Active group-containing resin composition and application thereof, double-active group resin and application thereof

Abstract

The invention provides a composition containing active group resin and application thereof, and double-active group resin and application thereof. The composition containing the active group resin comprises the following components in parts by mass: 50-65 parts of the active group resin, 10-20 parts of an alkenyl-containing carboxylic acid monomer, 5-15 parts of a cross-linking agent, 0.5-2 parts of a photoinitiator 1, 1-15 parts of a photoinitiator 2 and 5-30 parts of a solvent, wherein the photoinitiator 1 is an acylphosphine oxide free radical photoinitiator; and the photoinitiator 2 is a non-acylphosphine oxide free radical photoinitiator. According to the composition containing the active group resin provided by the invention, by blending a formula system, especially matching between the photoinitiators and matching between the photoinitiators and the active group resin, the prepared photoresist can be straight in line, upright and regular in morphology, excellent in chemical resistance and clear in resolution ratio, and on the basis, the composition has the advantages of being simple in preparation process, low in cost and the like. The developing time can be obviously shortened, and even if the film thickness of a photoresist sample is increased, the developing time can also be obviously shortened.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithography processes, and particularly relates to a composition of a resin containing active groups and its applications, a resin with dual active groups and its applications. Background Art

[0002] In the manufacture of miniaturized electronic components, microfabrication is carried out through lithography using photoresists. Microfabrication is to transfer the required fine patterns from a mask plate to a silicon wafer to be processed through exposure and development using a photochemical reaction, and then processes such as etching, diffusion, ion implantation, and metallization are carried out. Therefore, photoresists are key chemical raw materials in the electronics industry. The resin containing active groups and photoinitiator in the photoresist are the most important components, and their chemical and physical properties will directly affect performance indicators such as the development speed, resolution, and morphology of the photoresist, thus affecting the use effect in large-scale integrated circuits.

[0003] Among the existing resins containing active groups, acrylic resins are widely used due to their good optical stability, simple preparation, and low cost. When using existing acrylic resins, photoinitiators, solvents, etc. to prepare photoresists, there are problems such as relatively poor morphology, slow development speed, and even slower development speed when increasing the thickness of the photoresist. Moreover, the existing acrylic resins also have the disadvantage of low activity. Aiming at the problems of slow development speed of existing photoresists when developing, even slower development speed when increasing the thickness of the photoresist, relatively poor morphology, and the problem of low activity of existing acrylic resins, how to provide a composition of a resin containing active groups, which has a fast development speed when used in photoresists, relatively fast development speed even when increasing the thickness of the photoresist, good morphology, clear resolution, and excellent chemical resistance. At the same time, how to provide a resin with dual active groups, which further improves the storage stability, application performance stability, and chemical resistance of the resin with dual active groups on the basis of high activity, is an urgent problem to be solved by the present invention. Summary of the Invention

[0004] The purpose of the present invention is to provide a composition of a resin containing active groups and its applications, a resin with dual active groups and its applications, so as to solve the problems raised in the above background art.

[0005] On the one hand, the present invention provides a composition of a resin containing active groups, which composition comprises the following components in parts by mass: 50 - 65 parts of a resin containing active groups, 10 - 20 parts of a carboxylic acid monomer containing alkenyl, 5 - 15 parts of a crosslinking agent, 0.5 - 2 parts of photoinitiator 1, 1 - 15 parts of photoinitiator 2, 5 - 30 parts of a solvent;

[0006] Photoinitiator 1 is an acylphosphine oxide-based free radical photoinitiator; photoinitiator 2 is a non-acylphosphine oxide-based free radical photoinitiator;

[0007] The resin containing active groups includes one or more of the resin with a single active group and the resin with double active groups;

[0008] The weight-average molecular weight of the resin containing active groups is 5000 - 15000;

[0009] The relative molecular weight of the carboxylic acid monomer containing alkenyl is 50 - 1000.

[0010] In some embodiments of the present invention, optionally, the mass fraction of photoinitiator 1 can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part, 2 parts or the numerical range between any two of them. When the mass fraction of photoinitiator 1 is greater than 2 parts, it will cause excessive progress of the chemical reaction, and when the composition of the resin containing active groups prepared is applied to the photoresist, the photoresist is difficult to develop. When the mass fraction of photoinitiator 1 is less than 0.5 part, it will lead to incomplete chemical reaction and insufficient crosslinking degree, and when the composition of the resin containing active groups prepared is applied to the photoresist, the photoresist is easy to develop, but the morphology after development is easily damaged.

[0011] In some embodiments of the present invention, optionally, the mass fraction of photoinitiator 2 can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts or the numerical range between any two of them. When the mass fraction of photoinitiator 2 is greater than 15 parts, it will cause excessive progress of the chemical reaction, and when the composition of the resin containing active groups prepared is applied to the photoresist, the photoresist is difficult to develop. When the mass fraction of photoinitiator 2 is less than 1 part, it will lead to incomplete chemical reaction and insufficient crosslinking degree, and when the composition of the resin containing active groups prepared is applied to the photoresist, the photoresist is easy to develop, but the morphology after development is easily damaged.

[0012] In some embodiments of the present invention, optionally, the acylphosphine oxide-based free radical photoinitiator includes one or more of photoinitiator TPO, photoinitiator BAPO, and photoinitiator TPO-L; the non-acylphosphine oxide-based free radical photoinitiator includes one or more of photoinitiator 651, photoinitiator BP, and photoinitiator PBZ.

[0013] In some embodiments of the present invention, in order to make the composition of the resin containing active groups have straight lines, upright and relatively regular morphology when applied to the photoresist, optionally, the mass ratio of the acylphosphine oxide-based free radical photoinitiator to the non-acylphosphine oxide-based free radical photoinitiator is 0.03 - 2:1.

[0014] In some embodiments of the present invention, in order to make the composition of the resin containing active groups have straight lines, upright and regular topography when applied to a photoresist, further optionally, the mass ratio of acylphosphine oxide radical photoinitiators to non-acylphosphine oxide radical photoinitiators is 0.1-0.9:1.

[0015] In some embodiments of the present invention, the mass fraction of the resin containing active groups can be 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts or the numerical range between any two of them. When the mass fraction of the resin containing active groups is greater than 65 parts, when the composition of the resin containing active groups prepared is applied to a photoresist, the photoresist is too thick, resulting in the product thickness not meeting the requirements, and it will also cause the exposure time of the pattern during development to be too long, the topography of the photoresist is poor, and at the same time, it will cause the resin containing active groups to swell, and the inside of the resin containing active groups is not developed, resulting in easy glue dropping or partial film opening failure. When the mass fraction of the resin containing active groups is less than 50 parts, when the composition of the resin containing active groups prepared is applied to a photoresist, the photoresist is too thin, resulting in the product thickness still not meeting the requirements, and at the same time, it will also cause the exposure time of the pattern during development to be too short, affecting the topography after development.

[0016] In some embodiments of the present invention, the weight-average molecular weight of the resin containing active groups is 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000 or the numerical range between any two of them. When the weight-average molecular weight of the resin containing active groups is lower than 5000, although the activity is relatively high, the storage stability and the stability of application performance still need to be further improved. When the weight-average molecular weight of the resin containing active groups is higher than 15000, the viscosity of the resin containing active groups is large (the viscosity at 25°C is greater than 10000 mPa·s). When preparing a photoresist with a resin containing active groups having a relatively large viscosity, it is not easy for the subsequent cross-linking reaction to proceed.

[0017] In some embodiments of the present invention, in order to make the development time of the photoresist short after exposure when the resin containing active groups is made into a photoresist, the resin containing active groups includes one or more of a single-active-group resin and a double-active-group resin.

[0018] In some embodiments of the present invention, optionally, the single-active-group resin includes one or more of an acid anhydride resin and an alkenyl resin.

[0019] In some embodiments of the present invention, the anhydride resin includes but is not limited to one selected from Dow (model Bynel 4104) and Arkema (model Orevac 18300), and the vinyl resin includes but is not limited to one selected from Daicel (model AD 032).

[0020] In some embodiments of the present invention, in order to shorten the development time of the photoresist after exposure when making the resin containing active groups into a photoresist, that is, even when the thickness of the photoresist increases, the development speed is also shortened. Optionally, the dual-active-group resin includes one or more of dual-active-group resin A and dual-active-group resin B.

[0021] In some embodiments of the present invention, optionally, the dual-active-group resin at least includes dual-active-group resin A, and further optionally, the dual-active-group resin is dual-active-group resin A.

[0022] In some embodiments of the present invention, optionally, the dual-active-group resin A has the structure shown in Formula I-1 as follows:

[0023]

[0024] Wherein, n1 and m1 both represent integers, and * represents the bonding point of the chemical bond.

[0025] In some embodiments of the present invention, optionally, n1:m1 = 2 - 4:1.

[0026] In some embodiments of the present invention, further optionally, n1:m1 = 2 - 3:1.

[0027] In some embodiments of the present invention, optionally, the dual-active-group resin B has the structure shown in Formula I-2 as follows:

[0028]

[0029] Wherein, n2 and m2 both represent integers, and n2:m2 = 1.5 - 4:1;

[0030] R represents

[0031] R1 represents -H, C1-C3 alkyl, R2 represents C1-C3 alkylene, and R3 represents -H, hydroxyl, hydroxymethyl or C1-C3 alkyl;

[0032] * represents the bonding point of the chemical bond.

[0033] In some embodiments of the present invention, optionally, n2:m2 = 2 - 4:1.

[0034] In some embodiments of the present invention, further optionally, n2:m2 = 2 - 3:1.

[0035] In some embodiments of the present invention, the dual-active-group resin A includes but is not limited to resins with model numbers SMA1000, SMA2000, and SMA3000 respectively from Nanjing Yinxin Chemical Co., Ltd.

[0036] In some embodiments of the present invention, in order to make the resin containing active groups have a suitable acid value, and when using the resin containing active groups to make a photoresist, the development time after exposure of the photoresist is shorter, that is, even when the thickness of the photoresist increases, the development speed is relatively shorter, and at the same time, the chemical resistance and resolution of the photoresist are improved. Optionally, the dual-active-group resin at least contains the dual-active-group resin B, and further optionally, the dual-active-group resin is the dual-active-group resin B.

[0037] In some embodiments of the present invention, optionally, the dual-active-group resin contains the dual-active-group resin B and the dual-active-group resin A.

[0038] In some embodiments of the present invention, optionally, R in the dual-active-group resin B is selected from the structures of the following formulas II-1 to II-3:

[0039]

[0040]

[0041] In some embodiments of the present invention, further optionally, R in the dual-active-group resin B is selected from one of the structures of the following formulas II-1-1, II-2-1 to II-2-4, and II-3-1:

[0042]

[0043] In some embodiments of the present invention, in order to make the composition of the resin containing active groups used in a photoresist have straight and thick lines, upright and regular morphology, optionally, the mass ratio of the acylphosphine oxide radical photoinitiator to the non-acylphosphine oxide radical photoinitiator is 0.1 - 0.9:1, and the weight-average molecular weight of the dual-active-group resin B is 8000 - 15000, and the ratio of n2:m2 is 1.5 - 4:1.

[0044] In some embodiments of the present invention, the mass fraction of the carboxylic acid monomer containing an alkenyl group can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or a numerical range between any two of them. When the mass fraction of the carboxylic acid monomer containing an alkenyl group is greater than 20 parts, when the composition of the resin containing active groups is applied to a photoresist, the development speed is too fast. When the mass fraction of the carboxylic acid monomer containing an alkenyl group is less than 10 parts, when the composition of the resin containing active groups is applied to a photoresist, the development speed is too slow.

[0045] In some embodiments of the present invention, in order to shorten the development time when the prepared composition of the resin containing active groups is applied to a photoresist, and when the film thickness of the photoresist sample increases, the development time also significantly decreases, the relative molecular mass of the carboxylic acid monomer containing an alkenyl group is 50 - 1000. Optionally, the carboxylic acid monomer containing an alkenyl group includes one or more of acrylic acid, methacrylic acid, and myristoleic acid.

[0046] In some embodiments of the present invention, the mass fraction of the crosslinking agent can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, or a numerical range between any two of them. When the mass fraction of the crosslinking agent is greater than 15 parts, the composition of the resin containing active groups is over-crosslinked, resulting in a relatively high hardness of the resin containing active groups. When used to prepare a photoresist, the photoresist is not easily developed after exposure. When the mass fraction of the crosslinking agent is less than 5 parts, the composition of the resin containing active groups is under-crosslinked, resulting in a relatively low hardness of the resin containing active groups. When used to prepare a photoresist, it is prone to collapse after development and is not easily shaped.

[0047] In some embodiments of the present invention, optionally, the crosslinking agent includes one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethoxylated pentaerythritol tetraacrylate.

[0048] In some embodiments of the present invention, the mass fraction of the solvent can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, or a numerical range between any two of them. When the mass fraction of the solvent is greater than 30 parts, the film thickness of the composition of the resin containing active groups will be too thin. When the mass fraction of the solvent is less than 5 parts, the film thickness of the composition of the resin containing active groups will be too thick.

[0049] In some embodiments of the present invention, the solvent is a conventional solvent used when the composition of the resin containing active groups is applied to the field of lithography process technology in integrated circuits.

[0050] In some embodiments of the present invention, optionally, the solvent includes but is not limited to propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate.

[0051] In some embodiments of the present invention, optionally, the solvent includes but is not limited to one, two, three or multiple others, and can be reasonably added according to actual needs. At the same time, for solvents containing two, three or multiple others, reasonable ratios can also be adjusted according to needs.

[0052] On the other hand, the present invention also provides a resin with two reactive groups, and the

[0053] resin with two reactive groups has the structure shown in Formula I-2 below:

[0054]

[0055] wherein, n2:m2 = 1.5-4:1, and both n2 and m2 represent integers;

[0056] R represents

[0057] R1 represents -H, C1-C3 alkyl, R2 represents C1-C3 alkylene, and R3 represents -H, hydroxyl, hydroxymethyl or C1-C3 alkyl;

[0058] * represents the bonding position of the chemical bond.

[0059] In some embodiments of the present invention, in order to make the synthesized resin with two reactive groups have high activity and relatively good chemical resistance, storage stability and application performance stability, n2:m2 is 1.5-4:1.

[0060] In some embodiments of the present invention, optionally, in order to make the synthesized resin with two reactive groups have higher activity, a more suitable acid value, and the acid value is in the range of 90-150 mgKOH / g, and better chemical resistance, storage stability and application performance stability, optionally, n2:m2 is 2-4:1. In order to make the resin with two reactive groups have a more suitable acid value and the acid value is in the range of 100-140 mgKOH / g, further optionally, n2:m2 is 2-3:1.

[0061] In some embodiments of the present invention, the ratio of n2:m2 can be one of 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or a numerical range between any two of them. When the ratio of n2:m2 is greater than 4:1, the acid value of the synthesized dual-active group resin is relatively low. When developing the composition of the resin containing active groups prepared from the dual-active group resin with a low acid value after spin coating, pre-baking, and exposure, the development rate is slow. When the ratio of n2:m2 is less than 1.5:1, the acid value of the synthesized high-active resin is relatively high. When developing the composition of the resin containing active groups prepared from the dual-active group resin with a high acid value after spin coating, pre-baking, and exposure, the development rate is slow.

[0062] In some embodiments of the present invention, in order to improve the activity of the dual-active group resin and simultaneously improve the comprehensive properties such as the storage stability and application performance stability of the dual-active group resin, optionally, R in the dual-active group resin is selected from the structures of Formula II-1 to II-3 as follows:

[0063]

[0064] In some embodiments of the present invention, in order to further improve the activity of the dual-active group resin, optionally, R in the dual-active group resin is selected from one of the structures of Formula II-1-1, Formula II-2-1 to Formula II-2-4, and Formula II-3-1:

[0065]

[0066] In some embodiments of the present invention, optionally, the dual-active group resin is prepared by reacting a styrene maleic anhydride copolymer with a graft monomer, and the graft monomer has the structure shown in Formula III as follows:

[0067]

[0068] For the benefit of subsequent reaction with the crosslinking agent, the viscosity of the dual-active group resin needs to be in the range of 1000 - 10000 mPa·s at 25°C. Through a large number of experiments, the present invention finds that when the weight-average molecular weight of the styrene maleic anhydride copolymer is 1000 - 10000, the viscosity of the dual-active group resin can be in the range of 1000 - 10000 mPa·s at 25°C. Optionally, the weight-average molecular weight of the styrene maleic anhydride copolymer is 5000 - 10000, and further optionally, the weight-average molecular weight of the styrene maleic anhydride copolymer is 6000 - 10000.

[0069] In some embodiments of the present invention, the weight-average molecular weight of the styrene maleic anhydride copolymer is 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 6,500, 7,000, 8,000, 9,000, 10,000 or a numerical range between any two of them. When the weight-average molecular weight of the styrene maleic anhydride copolymer is lower than 1,000, the weight-average molecular weight of the dual-active-group resin formed by the reaction of the styrene maleic anhydride copolymer and the graft monomer is lower than 5,000, resulting in the viscosity of the dual-active-group resin not meeting the standard (the viscosity meets the standard when the viscosity at 25 °C is 1,000-10,000 mPa·s). When using the dual-active-group resin with unqualified viscosity to prepare a photoresist, it is not easy for the subsequent cross-linking reaction to proceed. When the weight-average molecular weight of the styrene maleic anhydride copolymer is higher than 10,000, the weight-average molecular weight of the highly active resin formed by the reaction of the styrene maleic anhydride copolymer and the graft monomer is higher than 15,000, resulting in the viscosity of the dual-active-group resin not meeting the standard (the viscosity meets the standard when the viscosity at 25 °C is 1,000-10,000 mPa·s). When using the dual-active-group resin with unqualified viscosity to prepare a photoresist, it is not easy for the subsequent cross-linking reaction to proceed.

[0070] In some embodiments of the present invention, in order to make the reaction between the dual-active-group resin and the cross-linking agent complete and the viscosity of the dual-active-group resin meet the standard (the viscosity meets the standard when the viscosity at 25 °C is 1,000-10,000 mPa·s), optionally, the weight-average molecular weight of the dual-active-group resin is 8,000-15,000, and further optionally, the weight-average molecular weight of the dual-active-group resin is 10,000-13,000.

[0071] In some embodiments of the present invention, the weight-average molecular weight of the dual-active-group resin can be 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000, 15,000 or a numerical range between any two of them.

[0072] In some embodiments of the present invention, in order to further shorten the development time when the composition of the resin containing active groups prepared from the dual-active-group resin is used in a photoresist, that is, even when the film thickness of the photoresist sample increases, the shortening of the development time is more obvious. Optionally, n2:m2 is 1.5-4:1, and the weight-average molecular weight of the dual-active-group resin is 8,000-15,000; further optionally, n2:m2 is 2-4:1, and the weight-average molecular weight of the dual-active-group resin is 8,000-15,000; more preferably, n2:m2 is 2-3:1, and the weight-average molecular weight of the dual-active-group resin is 8,000-15,000.

[0073] On the other hand, the present invention also provides the application of the composition of the resin containing active groups.

[0074] On the other hand, the present invention also provides an application of the resin with dual reactive groups.

[0075] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0076] The composition of the resin containing reactive groups provided by the present invention can, by formulating the formulation system, especially the combination between photoinitiators and the combination between them and the resin containing reactive groups, make the prepared photoresist lines straight, with upright and relatively regular morphology, excellent chemical resistance, clear resolution, and can meet the actual production needs. On this basis, it can significantly shorten the development time, and even if the film thickness of the photoresist sample is increased, the development time can also be significantly shortened.

[0077] In addition, the resin with dual reactive groups provided by the present invention, especially the dual-reactive-group resin B, can significantly improve the chemical resistance and resolution of the photoresist, and also makes an important contribution to shortening the development time. When the resin composition containing the dual-reactive-group resin is used as a photoresist, the development time is shortened regardless of whether the film thickness of the photoresist sample is increased. Description of the Drawings

[0078] Figure 1 It is the morphology diagram of the photoresist prepared in Example 1 of the present invention;

[0079] Figure 2 It is the morphology diagram of the photoresist prepared in Example 5 of the present invention;

[0080] Figure 3 It is the morphology diagram of the photoresist prepared in Comparative Example 2 of the present invention;

[0081] Figure 4 It is the morphology diagram of the photoresist prepared in Comparative Example 3 of the present invention;

[0082] Figure 5 It is the HPLC diagram of the residual graft monomer used in the dual-reactive-group resin B1 of the present invention. Detailed Embodiments

[0083] The present invention will be further illustrated below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In the following examples and comparative examples, except for the dual-active group resins B1, B2, B3, and B4, the compound monomers and related reagents used can be purchased from the market. Among them, the dual-active group resin A1 is purchased from Nanjing Yinxin Chemical Co., Ltd., with the model SMA2000; the dual-active group resin A2 is purchased from Nanjing Yinxin Chemical Co., Ltd., with the model SMA3000; the dual-active group resin A3 is purchased from Nanjing Yinxin Chemical Co., Ltd., with the model SMA1000; polyacrylic acid (CAS: 9003-01-4) is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; styrene maleic anhydride copolymer A is XIRAN 3000 from Polyscope; styrene maleic anhydride copolymer B is XIRAN 2000 from Polyscope; styrene maleic anhydride copolymer C is XIBOND 2025 from Polyscope; styrene maleic anhydride copolymer D is SMAXIRANSZ30010 from Polyscope; the inactive resin is Huayi W4315 from Huayi Chemical Group, the scanning electron microscope is purchased from Thermofisher, with the model Apreo 2S; the potentiometric titrator is purchased from Metrohm, with the model 888 Titrando; the spin coater is purchased from mikasa, with the model MS-B150.

[0084] The preparation method of the dual-active group resin B1 includes the following steps: Add 100.00 g of propylene glycol methyl ether acetate, 74.69 g of styrene maleic anhydride copolymer A (in the styrene maleic anhydride copolymer, n2:m2 is 3:1, and the weight-average molecular weight is 10,000), and 2.90 g of triethylamine into a 500 ml four-necked round-bottom flask equipped with a thermometer, a reflux condenser, and a stirrer. After stirring to dissolve it, add 22.11 g of hydroxyethyl acrylate and 0.29 g of hydroquinone into the flask, and then heat it to 90 °C and let it stir and reflux for 12 h. Cool down and discharge to obtain the dual-active group resin B1. After detection, the average weight-average molecular weight of the dual-active group resin B1 is 11,000. When the anhydride ring-opening in the styrene maleic anhydride copolymer A reacts with hydroxyethyl acrylate, the anhydride characteristic absorption peak at 1779 cm -1 in the infrared spectrum after the reaction is relatively weak, and it can be seen from Figure 5 that after the reaction of styrene maleic anhydride copolymer A and hydroxyethyl acrylate to synthesize the dual-active group resin B1, the residual amount of hydroxyethyl acrylate in the dual-active group resin B1 is less than 5%.

[0085] Preparation method of dual-active-group resin B2, comprising the following steps: Add 100.00 g of propylene glycol methyl ether acetate, 69.41 g of styrene maleic anhydride copolymer B (in the styrene maleic anhydride copolymer, n2:m2 is 2:1, and the weight-average molecular weight is 6500), and 4.95 g of triethylamine into a 500 ml four-necked round-bottom flask equipped with a thermometer, a reflux condenser, and a stirrer. After stirring to dissolve, add 27.40 g of hydroxyethyl acrylate and 0.29 g of hydroquinone into the flask, then heat up to 90 °C and let it stir and reflux for 12 h. Cool down and discharge to obtain dual-active-group resin B2. Among them, the average weight-average molecular weight of dual-active-group resin B2 is 9000.

[0086] Preparation method of dual-active-group resin B3, comprising the following steps: Add 120.00 g of propylene glycol methyl ether acetate, 78.23 g of styrene maleic anhydride copolymer C (in the styrene maleic anhydride copolymer, n2:m2 is 4:1, and the weight-average molecular weight is 6500), and 4.95 g of triethanolamine into a 500 ml four-necked round-bottom flask equipped with a thermometer, a reflux condenser, and a stirrer. After stirring to dissolve, add 20.81 g of hydroxypropyl acrylate and 0.19 g of hydroquinone into the flask, then heat up to 90 °C and let it stir and reflux for 12 h. Cool down and discharge to obtain dual-active-group resin B3. Among them, the average weight-average molecular weight of dual-active-group resin B3 is 7000.

[0087] Preparation method of dual-active-group resin B4, comprising the following steps: Add 150.00 g of propylene glycol methyl ether acetate, 60.80 g of styrene maleic anhydride copolymer D (in the styrene maleic anhydride copolymer, n2:m2 is 1:1, and the weight-average molecular weight is 9000), and 1.90 g of dimethylamine into a 500 ml four-necked round-bottom flask equipped with a thermometer, a reflux condenser, and a stirrer. After stirring to dissolve, add 44.07 g of glycerol methacrylate and 0.48 g of p-methoxy phenol into the flask, then heat up to 90 °C and let it stir and reflux for 12 h. Cool down and discharge to obtain dual-active-group resin B4. Among them, the average weight-average molecular weight of dual-active-group resin B4 is 12000.

[0088] Perform activation time, acid value, chemical resistance, storage stability, and application performance stability tests on the prepared dual-active-group resins B1-B4, dual-active-group resins A1-A3, and non-active resins. The test results are shown in Table 1. The specific test methods are as follows:

[0089] Activation time test: Conduct the test with reference to the GB7193.4-87 standard;

[0090] Acid value range test: Dilute the resin to be tested (the mass of the resin to be tested is represented by m) with acetone until the electrodes are submerged, and perform titration using the acid value test program of a potentiometric titrator. During titration, use sodium hydroxide solution for titration. The volume consumption of the sodium hydroxide solution is represented by v, and the mass concentration of the sodium hydroxide solution is represented by c. The acid value of the resin to be tested (the acid value is represented by a, with the unit of mg KOH / g) is calculated by the following formula:

[0091] a = 56.1vc / m. Optionally, the acid value is 90 - 150 mg KOH / g. Further optionally, the acid value is 100 - 140 mg KOH / g;

[0092] Chemical resistance: Seal one end of a glass tube with an inner diameter of 50 mm using a sealing material that is not eroded by chemical reagents. Prepare a coating from the resin to be tested under certain conditions, cut out a coating resin of the same size that can fit into the glass tube and bond it to the center of the sealed part to ensure good contact and sealing. Pour a 5% (v / v) HCl solution into the tube to a liquid level height of 20 mm ± 2 mm, cover the tube tightly with a glass slide, let it stand for 24 h, then remove the specimen, wash and dry it. Then, continue to bond the coating resin to the center of the sealed part to ensure good contact and sealing. Pour a 5% (m / m) NaOH solution into the tube to a liquid level height of 20 mm ± 2 mm, cover the tube tightly with a glass slide, let it stand for 24 h, then remove the specimen, wash and dry it, and visually inspect whether there are any abnormal phenomena such as blistering, discoloration, peeling, etc. at the experimental site;

[0093] Storage stability: Place 50 g of the resin to be tested in a sealed bottle, first place it in an oven at 50 °C for 15 days, then place it in a refrigerator at -10 °C for 15 days and then take it out, and detect the activity of the resin to be tested;

[0094] Test for the stability of application performance: Spin-coat the resin to be tested on a 4-inch circular silicon wafer. During spin-coating, the rotation speed of the spin coater is 1400 rpm, and the spin-coating time is 30 s. After spin-coating, observe the flatness and uniformity of the coating.

[0095] Table 1

[0096]

[0097]

[0098] Comparing the dual-active-group resin B1 - B3 with the non-active resin, it can be seen that the dual-active-group resin B provided in this application has higher activity, an acid value within a suitable range, and good chemical resistance, storage stability, and stability of application performance;

[0099] Compared with the dual-reactive-group resins A1-A3, the dual-reactive-group resins B1-B3 provided in this application have a shorter activation time, higher activity, a more suitable acid value range, and better storage stability.

[0100] When the ratio of n2:m2 is within a suitable range for the comparison between the dual-reactive-group resins B1-B3 and the dual-reactive-group resin B4, the activation time is shortened and the acid value range is within a suitable range.

[0101] When the weight-average molecular weight of the dual-reactive-group resin B is within a suitable range for the comparison between the dual-reactive-group resins B1-B2 and the dual-reactive-group resin B3, the activation time, storage stability, and application performance stability can be improved to a certain extent, and at the same time, the acid value range of the dual-reactive-group resin B is more suitable.

[0102] Prepare the composition according to the formula in Table 2-3 below. The specific preparation method includes the following steps: accurately weigh each raw material and add it to a bottle, seal it, and then place it in a drum for stirring for 24 h at a stirring speed of 60 rpm. After dissolution, the composition is obtained.

[0103] The components and component contents used in Examples 1-9 and Comparative Examples 1-4 are shown in Table 2-3:

[0104] Table 2

[0105]

[0106] Figure 3

[0107]

[0108]

[0109] Perform development time, resolution, chemical resistance, and morphology tests on the compositions prepared in Examples 1-9 and Comparative Examples 1-4. The specific test methods are as follows. Among them, a spin coater is used during spin coating:

[0110] Chemical resistance test: Let the compositions prepared in Examples 1-9 and Comparative Examples 1-4 stand still until the foam disappears, then perform spin coating and pre-baking. After spin coating and pre-baking, place the samples in a hydrochloric acid solution with a volume percentage concentration of 3% and soak for 24 h, then wash and dry with deionized water, and then place them in a sodium hydroxide solution with a mass percentage concentration of 3% and soak for 24 h. Observe the changes in the photoresist samples to test their acid resistance and alkali resistance. Among them, the film thickness of the photoresist samples is 15 μm. During spin coating, the spin coating time of the spin coater is 30 s and the rotation speed is 1400 rpm. During pre-baking, the drying temperature is 110 °C and the drying time is 90 s.

[0111] Development time test: After the compositions prepared in Examples 1-9 and Comparative Examples 1-4 were allowed to stand until the foam disappeared, they were spin-coated, pre-baked, exposed, and developed. Then, the exposed or unexposed parts of the photoresist were washed away, and the time required to obtain the desired pattern on the wafer was the development time. The time from when the photoresist after exposure was applied to the developer until the desired pattern was obtained was calculated. Among them, the film thickness of the photoresist was 15 μm. During spin-coating, the spin-coating time of the spin coater was 30 s and the rotation speed was 1400 rpm. During pre-baking, the drying temperature was 110 °C and the drying time was 90 s. During exposure, the ultraviolet energy was 180 mj / cm 2 , and the developer used was a TMAH solution with a mass percentage concentration of 2.38%; the film thickness of the photoresist was 20 μm. During spin-coating, the spin-coating time of the spin coater was 30 s and the rotation speed was 1000 rpm. During pre-baking, the drying temperature was 110 °C and the drying time was 90 s. During exposure, the ultraviolet energy was 210 mj / cm 2 , and the developer used was a 2.38% TMAH solution.

[0112] Resolution test method: After the compositions prepared in Examples 1-9 and Comparative Examples 1-4 were allowed to stand until the foam disappeared, they were spin-coated, pre-baked, exposed, and developed. Then, the exposed or unexposed parts of the photoresist were washed away, and the desired pattern was obtained on the wafer. The minimum resolution capable of reproducing the pattern size was observed under a scanning electron microscope, and the resolution of the photoresist sample was observed under the scanning electron microscope.

[0113] Morphology test method: After the compositions prepared in Examples 1-9 and Comparative Examples 1-4 were allowed to stand until the foam disappeared, they were spin-coated, pre-baked, exposed, and developed. Then, the exposed or unexposed parts of the photoresist were washed away, and the desired pattern was obtained on the wafer. Under a scanning electron microscope, the photoresist lines and surface morphology were observed at the best magnification and clearest field of view. Among them, it met the requirements when the lines were straight, the morphology was upright and relatively regular, or the lines were thick and straight, and the morphology was upright and relatively regular. Optionally, the lines were straight and the morphology was upright and regular. Further optionally, the lines were thick and straight and the morphology was upright and regular.

[0114] The test results are shown in Table 4 as follows:

[0115] Table 4

[0116]

[0117]

[0118]

[0119] It can be seen from the comparison between Example 5 and Examples 8-9 that when the mass ratio of Photoinitiator 1 and Photoinitiator 2 is within a suitable range, when the composition of the resin containing active groups prepared is applied to a photoresist, the lines are straight, the morphology is upright and regular, and the morphology is excellent.

[0120] It can be seen from the comparison between Example 5 and Comparative Examples 1-2 that when Photoinitiator 1 and Photoinitiator 2 are used in combination and the mass parts of Photoinitiator 1 and Photoinitiator 2 are within a suitable range, when the composition of the resin containing active groups prepared is applied to a photoresist, the lines are straight, the morphology is upright and regular, and the morphology is excellent.

[0121] It can be seen from the comparison between Example 5 and Comparative Example 3 that the use of the dual-active-group resin A shortens the development time, and when the film thickness of the photoresist sample increases, the development time also decreases significantly.

[0122] It can be seen from the comparison between Example 5 and Comparative Example 4 that when the carboxylic acid monomer containing alkenyl is used instead of the carboxylic acid polymer containing alkenyl, the development time can be shortened to a certain extent, and when the film thickness of the photoresist sample increases, the development time also decreases.

[0123] It can be seen from the comparison between Examples 1-3 and Examples 4-9 that when the composition of the resin containing active groups prepared using the dual-active-group resin B provided in the present application is applied to a photoresist, the chemical resistance and resolution of the photoresist can be improved, the development time can be shortened. Even when the film thickness of the photoresist sample is increased, the development time can be significantly shortened, and the lines are straight, and the morphology is upright and regular.

[0124] It can be seen from the comparison between Examples 1-2 and Examples 3-4 that when the ratio of n2:m2 in the dual-active-group resin B and the weight-average molecular weight of the dual-active-group resin B are both within a suitable range, the line thickness is straight, the morphology is upright and regular, the chemical resistance is excellent and the resolution is clear, and the development time is further shortened. Even when the film thickness of the photoresist sample is increased, the shortening of the development time is more obvious, meeting the requirements for miniaturized electronic components with higher performance requirements.

[0125] It can be seen from the comparison between Examples 1-9 that the composition of the resin containing active groups prepared using the components and contents provided in the present application has straight lines, an upright and relatively regular morphology, relatively excellent chemical resistance and relatively clear resolution, and the development time is shortened. Even when the film thickness of the photoresist sample is increased, the development time is appropriately shortened.

[0126] In summary, the composition of the resin containing active groups provided by the present invention can make the lines of the prepared photoresist straight, the morphology upright and relatively regular, and have relatively excellent chemical resistance and relatively clear resolution by adjusting the formulation system, especially the combination between photoinitiators and the combination between them and the resin containing active groups, which can meet the actual production needs. On this basis, the development time can be significantly shortened. Even when the film thickness of the photoresist sample is increased, the development time can also be significantly shortened.

[0127] In addition, the dual-active-group resin B provided by the present invention can significantly improve the chemical resistance and resolution of the photoresist, and also makes an important contribution to shortening the development time. When the resin composition containing it is used as a photoresist, regardless of whether the film thickness of the photoresist sample increases or not, the development time is shortened.

[0128] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0129] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents. Obviously, the embodiments described in the present invention are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts fall within the scope of protection of the present invention.

Claims

1. A composition of a resin containing reactive groups, characterized in that: The composition containing the resin with active groups comprises the following components in parts by mass: 50 - 65 parts of the resin with active groups, 10 - 20 parts of the carboxylic acid monomer containing alkenyl, 5 - 15 parts of the crosslinking agent, 0.5 - 2 parts of photoinitiator 1, 1 - 15 parts of photoinitiator 2, and 5 - 30 parts of the solvent; Among them, the photoinitiator 1 is an acylphosphine oxide - type free - radical photoinitiator; the photoinitiator 2 is a non - acylphosphine oxide - type free - radical photoinitiator; The resin with active groups includes one or more of the single - active - group resin and the double - active - group resin; The weight - average molecular weight of the resin with active groups is 5000 - 15000; The relative molecular weight of the carboxylic acid monomer containing alkenyl is 50 - 1000.

2. The composition of the resin containing active groups according to claim 1, characterized in that: The acylphosphine oxide - type free - radical photoinitiator includes one or more of photoinitiator TPO, photoinitiator BAPO, and photoinitiator TPO - L; The non - acylphosphine oxide - type free - radical photoinitiator includes one or more of photoinitiator 651, photoinitiator BP, and photoinitiator PBZ; Optionally, the mass ratio of the acylphosphine oxide - type free - radical photoinitiator to the non - acylphosphine oxide - type free - radical photoinitiator is 0.03 - 2:

1.

3. The composition of the resin containing active groups according to claim 1, characterized in that: The single - active - group resin includes one or more of the anhydride - type resin and the alkenyl - type resin.

4. The composition containing the resin with active groups according to claim 1, characterized in that: The double - active - group resin includes one or more of double - active - group resin A and double - active - group resin B; Optionally, the double - active - group resin contains at least double - active - group resin A; Optionally, the double - active - group resin contains at least double - active - group resin B; Optionally, the double - active - group resin contains double - active - group resin A and double - active - group resin B; Optionally, the double - active - group resin A has the structure shown in Formula Ⅰ - 1 as follows: Wherein, n1 and m1 both represent integers, and * represents the bonding position of the chemical bond; Optionally, n1:m1 = 2 - 4:1; Further optionally, n1:m1 = 2 - 3:1; Optionally, the double - active - group resin B has the structure shown in Formula Ⅰ - 2 as follows: Wherein, n2 and m2 both represent integers, and n2:m2 = 1.5 - 4:1; R represents R1 represents - H, C1 - C3 alkyl, R2 represents C1 - C3 alkylene, and R3 represents - H, hydroxyl, hydroxymethyl, or C1 - C3 alkyl; * represents the bonding position of the chemical bond; Optionally, n2:m2 = 2 - 4:1; Further optionally, n2:m2 = 2 - 3:

1.

5. The composition of the resin containing active groups according to claim 4, characterized in that: The R in the double - active - group resin B is selected from the structures shown in Formula Ⅱ - 1 to II - 3 as follows: Optionally, the R in the double - active - group resin B is selected from one of the structures shown in Formula Ⅱ - 1 - 1, Formula Ⅱ - 2 - 1 to Formula Ⅱ - 2 - 4, and Formula Ⅱ - 3 - 1; 6. The composition of the resin containing active groups according to claim 1, characterized in that: The carboxylic acid monomer containing alkenyl includes one or more of acrylic acid, methacrylic acid, and myristoleic acid; Optionally, the crosslinking agent includes one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethoxylated pentaerythritol tetraacrylate.

7. A dual-active-group resin, characterized in that: The double - active - group resin has the structure shown in Formula Ⅰ - 2 as follows: Among them, n2:m2 = 1.5 - 4:1, and both n2 and m2 represent integers; R represents R1 represents -H, C1-C3 alkyl, R2 represents C1-C3 alkylene, and R3 represents -H, hydroxy, hydroxymethyl or C1-C3 alkyl; * represents the bonding site of the chemical bond; Optionally, n2:m2 = 2 - 4:1; Further optionally, n2:m2 = 2 - 3:

1.

8. The dual-active-group resin according to claim 7, characterized in that: The dual-active group resin is prepared by reacting a styrene maleic anhydride copolymer with a graft monomer, and the graft monomer has the structure shown in Formula III below: Optionally, the weight-average molecular weight of the styrene maleic anhydride copolymer is 1000 - 10000; Optionally, the weight-average molecular weight of the dual-active group resin is 8000 - 15000.

9. The dual-active group resin according to claim 7, wherein: R is selected from the structures shown in Formula II-1 to II-3 below: Further optionally, R is selected from one of the structures of Formula II-1-1, Formula II-2-1 to Formula II-2-4, and Formula II-3-1; 10. Use of the resin composition containing active groups according to any one of claims 1 - 6.

11. Use of the dual-active group resin according to any one of claims 7 - 9.

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