Resin mixture and resin composition

Abstract

The invention provides a resin mixture which comprises first resin, second resin and a solvent, and the first resin and the second resin are dissolved in the solvent. The structure of the first resin is as shown in formula I, wherein R1, R2 and R3 are independently selected from H or C1-C5 alkyl; r4 is selected from H or C1-C5 alkyl groups or C1-C5 alkyl groups substituted by monohydroxyl groups; a and b are positive integers greater than 1, a / (a + b) = 10%-90%, and b / (a + b) = 10%-90%; the structural formula of the second resin is as shown in the following formula II, wherein R5, R6 and R8 are independently selected from H or C1-C5 alkyl; r7 is selected from C1-C5 alkyl groups, C1-C5 alkyl groups substituted by methacryloyloxy groups or C1-C5 alkyl groups substituted by acryloyloxy groups; c and d are positive integers greater than 1, c / (c + d) = 10%-90%, and d / (c + d) = 10%-90%. The invention also provides a resin composition. The resin mixture provided by the invention can be fully cured at a relatively low temperature.

Description

Technical Field

[0001] This application relates to the field of semiconductor manufacturing technology, and in particular to a resin mixture and resin composition. Background Technology

[0002] With the development of the microelectronics industry, the requirements for the resolution of photolithography technology are becoming increasingly stringent. In the photolithography process, using organic planarization coatings (Spin-On Carbon, SOC) to eliminate standing wave effects, recess effects, and planarize the substrate has become a common method in the industry to improve the uniformity of critical dimensions and pattern resolution.

[0003] Currently, all SOCs used in the industry have a curing temperature above 200℃, so the post-apply bake (PAB) for SOCs is also at 200℃. However, the PAB temperature for photoresist is below 150℃. Therefore, photoresist and SOCs cannot be baked on the same hot plate. Typically, SOCs are mounted on a bottom anti-reflective coating machine for processing, which not only reduces the machine's efficiency but also increases its cost.

[0004] Meanwhile, during the manufacturing process, the wafer will warp under stress, which will cause the edge of the wafer to not adhere tightly to the hot plate during baking. As a result, the edge of the wafer cannot reach the set temperature, and the SOC coated on the edge of the wafer surface cannot be cured, resulting in defects such as wrinkles.

[0005] In addition, some SOCs release a large amount of gas during the curing process, which can easily cause defects in the SOC during curing.

[0006] Therefore, in order to meet the requirements of SOC curing process in chip manufacturing for equipment utilization efficiency, curing completeness, and reduced gas release, it is necessary to develop resin mixtures that can be fully cured at lower temperatures as raw materials for organic planarization coatings. Summary of the Invention

[0007] The purpose of this application is to provide a resin mixture that can be fully cured at a lower temperature as a raw material for an organic planarization coating.

[0008] In a first aspect, this application provides a resin mixture comprising: a first resin, the structure of which is shown in Formula I:

[0009]

[0010] Wherein, R1, R2, and R3 are each independently selected from H or C1-C5 alkyl groups; R4 is selected from H or C1-C5 alkyl groups or monohydroxy-substituted C1-C5 alkyl groups; a and b are positive integers greater than 1, a / (a+b) = 10%-90%, b / (a+b) = 10%-90%; the second resin has the following structural formula II:

[0011]

[0012] R5, R6, and R8 are each independently selected from H or C1-C5 alkyl groups; R7 is selected from C1-C5 alkyl groups, methacryloyloxy-substituted C1-C5 alkyl groups, or acryloyloxy-substituted C1-C5 alkyl groups; c and d are positive integers greater than 1, c / (c+d) = 10%-90%, d / (c+d) = 10%-90%; and a solvent, wherein the first resin and the second resin are dissolved in the solvent.

[0013] In some embodiments, the weight-average molecular weight of the first resin is 2,000 to 30,000, and the weight-average molecular weight of the second resin is 2,000 to 30,000.

[0014] In some embodiments, the solvent has a boiling point of 100–300°C.

[0015] In some embodiments, the resin mixture further includes monomers, the monomers including at least one of monofunctional monomers, difunctional monomers, or polyfunctional monomers containing two or more functional groups.

[0016] In some embodiments, the content of the monomer is 0.1 to 10% of the total mass of the first resin and the second resin.

[0017] In some embodiments, the resin mixture further includes a thermally polymerizing free radical initiator and a leveling agent, wherein the thermally polymerizing free radical initiator includes at least one of azo free radical initiators, peroxide free radical initiators, and redox free radical initiators; and the leveling agent includes at least one of acrylic leveling agents, silicone leveling agents, and fluorocarbon leveling agents.

[0018] In some embodiments, based on a total mass of 100 parts by weight of the resin mixture, the content of the first resin is 0.1 to 25 parts by weight, the content of the second resin is 0.1 to 25 parts by weight, the content of the thermal polymerization free radical initiator is 0.1 to 10 parts by weight, the content of the additive is 0.01 to 5 parts by weight, and the content of the solvent is 10 to 90 parts by weight.

[0019] Secondly, this application also provides a resin composition comprising: a first network crosslinked structure formed by a first resin and a second resin through a click reaction; and a second network crosslinked structure formed by the first resin and the second resin through a Diels-Alder reaction; the structure of the first resin is shown in Formula I below:

[0020]

[0021] Wherein, R1, R2, and R3 are each independently selected from H or C1-C5 alkyl groups; R4 is selected from H or C1-C5 alkyl groups or monohydroxy-substituted C1-C5 alkyl groups; a and b are positive integers greater than 1, a / (a+b) = 10%-90%, b / (a+b) = 10%-90%; and the structural formula of the second resin is shown in Formula II below:

[0022]

[0023] R5, R6, and R8 are each independently selected from H or C1-C5 alkyl groups; R7 is selected from C1-C5 alkyl groups, methacryloyloxy-substituted C1-C5 alkyl groups, or acryloyloxy-substituted C1-C5 alkyl groups; c and d are positive integers greater than 1, c / (c+d) = 10%-90%, and d / (c+d) = 10%-90%.

[0024] In some embodiments, the resin composition further includes a third network crosslinking structure formed by the second resin and the monomer through a click reaction, wherein the monomer includes at least one of a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer containing two or more functional groups.

[0025] In some embodiments, the weight-average molecular weight of the first resin is 2,000 to 30,000, and the weight-average molecular weight of the second resin is 2,000 to 30,000.

[0026] The beneficial effects of the resin mixture provided in this application include, but are not limited to, the following:

[0027] At a baking temperature far lower than that of existing organic planarization coatings (which are typically above 200°C), for example below 150°C, the first and second mixtures in the resin mixture provided in this application can react to form a cross-linked network structure, thus completing the resin curing. When the resin mixture provided in this application is used as a raw material for the organic planarization coating, since the curing temperature of the resin mixture is similar to that of the photoresist, the same hot plate can be used to bake both the organic planarization coating and the photoresist, improving the efficiency of the baking machine and reducing production costs.

[0028] In addition, the resin mixture provided in this application has a fast curing rate, complete curing reaction, and low content of small molecular weight volatile components, which results in a small amount of gas release during the curing process of the organic planarization coating formed by the resin mixture as raw material, thereby avoiding too many defects in the cured organic planarization coating. Detailed Implementation

[0029] The following description provides specific application scenarios and requirements for this application, intended to enable those skilled in the art to make and use the content of this application. Various partial modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but rather to the widest scope consistent with the claims.

[0030] This application provides a resin mixture, comprising: a first resin, the structure of which is shown in Formula I:

[0031]

[0032] R1, R2 and R3 are each independently selected from H or C1 to C5 alkyl; R4 is selected from H or C1 to C5 alkyl or monohydroxy-substituted C1 to C5 alkyl; a and b are positive integers greater than 1, a / (a+b) = 10% to 90%, b / (a+b) = 10% to 90%;

[0033] The second resin has the following structural formula II:

[0034]

[0035] Wherein, R5, R6, and R8 are each independently selected from H or C1-C5 alkyl groups; R7 is selected from C1-C5 alkyl groups, methacryloyloxy-substituted C1-C5 alkyl groups, or acryloyloxy-substituted C1-C5 alkyl groups; c and d are positive integers greater than 1, c / (c+d) = 10%-90%, d / (c+d) = 10%-90%; and

[0036] The solvent in which the first resin and the second resin are dissolved.

[0037] At a baking temperature far lower than that of existing organic planarization coatings (which are typically above 200°C), for example below 150°C, the first and second mixtures in the resin mixture provided in this application can react to form a cross-linked network structure, thus completing the resin curing. When the resin mixture provided in this application is used as a raw material for the organic planarization coating, since the curing temperature of the resin mixture is similar to that of the photoresist, the same hot plate can be used to bake both the organic planarization coating and the photoresist, improving the efficiency of the baking machine and reducing production costs.

[0038] The resin mixture provided in this application will be described in detail below with reference to the embodiments.

[0039] This application provides a resin mixture comprising: a first resin, a second resin, and a solvent, wherein the first resin and the second resin are dissolved in the solvent, and the structure of the first resin is shown in Formula I below:

[0040]

[0041] R1, R2 and R3 are each independently selected from H or C1 to C5 alkyl; R4 is selected from H or C1 to C5 alkyl or monohydroxy-substituted C1 to C5 alkyl; a and b are positive integers greater than 1, a / (a+b) = 10% to 90%, b / (a+b) = 10% to 90%;

[0042] The structural formula of the second resin is shown in Formula II below:

[0043]

[0044] R5, R6, and R8 are each independently selected from H or C1-C5 alkyl groups; R7 is selected from C1-C5 alkyl groups, methacryloyloxy-substituted C1-C5 alkyl groups, or acryloyloxy-substituted C1-C5 alkyl groups; c and d are positive integers greater than 1, c / (c+d) = 10%-90%, and d / (c+d) = 10%-90%.

[0045] The resin mixture provided in this application can be cured at baking temperatures far lower than those used in prior art organic planarization coatings, for example, below 150°C. When the resin mixture is baked and heated, the acrylic structural units of the first resin and the thiol structural units of the second resin undergo a click reaction to form a first network crosslinked structure, and the furan structural units of the first resin and the maleimide structural units of the second resin undergo a Diels-Alder reaction to form a second network crosslinked structure, thereby curing the resin mixture.

[0046] In some embodiments, the weight-average molecular weight of the first resin is 2,000 to 30,000, and the weight-average molecular weight of the second resin is 2,000 to 30,000.

[0047] In some embodiments, the boiling point of the solvent is 100–300°C.

[0048] In some embodiments, the solvent includes at least one selected from alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

[0049] Preferably, the solvent includes at least one selected from alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

[0050] Preferably, the solvent includes at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate.

[0051] In some embodiments, the resin mixture further includes a monomer, which includes at least one of a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer containing two or more functional groups; preferably, the monomer is a polyfunctional monomer containing two or more functional groups.

[0052] During the baking of the resin mixture, the monomer reacts with the thiol structural units of the second resin via a click reaction to form a third network crosslinked structure. Adding an appropriate amount of monomer can further increase the final crosslinking density of the resin mixture, and the type and amount of monomer can also be adjusted according to the subsequent etching rate of the organic planarization coating.

[0053] In some embodiments, the monofunctional monomer includes at least one of nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

[0054] In some embodiments, the bifunctional monomer includes at least one of 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentyl glycol di(meth)acrylate.

[0055] In some embodiments, the multifunctional monomer includes at least one of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0056] In some embodiments, the monomer content is 0.1% to 10% of the total mass of the first resin and the second resin; for example, 0.1%, 1%, 3%, 5%, 8%, or 10%. Preferably, the monomer content is 5% of the total mass of the first resin and the second resin. If the amount of monomer added is too low, the effect will be insignificant; if the amount added is too high, some monomer will volatilize during the heating and curing of the resin mixture, resulting in gas release and causing defects in the film layer formed by the curing of the resin mixture.

[0057] In some embodiments, the resin mixture further includes a thermally polymerizing free radical initiator and additives.

[0058] The thermal polymerization free radical initiator includes at least one of the following compounds: azo free radical initiator, peroxide free radical initiator, and redox free radical initiator.

[0059] In some embodiments, the thermal polymerization free radical initiator includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and azobisisobutylamidine hydrochloride; the peroxide free radical initiator includes at least one of benzoyl peroxide, methyl ethyl ketone peroxide, and benzoyl tert-butyl peroxide; and the redox free radical initiator includes at least one of benzoyl peroxide-DMA and benzoyl peroxide-DMT.

[0060] It should be noted that the imide group of the second resin can serve as an amine co-initiator for the thermal polymerization free radical initiator to enhance the initiation efficiency.

[0061] In some embodiments, the leveling agent includes at least one of acrylic leveling agents, silicone leveling agents, and fluorocarbon leveling agents.

[0062] In some embodiments, based on 100 parts by weight of the total mass of the resin mixture, the content of the first resin is 0.1 to 25 parts by weight; the content of the second resin is 0.1 to 25 parts by weight; the content of the thermal polymerization free radical initiator is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight; the content of the additive is 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight; and the content of the solvent is 10 to 90 parts by weight, preferably 15 to 85 parts by weight.

[0063] This application also provides a resin composition comprising: a first network cross-linked structure formed by a first resin and a second resin through a click reaction; and a second network cross-linked structure formed by a Diels-Alder reaction between the first resin and the second resin;

[0064] The structure of the first resin is shown in Formula I below:

[0065]

[0066] Wherein, R1, R2, and R3 are each independently selected from H or C1-C5 alkyl groups; R4 is selected from H or C1-C5 alkyl groups or monohydroxy-substituted C1-C5 alkyl groups; a and b are positive integers greater than 1, a / (a+b) = 10%-90%, b / (a+b) = 10%-90%; and

[0067] The structural formula of the second resin is shown in Formula II below:

[0068]

[0069] R5, R6, and R8 are each independently selected from H or C1-C5 alkyl groups; R7 is selected from C1-C5 alkyl groups, methacryloyloxy-substituted C1-C5 alkyl groups, or acryloyloxy-substituted C1-C5 alkyl groups; c and d are positive integers greater than 1, c / (c+d) = 10%-90%, and d / (c+d) = 10%-90%.

[0070] In some embodiments, the weight-average molecular weight of the first resin is 2,000 to 30,000, and the weight-average molecular weight of the second resin is 2,000 to 30,000.

[0071] In some embodiments, the resin composition further includes a third network crosslinking structure formed by the first resin and the monomer through a click reaction, wherein the monomer includes at least one of a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer containing two or more functional groups.

[0072] In some embodiments, the monofunctional monomer includes at least one of nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

[0073] In some embodiments, the bifunctional monomer includes at least one of 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentyl glycol di(meth)acrylate.

[0074] In some embodiments, the multifunctional monomer includes at least one of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0075] The resin mixtures and resin compositions provided in this application will be described in detail below with reference to specific embodiments.

[0076] Unless otherwise specified, the raw materials, reagents, or apparatus used in the following examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0077] Preparation of raw materials

[0078] Preparation of the first resin

[0079] Preparation Example 1

[0080] In a 500 mL flask equipped with a reflux condenser, dropping funnel, and stirrer, nitrogen gas was introduced at a rate of 0.01 L / min to create a nitrogen atmosphere. Then, 200 g of propylene glycol monomethyl ether acetate was added. After heating to 87 °C, 0.6 mol of monomer A (the structural formula of monomer A is...) was added to the flask. 0.6 mol of monomer B (the structural formula of monomer B is...) After thorough mixing, 3.6 g of azobisisobutyronitrile (AIBN) was dissolved in 50 g of propylene glycol methyl ether acetate to obtain a first mixed solution. This solution was slowly added dropwise to the flask via a dropping funnel over 1 hour, and the mixture was stirred for 5 hours after the addition was complete. A second mixed solution, obtained by dissolving 0.3 mol of methacrylic anhydride in 20 g of propylene glycol methyl ether acetate, was then slowly added dropwise to the flask via a dropping funnel over 1 hour, and the mixture was stirred for 1 hour to obtain the first resin. The weight-average molecular weight of the first resin was determined to be 8000 by gel permeation chromatography (GPC).

[0081] Preparation Example 2

[0082] The preparation method in this example is largely the same as that in Preparation Example 1, except that methacrylic anhydride is replaced with acrylic anhydride. The weight-average molecular weight of the first resin obtained is 8000.

[0083] Preparation of the second resin

[0084] Preparation Example 3

[0085] In a 500 mL flask equipped with a reflux condenser, dropping funnel, and stirrer, nitrogen gas was introduced at a rate of 0.01 L / min to create a nitrogen atmosphere. Then, 200 g of propylene glycol monomethyl ether acetate was added. After heating to 87 °C, 0.6 mol of monomer C (the structural formula of monomer C is...) was added to the flask. ) and 0.6 mol of monomer D (the structural formula of monomer D is ) After thorough mixing, the first mixed solution, obtained by dissolving 3.6 g of azobisisobutyronitrile in 50 g of propylene glycol methyl ether acetate, was slowly added dropwise to the flask through a dropping funnel over 1 hour. After the addition was complete, the mixture was stirred for 5 hours. The second mixed solution, obtained by dissolving 0.6 mol of maleic anhydride in 20 g of propylene glycol methyl ether acetate, was then slowly added dropwise to the flask through a dropping funnel over 1 hour. The mixture was stirred for 1 hour. The third mixed solution, obtained by dissolving 0.3 mol of methacrylic anhydride in 20 g of propylene glycol methyl ether acetate, was then slowly added dropwise to the flask through a dropping funnel over 1 hour. The mixture was stirred for 1 hour, thus obtaining the second resin. According to gel permeation chromatography (GPC), the weight-average molecular weight of the second resin was 12000.

[0086] Preparation Example 4

[0087] The preparation method in this example is largely the same as that in Preparation Example 1, except that methacrylic anhydride is replaced with acrylic anhydride. The weight-average molecular weight of the second resin obtained is 12,000.

[0088] Preparation of resin mixtures

[0089] Example 1

[0090] Based on a total mass of 100 parts by weight of the resin mixture, 16 parts by weight of the first resin prepared in Preparation Example 1, 4 parts by weight of the second resin prepared in Preparation Example 3, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0091] Example 2

[0092] Based on a total mass of 100 parts by weight of the resin mixture, 10 parts by weight of the first resin prepared in Preparation Example 1, 10 parts by weight of the second resin prepared in Preparation Example 3, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0093] Example 3

[0094] Based on a total mass of 100 parts by weight of the resin mixture, 4 parts by weight of the first resin prepared in Preparation Example 1, 16 parts by weight of the second resin prepared in Preparation Example 3, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0095] Example 4

[0096] Based on a total mass of 100 parts by weight of the resin mixture, 16 parts by weight of the first resin prepared in Preparation Example 2, 4 parts by weight of the second resin prepared in Preparation Example 4, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0097] Example 5

[0098] Based on a total mass of 100 parts by weight of the resin mixture, 10 parts by weight of the first resin prepared in Preparation Example 2, 10 parts by weight of the second resin prepared in Preparation Example 4, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0099] Example 6

[0100] Based on a total mass of 100 parts by weight of the resin mixture, 4 parts by weight of the first resin prepared in Preparation Example 2, 16 parts by weight of the second resin prepared in Preparation Example 4, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of azobisisobutyronitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0101] Comparative Example 1

[0102] Based on a total mass of 100 parts by weight of the resin mixture, 20 parts by weight of the first resin prepared in Preparation Example 1, 2 parts by weight of dipentaerythritol hexaacrylate (Sartoma), 0.7 parts by weight of azobisisoheptanenitrile, 0.05 parts by weight of azobisisoheptanenitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0103] Comparative Example 2

[0104] Based on a total mass of 100 parts by weight of the resin mixture, 20 parts by weight of the second resin prepared in Preparation Example 4, 2 parts by weight of pentaerythritol triacrylate (Sartoma), 0.7 parts by weight of azobisisoheptanenitrile, 0.05 parts by weight of azobisisoheptanenitrile, 0.05 parts by weight of leveling agent KF563 (Takeda Chemical), and 77.25 mol of a solvent containing propylene glycol methyl ether acetate and propylene glycol methyl ether in a 7:3 ratio were mixed evenly to obtain the resin mixture.

[0105] Performance testing

[0106] Curing properties after baking

[0107] The resin mixtures obtained from Examples 1-6, Comparative Examples 1 and 2, and Comparative Examples 3-5 (comparative Examples 3-5 are commercial raw materials for organic planarization coatings NFC1400, AR40-800, and GF315, respectively) were spin-coated onto 12-inch silicon wafers. The wafers were then baked on a hot plate for 175°C-60s and 140°C-60s, respectively. After cooling to room temperature, the thickness of the organic planarization coating was measured using an ellipsometry. The wafers were then rinsed with OK73 solvent for 30s, rotated at 2000 rpm / min for 30s, and the thickness was measured again using an ellipsometry. The difference in thickness before and after rinsing was calculated. The performance test results are shown in Table 1.

[0108] Table 1. Thickness difference (THK loss) of organic planarization coatings obtained by spin coating in Examples 1-6 and Comparative Examples 1-5 before and after rinsing following baking at 175°C.

[0109]

[0110] As can be seen from Table 1, the thickness difference of the organic planarization coatings in Examples 1-6 and Comparative Examples 2 and 3 before and after rinsing is very small, indicating that the organic planarization coatings in Examples 1-6 and Comparative Examples 2 and 3 are well cured after baking at 175°C; the organic planarization coatings in Comparative Examples 1, 4 and 5 have obvious thickness differences before and after rinsing, indicating that the organic planarization coatings in Comparative Examples 1, 4 and 5 are not completely cured after baking at 175°C.

[0111] Furthermore, the resin mixtures of Examples 1-6, Comparative Example 2, and the organic planarization coating of Comparative Example 3 were spin-coated onto a 12-inch silicon wafer, then baked at 140°C for 60 seconds on a hot plate. After cooling the silicon wafer to room temperature, the thickness of the bottom organic planarization coating was measured using an ellipsometry. The wafer was then rinsed with OK73 solvent for 30 seconds, rotated at 2000 rpm / min for 30 seconds, and the thickness of the organic planarization coating was measured again using an ellipsometry. The difference in film thickness before and after rinsing was calculated. The performance test results are shown in Table 2.

[0112] Table 2. Thickness difference (THK) of the organic planarization coatings obtained from the resin mixtures of Examples 1-6 and 8 and the organic planarization coating of Comparative Example 1 before and after rinsing after baking at 140°C.

[0113] loss)

[0114]

[0115] As can be seen from Table 2, the thickness difference of the organic planarization coatings in Examples 1-6 before and after rinsing is minimal, indicating that the organic planarization coatings prepared by the resin mixture provided in this application can also exhibit good curing performance at low temperatures, i.e., 140°C. Although the resin mixture in Comparative Example 2 exhibits good curing performance at 175°C, it cannot be completely cured at 140°C, indicating that the mixture of the second resin and pentaerythritol triacrylate alone cannot achieve curing at low temperatures. The prior art organic planarization coating in Comparative Example 3 shows a huge difference in thickness before and after rinsing, indicating that the organic planarization coating in Comparative Example 3 has extremely poor curing performance at 140°C.

[0116] Gas release performance

[0117] Based on the results of the above curing performance tests, the resin mixtures obtained in Examples 1-6 were spin-coated onto 4-inch silicon wafers and baked at 140°C for 60 seconds on a hot plate. The organic planarization coatings of Comparative Examples 3-5 were spin-coated onto 4-inch silicon wafers and baked at 210°C for 60 seconds on a hot plate, so that the resin mixtures obtained in Examples 1-6 and the organic planarization coatings obtained by spin-coating in Comparative Examples 3-5 were completely cured. During this period, the weight of volatiles was collected using a micro-quartz balance, and the outgassing weights of Examples 1-6 and Comparative Examples 3-5 were compared. The performance test results are shown in Table 3.

[0118] Table 3. Gas release weights during the curing process of the organic planarization coatings obtained by spin coating in Examples 1-6 and Comparative Examples 3-5.

[0119]

[0120] As can be clearly seen from Table 3, the release weight of the organic planarization coating obtained by spin coating of the resin mixtures in Examples 1-6 is much smaller than that of the organic planarization coatings in Comparative Examples 3-5. This is because the resin mixtures provided in Examples 1-6 of this application have a fast curing rate, complete curing reaction, and low content of small molecular weight volatile components, resulting in a small amount of gas release during the curing process of the organic planarization coating, thereby avoiding too many defects in the cured organic planarization coating.

[0121] The beneficial effects of the resin mixture provided in this application include, but are not limited to, the following:

[0122] At a baking temperature far lower than that of existing organic planarization coatings (which are typically above 200°C), for example below 150°C, the first and second mixtures in the resin mixture provided in this application can react to form a cross-linked network structure, thus completing the resin curing. When the resin mixture provided in this application is used as a raw material for the organic planarization coating, since the curing temperature of the resin mixture is similar to that of the photoresist, the same hot plate can be used to bake both the organic planarization coating and the photoresist, improving the efficiency of the baking machine and reducing production costs.

[0123] In addition, the resin mixture provided in this application has a fast curing rate, complete curing reaction, and low content of small molecular weight volatile components, which results in a small amount of gas release during the curing process of the organic planarization coating formed by the resin mixture as raw material, thereby avoiding too many defects in the cured organic planarization coating.

[0124] In summary, after reading this application, those skilled in the art will understand that the foregoing application content is presented by way of example only and is not restrictive. Although not explicitly stated herein, those skilled in the art will understand that this application is intended to encompass various reasonable changes, improvements, and modifications to the embodiments. These changes, improvements, and modifications are all within the spirit and scope of the exemplary embodiments of this application.

Claims

1. A resin mixture, characterized by, comprises: a first resin, a structure of the first resin is shown in the following formula I: wherein R1, R2 and R3 are each independently selected from H or C1-C5 alkyl; R4 is selected from H or C1-C5 alkyl or monohydroxyl-substituted C1-C5 alkyl; a, b are positive integers greater than 1, a / (a+b)=10%-90%, b / (a+b)=10%-90%; a second resin, a structure of the second resin is shown in the following formula II: wherein R5, R6 and R8 are each independently selected from H or C1-C5 alkyl; R7 is selected from C1-C5 alkyl, methacryloyloxy-substituted C1-C5 alkyl or acryloyloxy-substituted C1-C5 alkyl; c, d are positive integers greater than 1, c / (c+d)=10%-90%, d / (c+d)=10%-90%; and a solvent, the first resin and the second resin are dissolved in the solvent.

2. The resin mixture according to claim 1, characterized in that, The weight average molecular weight of the first resin is 2000-30000, and the weight average molecular weight of the second resin is 2000-30000.

3. The resin mixture of claim 1, wherein The boiling point of the solvent is 100-300℃.

4. The resin mixture of claim 1, wherein Further comprising a monomer, the monomer comprises at least one of a monofunctional monomer, a bifunctional monomer or a multifunctional monomer containing two or more functional groups.

5. The resin mixture of claim 4, wherein, The content of the monomer is 0.1-10% of the total mass of the first resin and the second resin.

6. The resin mixture of claim 1, wherein, Further comprising a thermal polymerization free radical initiator and a leveling agent, the thermal polymerization free radical initiator comprises at least one of azo-based free radical initiators, peroxide-based free radical initiators and redox-based free radical initiator compounds; and the leveling agent comprises at least one of acrylic-based leveling agents, silicone-based leveling agents and fluorocarbon compound-based leveling agents.

7. The resin mixture of claim 6, wherein, According to the total mass of the resin mixture being 100 parts by weight, the content of the first resin is 0.1-25 parts by weight, the content of the second resin is 0.1-25 parts by weight, the content of the thermal polymerization free radical initiator is 0.1-10 parts by weight, the content of the auxiliary agent is 0.01-5 parts by weight, and the content of the solvent is 10-90 parts by weight.

8. A resin composition characterized by comprising: comprises: a first reticular crosslinked structure generated by click reaction of a first resin and a second resin; and a second reticular crosslinked structure generated by Diels-Alder reaction of the first resin and the second resin; a structure of the first resin is shown in the following formula I: wherein R1, R2 and R3 are each independently selected from H or C1-C5 alkyl; R4 is selected from H or C1-C5 alkyl or monohydroxyl-substituted C1-C5 alkyl; a, b are positive integers greater than 1, a / (a+b)=10%-90%, b / (a+b)=10%-90%; and a structure of the second resin is shown in the following formula II: wherein R5, R6 and R8 are each independently selected from H or C1-C5 alkyl; R7 is selected from C1-C5 alkyl, methacryloyloxy-substituted C1-C5 alkyl or acryloyloxy-substituted C1-C5 alkyl; c, d are positive integers greater than 1, c / (c+d)=10%-90%, d / (c+d)=10%-90%. wherein R5, R6 and R8 are each independently selected from H or C1-C5 alkyl; R7 is selected from C1-C5 alkyl, methyl acryloyloxy-substituted C1-C5 alkyl or acryloyloxy-substituted C1-C5 alkyl; c, d are positive integers greater than 1, c / (c+d)=10% to 90%, d / (c+d)=10% to 90%.

9. The resin composition according to claim 8, characterized by Also included is a third network crosslinked structure generated by a click reaction between the second resin and a monomer, the monomer including at least one of a monofunctional monomer, a bifunctional monomer or a multifunctional monomer containing two or more functional groups.

10. The resin composition according to claim 8, characterized by The first resin has a weight average molecular weight of 2000 to 30000, and the second resin has a weight average molecular weight of 2000 to 30000.

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