Photocurable components

Abstract

The photocurable composition can include a polymerizable material and a photoinitiator, and the polymerizable material can include 10 to 40 wt % of a monofunctional alkyl group of formula (1), wherein R1 is H or C1-C6 alkyl, and R2 and R3 are C1-C6 alkyl groups. 10 One or more substitutions of alkyl or alkyl-aryl, R4, R5 are H or C1-C 10 It is alkyl. [C31] TIFF2023554565000016.tif53129...(1) The photocurable composition may have a viscosity of 15 mPa·s or less, and a photocured layer of the photocurable composition may have a low thermal shrinkage rate when subjected to high-temperature baking treatment and a carbon content of at least 74%.

Description

[Technical Field]

[0001] This disclosure relates to a photocurable composition, and more particularly to a photocurable composition for inkjet-adaptive planarization adapted to form a photocurable layer having a low thermal shrinkage rate during a subsequent firing process. Background of the Invention

[0002] Inkjet Adaptive Planarization (IAP) is a process for planarizing the surface of a substrate, such as a wafer containing electrical circuits, by spraying droplets of a photocurable composition onto the substrate surface and bringing them into direct contact with a liquid to which a flattened superstraight has been added, thereby forming a flat liquid layer. The flattened liquid layer is typically solidified under exposure to UV light, and after removal of the superstraight, a flat polymer surface is obtained, which can then be subjected to subsequent processing steps, such as firing, etching, and / or further deposition steps.

[0003] The subsequent firing of the formed photocured layer is often carried out at a temperature higher than its glass transition temperature. This firing typically leads to the formation of a denser filler in the polymer layer, which can result in undesirable shrinkage of the layer and further challenges to planarization efficiency. Typically, thermal shrinkage during firing is greater than the shrinkage of the photocurable composition during photocuring.

[0004] There is a need for improved IAP materials that result in a planar photocurable layer with low shrinkage during subsequent processing. [Overview of the project]

[0005] In one embodiment, the photocurable composition may include a photoinitiator and a polymerizable material, the polymerizable material may include a monofunctional acrylate monomer having the structure of formula (1), where R1 is H or C1-C6 alkyl, and R2 and R3 are C1-C 10 It is a substitution of one or more alkyl or alkyl-aryl groups, where R4, R5 is H or C1-C 10 It is alkyl,

[0006] [ka] ...(1)

[0007] The amount of acrylate monomer in formula (1) may be at least 10% by weight and 30% by weight or less relative to the total weight of the polymerizable material, and the carbon content of the photocured layer of the photocurable composition may be at least 74% by weight.

[0008] In one embodiment, the polymerizable material may further comprise at least one polyfunctional acrylate monomer. In a particular embodiment, the at least one polyfunctional acrylate monomer may comprise a difunctional acrylate monomer, a trifunctional acrylate monomer, a tetrafunctional acrylate monomer, or any combination thereof. In a particular embodiment, the at least one polyfunctional acrylate monomer may comprise bisphenol A dimethacrylate (BPADMA).

[0009] In another specific embodiment of the photocurable composition, the amount of the polyfunctional acrylate monomer may be at least 10% by weight and 30% by weight or less, relative to the total weight of the polymerizable material.

[0010] In a particular embodiment of the photocurable composition, the monofunctional acrylate monomer may have the structure of formula (2), where R1 is H or CH3.

[0011] [ka] ...(2)

[0012] In one embodiment, the amount of the monofunctional acrylate monomer of formula (2) may be 25% by weight or less relative to the total weight of the polymerizable material.

[0013] In another embodiment, the amount of the monofunctional acrylate monomer of formula (2) may be 15% by weight or less with respect to the total weight of the polymerizable material.

[0014] In a further embodiment, the photocurable composition can be adapted such that the photocured layer of the composition has a heat shrinkage rate of 7.5 percent or less. The heat shrinkage rate is the difference in the thickness of the photocured layer before and after being subjected to a firing treatment at 250 °C for 2 minutes.

[0015] In another aspect, the viscosity of the photocurable composition can be 15 mPa·s or less.

[0016] In yet another aspect, the photocurable composition can be adapted such that the photocured layer of the composition has an Ohm number of 2.9 or less.

[0017] In one embodiment, the laminate can include a substrate and a photocured layer overlapping the substrate, and the photocured layer is formed from the above-described photocurable composition.

[0018] In one aspect of the laminate, the photocured layer can have a heat shrinkage rate of 7 percent or less. The heat shrinkage rate is the difference in the thickness of the photocured layer before and after being fired at 250 °C for 2 minutes.

[0019] In another aspect of the laminate, the photocured layer can have an Ohm number greater than 2.9.

[0020] In a further embodiment, a method of forming a photocured layer on a substrate can include applying a layer of a photocurable composition on the substrate, the photocurable composition can include a photoinitiator and a polymerizable material. The polymerizable substance can include 10 wt% to 30 wt% of a monofunctional acrylate monomer having the structure of formula (1), R1 is H or C1-C6 alkyl, and R2 and R3 are C1-C 10 alkyl or one or more substituents of alkyl-aryl, and R4, R5 are H or C1-C 10 alkyl.

[0021] [[ID= (34]]

Chemical formula

[0022] The method may include a step of bringing the photocurable composition into contact with a super straight, a step of irradiating the photocurable composition with light to form a photocured layer, and a step of removing the super straight from the cured layer.

[0023] In one aspect of the present method, the photocured layer can have a heat shrinkage rate of 7.5% or less. The heat shrinkage rate is the difference in the thickness of the photocured layer before and after being fired at 250°C for 2 minutes.

[0024] In another aspect of the present invention, the viscosity of the photocurable composition may be 15 mPa·s or less. [[ID=十六]] [[ID=十七]]

[0025] [[ID=十八]] [[ID=十九]] In one aspect of the method, the photocurable composition may further include bisphenol A dimethacrylate (BPADMA) in an amount of 10% to 30% by weight based on the total weight of the polymerizable composition.

[0026] In another embodiment, a method of forming an article may include a step of applying a layer of a photocurable composition on a substrate. The photocurable composition may include a photoinitiator and a polymerizable material. The polymerizable material includes 10% to 30% by weight of a monofunctional acrylate monomer having the structure of formula (1), where R1 is H or C1-C6 alkyl, and R2 and R3 are C1-C 10 One or more substitutions of alkyl or alkyl-aryl, and R4, R5 are H or C1-C 10 alkyl.

[0027]

Chemical formula

[0028] The method may include the steps of: contacting the Super Straight; irradiating the photocurable composition with light to form a photocurable layer; removing the Super Straight from the photocurable layer; forming a pattern on the substrate; processing the substrate on which the pattern was formed in the forming step; and manufacturing an article from the substrate processed in the processing step. [Modes for carrying out the invention]

[0029] The following description is provided to help understand the teachings disclosed herein and focuses on specific implementations and embodiments of the teachings. This focus is provided to help illustrate the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention pertains. Materials, methods, and examples are illustrative and not intended to limit the scope of this invention. Many details relating to specific materials and processing procedures, beyond what is described herein, are conventional and can be found in textbooks and other sources within the field of imprint and lithography techniques.

[0031] As used herein, the terms “equipped,” “having,” “including,” “containing,” “having,” “possessing,” or any other conjugation thereof shall cover non-restrictive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features and may include other features not expressly listed or that are inherent to such process, method, article, or apparatus.

[0032] As used herein, and unless explicitly stated otherwise, “or” refers to an inclusive disjunction and not an exclusive disjunction. For example, condition A or B is satisfied if A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist).

[0033] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is used simply for convenience to indicate the general meaning of the scope of the invention. This specification should be read as including one or at least one, and singular nouns include plural nouns unless it is evident that they are not plural.

[0034] The present invention relates to a photocurable composition comprising a photoinitiator and a polymerizable substance, wherein the polymerizable substance may include a monofunctional acrylate monomer having the structure of formula (1), where R1 is H or C1-C6 alkyl, and R2 and R3 are C1-C 10 One or more substituents of an alkyl or alkyl-aryl group, where R4 and R5 are H or C1-C 10 This relates to photocurable compositions using alkyl groups.

[0035] [ka] ...(1)

[0036] In certain embodiments, the monofunctional acrylate monomer may have the structure of formula (2), where R1 is H or CH3.

[0037] [ka] ...(2)

[0038] Surprisingly, it has been observed that certain combinations of the monomer of formula (1) and polyfunctional acrylate monomers can result in photocurable compositions having a low thermal shrinkage rate after curing. In one embodiment, the thermal shrinkage rate of a photocured layer formed from the photocurable composition may be 7.5% or less, e.g., 7.2% or less, 7.0% or less, 6.8% or less, 6.5% or less, 6.3% or less, or 6.0% when fired at 250°C for 2 minutes. As used herein, thermal shrinkage is calculated as the percentage difference in height of the photocured layer before and after the firing process.

[0039] In one embodiment, the polyfunctional acrylate monomer of the polymerizable material may be a difunctional acrylate monomer, a trifunctional acrylate monomer, a tetrafunctional acrylate monomer, or any combination thereof. Non-limiting examples of polyfunctional acrylate monomers may be bisphenol A dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, or any combination thereof.

[0040] In certain embodiments, the polyfunctional acrylate monomer may be a difunctional acrylate monomer. In certain embodiments, the difunctional acrylate monomer may be bisphenol A dimethacrylate having the structure shown in formula (3).

[0041] [ka] ...(3)

[0042] In one embodiment, the amount of the monofunctional acrylate monomer of formula (1) may be at least 10% by weight, for example, at least 15% by weight, or at least 20% by weight, relative to the total weight of the polymerizable material. In another specific embodiment, the amount of the monomer of formula (1) may be 40% by weight or less, or 30% by weight or less, or 25% by weight or less, or 20% by weight or less, or 15% by weight or less, or 12% by weight or less, or 10% by weight or less, relative to the total weight of the polymerizable material. The amount of the monomer of formula (1) may be a number within the range between any of the above minimum and maximum numbers.

[0043] In another embodiment, the amount of polyfunctional acrylate monomer may be at least 10% by weight, or at least 15% by weight, or at least 20% by weight, or at least 25% by weight, relative to the total weight of the polymerizable material. In another embodiment, the amount of polyfunctional acrylate monomer may be 50% by weight or less, for example, 40% by weight or less, or 30% by weight or less, or 25% by weight or less, or 20% by weight or less, relative to the total weight of the polymerizable material. The amount of polyfunctional acrylate monomer may be within any of the above minimum and maximum ranges, such as 10 wt% to 50 wt%, 15 wt% to 40 wt%, or 10 wt% to 30 wt%.

[0044] In a further embodiment, the weight percentage ratio of the multifunctional acrylate monomer to the monofunctional monomer of formula (1) may be 1:5 to 5:1, for example, 1:3 to 3:1, or 1:1 to 3:1.

[0045] A key aspect of monomer selection is maintaining a low viscosity of the polymerizable composition before curing. In one embodiment, the viscosity of the curable composition may be 30 mPa·s or less, for example, 25 mPa·s or less, or 20 mPa·s or less, or 15 mPa·s or less, or 10 mPa·s or less. In other specific embodiments, the viscosity may be at least 3 mPa·s, for example, at least 5 mPa·s, or at least 8 mPa·s. In a particularly preferred embodiment, the photocurable composition may have a viscosity of 15 mPa·s or less. As used herein, all viscosity values ​​relate to viscosity measured at a temperature of 23°C using the Brookfield method with a Brookfield viscometer.

[0046] The amount of polymerizable material in the photocurable composition may be at least 75% by weight, for example, at least 80% by weight, or at least 85% 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 99% by weight or less, for example, 98% by weight or less, or 97% by weight or less, or 95% by weight or less, based on the total weight of the photocurable composition. The amount of polymerizable material may be a value between any of the above minimum and maximum values. In a particular embodiment, the amount of polymerizable material may be at least 85% by weight and 98% by weight or less.

[0047] In another embodiment, the polymerizable material of the photocurable composition may include a certain amount of polymerizable monomers, oligomers, or polymers in addition to the monofunctional acrylate monomer of formula (1) and at least one multifunctional acrylate monomer. Not limited examples of such polymerizable compounds may be, for example, benzyl acrylate, 1-naphthyl acrylate, divinylbenzene, maleimide monomer, vinyl ether, or styrene derivative.

[0048] In one embodiment, the polymerizable material may include, in addition to the monofunctional acrylate monomer and multifunctional acrylate monomer of formula (1), at least one further monofunctional acrylate monomer, for example, at least two or three further monofunctional acrylate monomers. In a particular embodiment, the amount of the last additional monofunctional acrylate monomer may be at least 30% by weight, or at least 40% by weight, or at least 50% by weight, or at least 60% by weight, relative to the total weight of the polymerizable material. In a particular embodiment, the polymerizable material may include at least 40% by weight of benzyl acrylate as an additional monofunctional acrylate monomer.

[0049] In a further embodiment, the curable composition of the present disclosure may be solvent-free.

[0050] One or more photoinitiators can be included in the photocurable composition to initiate photocuring when exposed to light.

[0051] In some embodiments, curing can also be carried out by a combination of light and heat curing.

[0052] The photocurable composition may further contain one or more optional additives. Examples of optional additives include stabilizers, dispersants, solvents, surfactants, inhibitors, or any combination thereof.

[0053] In one embodiment, a photocurable composition can be applied to a substrate to form a photocurable layer. When used herein, the combination of a substrate and a photocurable layer superimposed on the substrate is referred to as a laminate.

[0054] The combination of monomers in the polymerizable material can result in a high carbon content in the photocured layer. In one embodiment, the carbon content of the photocured layer may be at least 70%, for example, at least 72%, or at least 73%, or at least 74%, or at least 75%, or at least 76%, or at least 77%. In certain embodiments, the carbon content may be at least 74%.

[0055] In another embodiment, the photocured layer of the laminate may have an Onishi number of 2.9 or less, or 2.8 or less, or 2.7 or less, or 2.6 or less. In another embodiment, the Onishi number may be at least 1.8, for example, at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at least 2.3.

[0056] In certain embodiments, the photocured layer may have a carbon content of at least 74% and an Onishi number of 2.9 or less.

[0057] This disclosure further relates to a method for forming a photocurable layer. This method may include coating a layer of the above-described photocurable composition onto a substrate, contacting the photocurable composition with a template or superstraight, irradiating the photocurable composition with light to form a photocurable layer, and removing the template or superstraight from the photocurable layer.

[0058] The substrate and solidified layer may be subjected to additional processing, such as an etching process, to transfer an image corresponding to the pattern of one or both of the patterns in the solidified layer and / or the patterned layer beneath the solidified layer onto the substrate. 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, moldable material removal, dicing, bonding, and packaging.

[0059] Furthermore, it may be used as an interlayer insulating film for semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, and D-RDRAMs, or as a resist film used in semiconductor manufacturing processes.

[0060] As will be further demonstrated in the examples, it has been surprisingly discovered that in photocurable compositions, certain combinations of polymerizable monomers containing a monofunctional acrylate monomer of formula (1) and at least one second monomer including a polyfunctional acrylate monomer can have properties that are particularly well-suited for IAP treatment. The photocurable compositions of the present invention can have a desired low viscosity of less than 15 mPa·s, and when exposed to high-temperature firing treatment, a photocured layer can be formed with low thermal shrinkage. Examples The following non-limiting examples illustrate the concepts described herein.

[0061] Example 1 Preparation of photocurable IAP compositions For each sample, monofunctional acrylate monomer 3-phenoxybenzyl acrylate (POBA) was replaced with a difunctional acrylate monomer. bisphenol Five photocurable compositions (Samples S1-S5) were prepared by combining A dimethacrylate (BPADMA) with two additional monomers selected from benzyl acrylate (BA), 1-naphthyl acrylate (1-NA), and ortho-phenylphenol EO acrylate (Miramer M1142 from Miwon Specialty Chemical Co., Ltd). The exact combinations and amounts of polymerizable material monomers for each composition are summarized in Table 1 below.

[0062] Furthermore, two comparative example photocurable compositions were prepared by combining bifunctional BPADMA with BA and 1-NA (composition C1 of the comparative example), and by combining BPADMA with BA, 1-NA and 1-adamantyl methacrylate (1-AMA) (composition C2 of the comparative example). The structure of 1-AMA is shown in formula (4).

[0063]

Chemical formula

[0064] The polymeric materials of the comparative example compositions C1 and C2 are also summarized in Table 1. All the photocurable compositions further contained Irgacure 819 as a photoinitiator in an amount of 1 to 5% by weight and C10GM2070 as a surfactant in an amount of 0.1 to 3% by weight.

[0065]

Table 1

[0066] From the photocurable compositions summarized in Table 1, a liquid film of the photocurable composition with a thickness of about 300 μm was applied onto a glass substrate and exposed to an ultraviolet intensity of 4 mW / cm 2 corresponding to a curing energy dose of 2.4 J / cm 2 for 600 seconds to prepare a photocured layer. After photocuring, all the photocured layers were solid.

[0067] Measurement of thermal shrinkage To evaluate the thermal shrinkage, the photocured layer was placed on a hot plate having a temperature of 250 °C for 2 minutes after photocuring. This is also referred to as baking in this specification. All the baking treatments were carried out under air. The thermal shrinkage was measured by using an ellipsometer to measure the change in the thickness of the tested layer before and after the baking treatment, and the thermal shrinkage (St) was obtained by calculating according to the formula: St = (T u - T b ) / T u , where T u is the thickness of the layer at the unbaked stage before baking, and Tb This is the thickness of the layer after firing.

[0068] Table 2 summarizes the results of the heat shrinkage tests for all samples. Table 2 further includes the calculated carbon content by weight % and the layer number. It can be seen that samples S1-S5 had a heat shrinkage rate approximately 1-3 percent lower than comparative examples C1 and C2.

[0069] [Table 2]

[0070] The viscosity of the samples was measured at 200 rpm and 23°C using a Brookfield viscometer LVDV-II + Pro with a spindle size of #18. For viscosity testing, approximately 6–7 mL of sample liquid was added to the sample chamber in an amount sufficient to cover the spindle head. At least three measurements were taken for each viscosity test, and the average value was calculated.

[0071] The Onishi number (ON) is known to be an empirical parameter, and is the total number of atoms (N) in the polymer repeating unit. t ) and the number of carbon atoms (Nc) and oxygen atoms (N) in the unit. O The ratio obtained by dividing by the difference between ) and ON=N t / (N C -N O ) is calculated as follows. For the calculation of the Onishi number, it was assumed that the cured material contains 100% by weight of polymer monomer units formed by addition polymerization (no atoms are lost during polymerization).

[0072] The description and examples of embodiments described herein are intended to provide a general understanding of the structures of various embodiments. This specification and examples do not exhaustively or comprehensively describe all elements and features of apparatus and systems that use the structures or methods described herein. Different embodiments may also be provided in combination in a single embodiment, and conversely, for the sake of 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 all values ​​within that range. Many other embodiments may be obvious to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure so that structural substitutions, logical substitutions, or other modifications may be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

Claims

1. A photocurable composition comprising a photoinitiator and a polymerizable material, The polymerizable material is, 3-phenoxybenzyl acrylate in an amount of 10% to 40% by weight relative to the total weight of the polymerizable material, A polyfunctional acrylate monomer in an amount of 10% to 40% by weight relative to the total weight of the polymerizable material, A monofunctional acrylate monomer selected from benzyl acrylate (BA), 1-naphthyl acrylate (1-NA), and ortho-phenylphenol EO acrylate, Includes, The aforementioned polyfunctional acrylate monomer includes bisphenol A dimethacrylate (BPADA), The weight ratio of the 3-phenoxybenzyl acrylate to the polyfunctional acrylate monomer in the polymerizable material is in the range of 1:3 to 3:

1. A photocurable composition characterized in that the photocurable layer obtained from the photocurable composition is adapted to have a thermal shrinkage rate of 5.32 percent or more and 7.5 percent or less, which is measured based on the difference in thickness of the photocurable layer before and after a firing treatment at 250°C for 2 minutes.

2. The photocurable composition according to claim 1, characterized in that the viscosity of the photocurable composition is 3 mPa·s or more and 15 mPa·s or less.

3. The photocurable composition according to claim 1 or 2, characterized in that the photocurable layer obtained from the photocurable composition is adapted to have an Onishi number of 1.8 or more and 2.9 or less.

4. A laminate comprising a substrate and a photocurable layer superimposed on the substrate, A laminate characterized in that the photocurable layer is formed from a photocurable composition according to any one of claims 1 to 3.

5. The laminate according to claim 4, characterized in that the photocured layer has a thermal shrinkage rate of 5.32 percent or more and 7.5 percent or less, which is measured based on the difference in the thickness of the photocured layer before and after a firing treatment at 250°C for 2 minutes.

6. The laminate according to claim 4 or 5, characterized in that the light-curing layer has an Onishi number of 1.8 or more and 2.9 or less.

7. A method for forming a photocurable layer on a substrate, A step of applying a layer of the photocurable composition according to any one of claims 1 to 3 onto the substrate, The steps include bringing the aforementioned photocurable composition into contact with the superstraight, The process involves irradiating the photocurable composition with light to form a photocurable layer, A step of removing the superstraight from the light-cured layer, A method characterized by including the following.

8. The method according to 7, characterized in that the photocured layer has a thermal shrinkage rate of 5.32 percent or more and 7.5 percent or less, which is measured based on the difference in the thickness of the photocured layer before and after a firing treatment at 250°C for 2 minutes.

9. The method according to 7 or 8, characterized in that the viscosity of the photocurable composition is 3 mPa·s or more and 15 mPa·s or less.

10. A method for forming an article, A step of coating a layer of the photocurable composition according to any one of claims 1 to 3 onto a substrate, The steps include bringing the photocurable composition into contact with Super Straight, The process involves irradiating the photocurable composition with light to form a photocurable layer, A step of removing the superstraight from the light-cured layer, The steps include forming a pattern on the substrate, A step of processing the substrate on which the pattern is formed, A process for manufacturing an article from the processed substrate, A method characterized by including the following.

11. The method according to claim 10, characterized in that the photocured layer has a thermal shrinkage rate of 5.32 percent or more and 7.5 percent or less, which is measured based on the difference in the thickness of the photocured layer before and after a firing treatment at 250°C for 2 minutes.

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