol and not more than 50,000 g / mol, the amount of reactive polymer may be at least 5 wt%, and the viscosity of the photocurable composition may be not more than 100 mPa·s. The photocurable composition has low linear shrinkage after curing, high carbon content, high etch resistance, and is suitable for IAP or NIL processing.

Description

[Technical field]

[0001] The present disclosure relates to photocurable compositions, and in particular to photocurable compositions for inkjet compatible planarization suitable for forming photocurable layers with high carbon content, low heat shrinkage, and high thermal stability. [Background technology]

[0002] Inkjet Adaptive Planarization (IAP) is a process of planarizing the surface of a substrate, e.g., a wafer containing electrical circuitry, by ejecting droplets of a photocurable composition onto the surface of the substrate and directly contacting a planar superstrate with the applied liquid to form a planar liquid layer. The planar liquid layer is typically solidified under UV light exposure, and after removal of the superstrate, a planar polymer surface is obtained that can be subjected to subsequent processing steps, e.g., baking, etching, and / or further deposition steps.

[0003] There is a need for improved IAP data that results in planar photocurable layers that have high etch resistance, high thermal stability, and low shrinkage during subsequent processing. Summary of the Invention

[0004] In one embodiment, the photocurable composition can include a polymerizable material and a photoinitiator, the polymerizable material can include at least one polymerizable monomer and at least one reactive polymer, the reactive polymer can include a carbon content of at least 75% based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer is at least 400 g / mol and not more than 50,000 g / mol, the amount of the reactive polymer is at least 5 wt% based on the total weight of the polymerizable material, and the viscosity of the photocurable composition can be not more than 100 mPa·s.

[0005] In one embodiment of the photocurable composition, the reactive polymer is represented by the formula (1): R1-X nThe compound may include a structure of -R2(1), where X is the same or different repeating monomer unit, n is 3 to 300, and R1 and R2 are different from each other or the same among vinyl groups, acrylate groups, methacrylate groups, and vinylbenzene groups. In one embodiment, X in formula (1) may be -O-Ar-, or Ar-C=O, or CH2-CHR3-CH2, R3 may be benzene, naphthene, anthracene, cyclohexane, isobornyl, or adamantane, and Ar is substituted or unsubstituted benzene, naphthalene, or anthracene.

[0006] In another embodiment of the photocurable composition, the reactive polymer has the formula (2): R1-X n -YX m The structure may include -R2(2), where X is the same or different repeating monomer unit, n is 3 to 150, m is 3 to 150, Y is a linking unit, and R1 and R2 are different from each other or the same among vinyl groups, acrylate groups, methacrylate groups, and vinylbenzene groups. In a specific embodiment, X in formula (2) may be -O-Ar- or Ar-C=O, and Ar is substituted or unsubstituted benzene, naphthalene, or anthracene.

[0007] In a further embodiment of the photocurable composition, the reactive polymer may comprise functional groups attached to its repeating monomer units, and the numerical ratio of the functional groups to the repeating monomer units may range from 1:3 to 1:100.

[0008] In another embodiment, the photocurable composition may be adapted such that after photocuring, the photocurable composition has a linear shrinkage of 6 percent or less.

[0009] In an embodiment, the viscosity of the photocurable composition may be 35 mPa·s or less.

[0010] In one embodiment, the total carbon of the photocurable composition after curing may be at least 69%.

[0011] In another embodiment, the molecular weight of the reactive polymer may be at least 800 g / mol and up to 10,000 g / mol.

[0012] In one embodiment, the amount of the reactive polymer may be at least 5% and no more than 30% by weight based on the total weight of the polymerizable material.

[0013] In certain embodiments, the amount of the polymerizable material may be at least 50% by weight, based on the total weight of the photocurable composition.

[0014] In another embodiment, the at least one polymerizable monomer of the polymerizable material can have a boiling point of at least 250°C.

[0015] In further embodiments, the at least one polymerizable monomer can include at least one acrylate monomer. In certain embodiments, the at least one acrylate monomer can include at least one multifunctional acrylate monomer.

[0016] In one embodiment, the photocurable composition is adapted for nanoimprint lithography (NIL) or inkjet adaptive planarization (IAP) processing.

[0017] In another embodiment of the photocurable composition, the thermal decomposition temperature of the photocurable composition after photocuring may be at least 300°C.

[0018] In one embodiment, a method of forming a photocurable layer on a substrate includes applying a layer of a photocurable composition onto the substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one polymerizable monomer and at least one reactive polymer, the reactive polymer comprising at least 75% carbon content based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer being at least 400 g / mol and up to 50,000 g / mol, the amount of the reactive polymer being at least 5 wt % based on the total weight of the photocurable composition, and the viscosity of the photocurable composition being up to 100 mPa·s; contacting the photocurable composition with a template or superstrate; irradiating the photocurable composition with light to form a photocurable layer; and removing the template or superstrate from the photocurable layer.

[0019] In one aspect of the method, the layer of photocurable composition after forming the photocured layer may have a linear heat shrinkage of 6 percent or less.

[0020] In another embodiment, a method of making an article includes applying a layer of a photocurable composition onto a substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one polymerizable monomer and at least one reactive polymer, the reactive polymer comprising at least 75% carbon content based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer being at least 400 g / mol and no more than 50,000 g / mol, the amount of the reactive polymer being at least 5 wt % based on the total weight of the photocurable composition, and the viscosity of the photocurable composition being no more than 100 mPa·s; contacting the photocurable composition with a template or superstrate; irradiating the photocurable composition with light to form a photocurable layer; removing the template or superstrate from the photocurable layer; forming a pattern on the substrate; treating the substrate with the pattern formed in the forming a pattern; and producing an article from the substrate treated in the treating a substrate. [Brief description of the drawings]

[0021] Embodiments are illustrated by way of example and not limitation in the accompanying figures. [Figure 1] 1 includes a graph showing dynamic TGA curves of photocured samples according to one embodiment. [Diagram 2] 1 includes a graph showing dynamic TGA curves of photocured samples according to one embodiment. [Diagram 3] 1 includes a graph showing an isothermal TGA curve of a photocured sample according to one embodiment. Those skilled in the art will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to aid in understanding embodiments of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The following description is provided to aid in understanding the teachings disclosed herein and focuses on specific implementations and embodiments of the teachings. This focus is provided to help explain the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and are not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing acts are conventional and can be found in textbooks and other sources within the imprint and lithography arts.

[0024] As used herein, the terms "comprises," "includes," "including," "including," "having," "having" or any other variations thereof are intended to cover an open-ended inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only those features and may include other features that are not expressly listed or that are inherent to such process, method, article, or apparatus.

[0025] As used herein, unless expressly stated to the contrary, "or" means an inclusive or, not an exclusive or. For example, condition A or B is satisfied by one of the following: 1) A is true (or present) and B is false (or absent), 2) A is false (or absent) and B is true (or present), or 3) both A and B are true (or present).

[0026] Additionally, the use of words without number terms is used to describe elements and components described herein. This is used merely for convenience and to give a general sense of the scope of the invention. The specification should be read to include one or at least one, and the singular also includes the plural, unless it is clear that no plural is intended.

[0027] The present disclosure relates to a photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one polymerizable monomer and at least one reactive polymer, the reactive polymer may have a carbon content of at least 75% based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer may be at least 400 g / mol and not more than 50,000 g / mol, the amount of reactive polymer may be at least 5 wt% based on the total weight of the polymerizable material, and the viscosity of the photocurable composition may be not more than 100 mPa·s.

[0028] Surprisingly, it has been observed that photocurable compositions comprising specific combinations of at least one polymerizable monomer and at least one reactive polymer can enable the formation of photocured layers having improved thermal stability and lower linear shrinkage compared to respective photocurable compositions that do not include a reactive polymer.

[0029] Without being bound by theory, it is hypothesized that the reactive polymer can participate during the photoinitiated polymerization of the monomers in the formation of the polymer matrix, thereby reducing shrinkage. The appropriate balance of the type and amount of reactive polymer and the type and amount of polymerizable monomer can facilitate the formation of a resist material with low viscosity, high carbon content, high thermal stability, and high etch resistance, which is highly suitable for NIL or IAP processing.

[0030] As used herein, the term "reactive polymer" refers to a polymer that includes functional groups that can react with functional groups of polymerizable monomers of a polymerizable material.

[0031] In one embodiment, the reactive polymer has the formula (1): R1-X nIn -R2(1), X is the same or different repeating monomer unit, n is 3 to 300, and R1 and R2 are different or the same among vinyl groups, acrylate groups, methacrylate groups, or vinylbenzene groups. In a specific embodiment, X can be -O-Ar-, or Ar-C=O, or CH2-CHR3-CH2-, R3 is benzene, naphthene, anthracene, cyclohexane, isobornyl, or adamantane, and Ar is substituted or unsubstituted benzene, naphthalene, or anthracene.

[0032] In another embodiment, the reactive polymer has the formula (2): R1-X n -YX m The structure of -R2(2) may be included, where X is the same or different repeating monomer unit, n is 3 to 150, m is 3 to 150, Y is a linking unit, and R1 and R2 are different from each other or the same among vinyl groups, acrylate groups, methacrylate groups, and vinylbenzene groups. In a specific embodiment, X may be -O-Ar- or Ar-C=O, where Ar is substituted or unsubstituted benzene, naphthalene, or anthracene. The linking unit Y may be alkyl, oxy-alkyl, Ar, or O-Ar-Ar-O-, where Ar is substituted or unsubstituted benzene, cyclohexane, naphthene, or anthracene. In a specific embodiment, the substituted Ar may include 1 to 3 methyl or ethyl groups per benzene ring.

[0033] In some embodiments, the repeating monomer unit X of formula (1) or (2) may not contain a functional group suitable for reacting with a vinyl or acrylate group of a monomer of the polymerizable material, and only the functional groups at the end positions of the reactive polymer are adapted to participate in polymerization during curing. In one embodiment, a first end of the reactive polymer may have a functional group and a second end may not contain a functional group. In another embodiment, both ends (first end and second end) of the reactive polymer may contain a functional group.

[0034] In certain embodiments, the functional group of the reactive polymer and the functional group of the at least one polymerizable monomer may be a vinyl group, an acrylate group, or a methacrylate group.

[0035] In another embodiment, the reactive polymer can include functional groups attached to the repeating monomer units of the reactive polymer and / or at their end positions, and the numerical ratio of the functional groups to the repeating monomer units of the reactive polymer can be in the range of 1:3 to 1:100, such as 1:3 to 1:50, or 1:3 to 1:20.

[0036] The reactive polymer can be selected by the criteria of having a high carbon content, being soluble in at least one polymerizable monomer of the polymerizable material, having a particular molecular weight range, and providing only a small contribution to the viscosity increase of the photocurable composition.

[0037] A high carbon content of the reactive polymer is desirable because it contributes to a high final carbon content of the photocured layer formed from the photocurable composition. In one embodiment, the carbon content of the reactive polymer can be at least 75%, e.g., at least 78%, at least 80%, at least 82%, at least 84%, at least 86%, at least 88%, at least 90%, or at least 92%, based on the total weight of the reactive polymer.

[0038] In certain aspects, the molecular weight of the reactive polymer may be at least 400 g / mol, at least 600 g / mol, or at least 800 g / mol, or at least 1,000 g / mol, or at least 2,000 g / mol, or at least 5,000 g / mol. In other aspects, the molecular weight of the reactive polymer may be 50,000 g / mol or less, or 40,000 g / mol or less, or 30,000 g / mol or less, or 15,000 g / mol or less, or 10,000 g / mol or less, or 8,000 g / mol or less, or 5,000 g / mol or less, or 3,000 g / mol or less. In certain embodiments, the molecular weight may be at least 1,000 g / mol and up to 10,000 g / mol.

[0039] In further embodiments, the amount of reactive polymer may be at least 5% by weight, e.g., at least 10% by weight, or at least 15% by weight, or at least 20% by weight, based on the total weight of the polymerizable material. In other embodiments, the amount of reactive polymer may be 40% by weight or less, or 30% by weight or less, or 25% by weight or less, or 22% by weight or less, based on the total weight of the polymerizable material. In certain embodiments, the amount of reactive polymer may be at least 10% by weight, 30% by weight or less, based on the total weight of the polymerizable material.

[0040] The photocurable composition can be designed to have a low viscosity before curing. In one embodiment, the viscosity of the curable composition can be 100 mPa·s or less, or 80 mPa·s or less, or 50 mPa·s or less, or 40 mPa·s or less, or 35 mPa·s or less, or 30 mPa·s or less, or 25 mPa·s or less, or 20 mPa·s or less, or 15 mPa·s or less. In other particular embodiments, the viscosity can be at least 5 mPa·s, such as at least 10 mPa·s, or at least 15 mPa·s. In a particularly preferred aspect, the photocurable composition can have a viscosity of 20 mPa·s to 60 mPa·s or less. As used herein, all viscosity values ​​refer to viscosities measured at a temperature of 23° C. using the Brookfield method using a Brookfield viscometer.

[0041] The at least one polymerizable monomer of the polymerizable material can include a monofunctional monomer, a multifunctional monomer, or a combination thereof. In certain embodiments, the at least one polymerizable monomer can include at least one multifunctional acrylate monomer, or at least one multifunctional vinyl monomer, or a combination of a multifunctional acrylate monomer and a multifunctional vinyl monomer.

[0042] Non-limiting examples of multifunctional acrylate monomers can be bisphenol A dimethacrylate, m-xylylene diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, or any combination thereof.

[0043] In further embodiments, the polymerizable monomers can have a boiling point of at least 250°C, or at least 260°C, or at least 280°C.

[0044] In another particular embodiment, the multifunctional vinyl monomer may be divinylbenzene.

[0045] In further particular aspects, the polymerizable material can include at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer. As used herein, the term acrylate monomer refers to both unsubstituted and alkyl-substituted acrylates, such as methacrylates.

[0046] In another embodiment, the amount of multifunctional monomer may be at least 10%, or at least 15%, or at least 20%, or at least 30%, or at least 50%, or at least 80% by weight of the polymerizable material, based on the total weight of the polymerizable material. In another embodiment, the amount of multifunctional monomer may be 95% or less, or 90% or less, or 70% or less, or 50% or less, or 30% or less by weight of the polymerizable material, based on the total weight of the polymerizable material.

[0047] In yet another embodiment, the weight percent ratio of monofunctional monomer to multifunctional monomer can be from 1:5 to 5:1, such as from 1:3 to 3:1, or from 1:1 to 3:1.

[0048] The amount of polymerizable material in the photocurable composition may be at least 30% by weight, for example at least 40% by weight, at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least 95% by weight, based on the total weight of the photocurable composition. In another embodiment, the amount of polymerizable material may be 98% by weight or less, for example 95% by weight or less, or 90% by weight or less, or 80% by weight or less, or 60% by weight or less, or 50% by weight or less, or 30% by weight or less. The amount of polymerizable material may be any value between the minimum and maximum values ​​listed above. In a particular embodiment, the amount of polymerizable material may be at least 50% by weight, but not more than 98% by weight.

[0049] The photocurable composition of the present disclosure can be adapted to have high thermal stability of the photocurable layer formed therefrom. In one embodiment, the onset temperature of thermal degradation of the photocurable layer can be greater than 250°C, or greater than 300°C, or greater than 350°C, or greater than 375°C, or greater than 400°C. As used herein, the onset thermal degradation temperature, also referred to as the "initial thermal degradation temperature" or "thermal degradation temperature", refers to the temperature of the TGA curve at which the deviation of the curve from the approximately linear plateau is first observed, immediately prior to the rapid degradation of the sample.

[0050] In one embodiment, the photocurable composition of the present disclosure may be essentially free of solvent. As used herein, unless otherwise indicated, the term solvent refers to a compound that can dissolve or disperse polymerizable monomers, but does not itself polymerize during photocuring of the photocurable composition. The term "essentially free of solvent" herein refers to an amount of solvent that is 5% by weight or less based on the total weight of the photocurable composition. In certain aspects, the amount of solvent can be 3% by weight or less, 2% by weight or less, 1% by weight or less based on the total weight or photocurable composition, or the photocurable composition can be solvent-free, except for unavoidable impurities.

[0051] In other specific embodiments, the photocurable composition can include a solvent in an amount of at least 5 wt%, or at least 8 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt%, or at least 30 wt%, or at least 50 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, based on the total weight of the photocurable composition. In other embodiments, the amount of solvent can be 95 wt% or less, or 80 wt% or less, or 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, or 15 wt% or less, based on the total weight of the photocurable composition.

[0052] In certain embodiments, the linear shrinkage of the photocurable composition may be 6% or less, such as 5.5% or less, 5.0% or less, 4.5% or less, 4.0% or less, 3.5% or less, or 3.0% or less.

[0053] One or more photoinitiators can be included in the photocurable composition to initiate photocuring of the composition when exposed to light, hi some embodiments, curing can also be achieved by a combination of light and thermal curing.

[0054] The photocurable composition may further contain one or more optional additives. Non-limiting examples of the optional additives may be stabilizers, dispersants, solvents, surfactants, inhibitors, or any combination thereof.

[0055] The photocurable compositions of the present disclosure can be adapted for use in inkjet adaptive planarization (IAP) or nanoimprint lithography (NIL).

[0056] In one embodiment, the photocurable composition can be coated onto a substrate to form a photocurable layer. As used herein, the combination of the substrate and the photocurable layer overlying the substrate is referred to as a laminate.

[0057] The inclusion of at least one reactive polymer of the polymerizable material may contribute to a high carbon content of the photocurable composition and the photocured layer formed. In one embodiment, the photocurable composition may be adapted such that the carbon content of the composition after curing may be at least 69%, or at least 70%, or at least 71%, at least 72%, at least 73%, at least 74%, or at least 75%.

[0058] The present disclosure further relates to a method of forming a photocurable layer, which method can include applying a layer of the photocurable composition described above onto a substrate, contacting the photocurable composition with a template or superstrate, irradiating the photocurable composition with light to form the photocurable layer, and removing the template or superstrate from the photocurable layer.

[0059] The substrate and solidified layer may be subjected to additional processing, such as an etching process, to transfer an image to the substrate that corresponds to the pattern of one or both of the solidified layer and / or the patterned layer underlying the solidified layer. The substrate may be further subjected to known steps and processes for device (article) manufacturing, including, for example, curing, oxidation, layering, deposition, doping, planarization, etching, formable material removal, dicing, bonding, and packaging.

[0060] The solidified layer may also be used as an interlayer insulating film in semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, or as a resist film used in semiconductor manufacturing processes. example The following non-limiting examples illustrate the concepts described herein. Example 1 photocurable composition Photocurable compositions were prepared that contained as reactive polymers a polyphenylene ether (PPE)-based polymer having the structure shown in Table 1 (NORYL SA9000 from Sabic), and two polyphenylene ether (PPE)-based polymers, OPE-2St-1200 and OPE-St-2200 from Mitsubishi Gas Chemicals (different molecular weights but the same structure) (see Table 1).

[0061] All photocurable compositions contained m-xylylene diacrylate (mXDA) with a carbon content of 68% as the polymerizable monomer, as well as 2% by weight of the photoinitiator Omnirad 907 and 1% by weight of the surfactant Capstone™ FS-3100. A summary of the reactive polymers tested is given in Table 1.

[0062] [Table 1]

[0063] A first series of photocurable compositions were prepared containing varying amounts of SA9000 (see summary in Table 2).

[0064] [Table 2]

[0065] A further series of photocurable samples was prepared by including two different amounts of OPE-2St-1200 and OPE-2St-2200 as reactive polymers, respectively (see summary in Table 3).

[0066] [Table 3]

[0067] viscosity The viscosity data in Tables 2 and 3 show that as the amount of reactive polymer increases, the viscosity increases.

[0068] The data in Table 3 further show that the viscosity increases with increasing molecular weight of the reactive PKK polymer. The lower molecular weight PKK (OPE-2St-1200) was much better soluble in MXDA monomer than the higher molecular weight PKK (OPE-2St-2000). The results indicate that for the use of reactive polymers with high molecular weight and / or high concentration, the use of a solvent may be recommended.

[0069] Viscosity was measured at 23°C using a Brookfield Viscometer LVDV-II+ Pro, 200 rpm, spindle size #18. For viscosity tests, approximately 6-7 mL of sample liquid was added to the sample chamber, enough to cover the spindle head. For all viscosity tests, at least three measurements were taken and the average value was calculated. thermal stability Photocurable layers were prepared from the photocurable compositions summarized in Tables 2 and 3 by applying a 300 micron thick layer of the photocurable composition onto a glass slide and photocuring the resist layer. Samples S1-S4 (including SA9000) were photocured at 14 mW / cm 2 UV light of 365 nm was applied for 342 seconds at a light intensity of 4.8 J / cm 2 The samples S5 to S8 were cured by irradiating them with 14 mW / cm 2 for 714 seconds (10 J / cm radiation energy).

[0070] The photocured layers were analyzed by thermal analysis (TGA). TGA was performed using a LINSEIS STA PT1000 instrument (Linseis Messgeraete GmbH, Germany). All measurements were performed under nitrogen at a rate of 5 liters per hour.

[0071] For dynamic TGA measurements, samples (approximately 25 mg per test) were heated at a rate of 20° C. / min and the weight loss was recorded continuously.

[0072] When isothermal TGA was performed, the set-up was the same as for dynamic TGA, except that the temperature was increased to 350° C. and kept stable at this temperature for at least 30 min or more while the weight loss was recorded.

[0073] FIG. 1 shows the dynamic TGA curves of photocured samples S1, S2, and S3 compared to C1. It can be seen that the inclusion of reactive polymer SA9000 increased the initial thermal decomposition of the cured data, even by using only 10 wt% amount of SA9000. No further increase in thermal stability was observed between data formed from compositions containing 20 wt% SA9000 (S3) and 30 wt% SA9000 (S4) (S4 not shown). Without being bound by theory, the reason for the similar results between 20 wt% and 30 wt% may be the high viscosity of the photocurable composition at 30 wt%, which may reduce the reactivity. The exact values ​​of the initial thermal decomposition temperatures are also listed in Table 2.

[0074] As used herein, the term "thermal degradation temperature" refers to the initial degradation temperature T(X), which is the temperature in the TGA curve at which the deviation of the curve from a nearly linear plateau shape is first observed immediately prior to a rapid loss in mass of the sample, i.e., degradation.

[0075] Figure 2 shows the dynamic TGA curves of photocured samples S5, S6, and S8. The exact initial decomposition temperatures are further listed in Table 3. All samples show increased initial thermal decomposition temperatures compared to sample C1, which does not contain reactive polymer. No significant differences were observed between the data generated with lower and higher molecular weight reactive polymers (OPE-2200 and OPE-1200).

[0076] Isothermal TGA measurements at 350°C confirmed the dynamic TGA measurements. As shown in Figure 3, light-cured samples S1, S2, and S3 had similar decomposition rates of about 0.4% / min, and comparative sample C1 (without SA9000) had a material loss of 0.5% / min. The curve for SA9000 alone showed no decomposition at 350°C, even after 40 minutes.

[0077] When photocured samples S1 to S4 were baked on a hot plate at 350° C. for 2 minutes under nitrogen, they showed a weight loss of approximately 0.8% or less, which was acceptable for the IAP treatment.

[0078] The same baking procedure for samples S5-S8, i.e., baking at 350 °C for 2 min under nitrogen, resulted in a weight loss of about 1.5%, which is also an acceptable value for IPA treatment. Linear shrinkage The shrinkage measurements were performed using an Anton Paar MCR-301 rheometer connected to a UV curing system and heater. For the test, a 7 μL droplet of resist composition was added onto the plate, and the temperature-controlled hood was released to insulate the droplet and the measurement unit. The resist amount was designed so that the thickness (hereinafter also referred to as height) of the resist layer was slightly greater than 0.1 mm. By presetting the target height to 0.1 mm, the length measuring unit lowered to the set value, and excess resist flowed out of the plate. This ensured that the exact height of the liquid resist before curing was 0.1 mm. Then, the UV output of 50 mW / cm was applied. 2 After the resist was cured, the height was measured again and SL = (L R -L CR / L R )×100%(L R is the thickness of the photocurable composition layer before curing, and L CR is the thickness of the photocurable composition layer after curing).

[0079] A summary of the measured linear shrinkage is shown in Table 4. It can be seen that both types of reactive polymers reduced the linear shrinkage with increasing amounts. An amount of 10 wt% reactive polymer reduced the linear shrinkage by about 0.5-1%, which increased further to about 1.5-2% shrinkage reduction at amounts of 20-30 wt%.

[0080] [Table 4]

[0081] Etching resistance Photocured films for testing etch resistance were prepared by dropping 0.5 μl of the resist composition onto a Si wafer, placing a rigid blank fused silica mold over the drop, and allowing the liquid to spread between the mold and the substrate for about 5 min to obtain a completely filled thin liquid layer. 2 The liquid layer was cured through the mold using an ultraviolet lamp having a 350 nm wavelength. After curing, the mold was separated from the cured film. The thickness of the cured film was about 700 nm.

[0082] To measure the etching resistance, dry etching was performed under oxygen / argon atmosphere using a Trion Oracle 3-Chamber Cluster System as the etching tool. The following etching conditions were applied: O2: 2 sccm; Argon: 10 sccm; RF power: 45 watts; Pressure: 10 mTorr; Etch time: 120 seconds; Chuck temperature: 7°C, Helium backside pressure: 5 Torr.

[0083] Table 5 shows the etch rates (nm / min) measured for photocured samples S5 (made with 10 wt% OPE-St-1200), S6 (made with 20 wt% OPE-St-1200), and comparative sample C1 (containing only MXDA as the polymerizable monomer, no reactive polymer in the photocurable composition). It can be seen that samples S5 and S6 etched significantly slower than sample C1. Photocured sample S6 made with 20 wt% OPE 1200 had an etch rate about 26% slower than comparative sample C1.

[0084] [Table 5]

[0085] Carbon Content Tables 2 and 3 show the calculated carbon content in the photocured layer after curing for the listed photocurable compositions. In calculating the carbon content, it was assumed that the polymerizable materials (reactive polymers and polymerizable monomers) amount to 100% of the layer material, and the carbon content was calculated relative to the calculated weight of all components per mole, with "%" representing the weight percent of carbon in the layer material. The calculated carbon content should be very close to the actual carbon content since there is no material loss during curing, such as forming gas or water.

[0086] The carbon content of the reactive polymers (shown in Table 1) is calculated relative to the molecular weight of the monomer units of the polymer and relates to weight percent per total weight of the reactive polymer.

[0087] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The specification and illustrations are not intended to be exhaustive and comprehensive descriptions of all of the elements and features of the apparatus and systems that use the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, for brevity, various features described in the context of a single embodiment may be provided separately or in any subcombination. Furthermore, references to values ​​described in ranges include each and every value within that range. Many other embodiments may be apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure, such that structural substitutions, logical substitutions, or other changes may be made without departing from the scope of this disclosure. Thus, this disclosure should be considered as illustrative and not restrictive.

Claims

1. A photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprises at least one polymerizable monomer and at least one reactive polymer; the reactive polymer comprises a carbon content of at least 75% based on the total weight of the reactive polymer; the molecular weight of said at least one reactive polymer is at least 400 g / mol and no more than 50,000 g / mol; the amount of said reactive polymer is at least 5% by weight based on the total weight of said polymerizable material; The viscosity of the photocurable composition is 100 mPa·s or less. A photocurable composition comprising:

2. The reactive polymer has the formula (1): R １ -X ｎ -R ２ (1), X is the same or different repeating monomer unit, n is 3 to 300, R １ and R ２ contains vinyl groups, acrylate groups, methacrylate groups, or vinylbenzene groups that are different from each other or the same as each other, The photocurable composition according to claim 1 .

3. X is -O-Ar-, Ar-C=O, or CH ２ -CHR ３ -CH ２ and R ３ is benzene, naphthene, anthracene, cyclohexane, isobornyl, or adamantane; Ar is substituted or unsubstituted benzene, naphthalene, or anthracene; The photocurable composition according to claim 2 .

4. The reactive polymer has the formula (2): R １ -X ｎ -Y-X ｍ -R ２ (2), X is the same or different repeating monomer unit, n is 3 to 150, m is 3 to 150, Y is a linking unit, R １ and R ２ contains vinyl groups, acrylate groups, methacrylate groups, or vinylbenzene groups that are different from each other or the same as each other, The photocurable composition according to claim 1 .

5. X is -O-Ar- or Ar-C=O, and Ar is a substituted or unsubstituted benzene, naphthalene, or anthracene; The photocurable composition according to claim 4 .

6. the reactive polymer comprises a functional group bonded to a repeating monomer unit of the reactive polymer, and the number ratio of the functional group to the repeating monomer unit is within the range of 1:3 to 1:100; The photocurable composition according to claim 1 .

7. The photocurable composition is adapted such that after photocuring, the photocurable composition has a linear shrinkage of 6 percent or less. The photocurable composition according to claim 1 .

8. The viscosity of the photocurable composition is 35 mPa·s or less. The photocurable composition according to claim 1 .

9. the total carbon content of the photocurable composition after curing is at least 69%; The photocurable composition according to claim 1 .

10. The molecular weight of the reactive polymer is at least 800 g / mol and not more than 10,000 g / mol; The photocurable composition according to claim 1 .

11. the amount of the reactive polymer is at least 5% by weight and not more than 30% by weight based on the total weight of the polymerizable material; The photocurable composition according to claim 1 .

12. the amount of said polymerizable material is at least 50% by weight based on the total weight of said photocurable composition; The photocurable composition according to claim 1 .

13. the at least one polymerizable monomer has a boiling point of at least 250° C.; The photocurable composition according to claim 1 .

14. the at least one polymerizable monomer comprises at least one acrylate monomer; The photocurable composition according to claim 1 .

15. the at least one acrylate monomer comprises at least one multifunctional acrylate monomer; The photocurable composition according to claim 14.

16. The photocurable composition is adapted for nanoimprint lithography (NIL) or inkjet adaptive planarization (IAP) processing; The photocurable composition according to claim 1 .

17. The photocurable composition after photocuring has a thermal degradation temperature of 300° C. or higher. The photocurable composition according to claim 1 .

18. 1. A method for forming a photocurable layer on a substrate, comprising: applying a layer of a photocurable composition onto the substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one polymerizable monomer and at least one reactive polymer, the reactive polymer comprising a carbon content of at least 75% based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer being at least 400 g / mol and no more than 50,000 g / mol, the amount of the reactive polymer being at least 5 wt % based on the total weight of the photocurable composition, and the viscosity of the photocurable composition being no more than 100 mPa s; contacting the photocurable composition with a template or superstrate; A step of irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstrate from the photocurable layer; The method according to claim 1, further comprising:

19. the linear thermal shrinkage of the photocurable composition layer after the photocurable layer is formed is 6 percent or less; 20. The method of claim 18 .

20. 1. A method for manufacturing an article, comprising: applying a layer of a photocurable composition onto a substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one polymerizable monomer and at least one reactive polymer, the reactive polymer comprising a carbon content of at least 75% based on the total weight of the reactive polymer, the molecular weight of the at least one reactive polymer being at least 400 g / mol and no more than 50,000 g / mol, the amount of the reactive polymer being at least 5 wt % based on the total weight of the photocurable composition, and the viscosity of the photocurable composition being no more than 100 mPa s; contacting the photocurable composition with a template or superstrate; A step of irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstrate from the photocurable layer; forming a pattern on the substrate; processing the substrate on which the pattern has been formed in the pattern forming step; manufacturing an article from the substrate processed in the step of processing the substrate; A manufacturing method comprising the steps of:

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