Resin containing active groups, compositions and uses thereof, di-active group resins and uses thereof

Abstract

The application provides a composition containing active group resin and application thereof, and a double active group resin and application thereof. The composition containing active group resin comprises the following components by mass fraction: 50-65 parts of active group resin, 10-20 parts of carboxylic acid monomer containing alkenyl, 5-15 parts of crosslinking agent, 0.5-2 parts of photoinitiator 1, 1-15 parts of photoinitiator 2, 5-30 parts of solvent, the photoinitiator 1 is an acyl phosphine oxide radical photoinitiator; and the photoinitiator 2 is a non-acyl phosphine oxide radical photoinitiator. The composition containing active group resin provided by the application can make the photoresist line straight, the appearance upright, the shape relatively regular, the chemical resistance excellent, the resolution clear, and the developing time obviously shortened on the basis of the above, even if the film thickness of the photoresist sample is increased, the developing time can also be obviously shortened.

Description

Technical Field

[0001] This invention belongs to the field of photolithography technology, specifically relating to compositions containing active group resins and their applications, and dual active group resins and their applications. Background Technology

[0002] In the manufacturing of miniaturized electronic components, photolithography using photoresist is employed for microfabrication. Microfabrication involves transferring the desired micro-pattern from a photomask to a silicon wafer through exposure and development via photochemical reactions, followed by etching, diffusion, ion implantation, and metallization processes. Therefore, photoresist is a crucial chemical raw material in the electronics industry. The active resin and photoinitiator within the photoresist are the most important components; their chemical and physical properties directly affect the photoresist's development speed, resolution, morphology, and other performance indicators, thus influencing its effectiveness in large-scale integrated circuits.

[0003] Among existing resins containing active groups, acrylic resins are widely used due to their good optical stability, simple preparation, and low cost. However, when using existing acrylic resins, photoinitiators, and solvents to prepare photoresists, there are problems such as relatively poor morphology, slow development speed, and even slower development speed with increasing photoresist thickness. Furthermore, existing acrylic resins also suffer from low activity. To address the issues of slow development speed, even with increased photoresist thickness, and relatively poor morphology, as well as the low activity of existing acrylic resins, this invention aims to provide a composition of resins containing active groups that achieves fast development speed for photoresists, maintaining a relatively fast development speed and good morphology even with increased photoresist thickness, while also exhibiting clear resolution and excellent chemical resistance. Additionally, this invention seeks to provide a dual-active-group resin that, in addition to high activity, further improves the storage stability, application performance stability, and chemical resistance of dual-active-group resins. These are the problems that this invention urgently needs to solve. Summary of the Invention

[0004] The purpose of this invention is to provide compositions containing resins with active groups and their applications, and resins with two active groups and their applications, in order to solve the problems mentioned in the background art.

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

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

[0007] Resins containing active groups include one or more of resins with single active groups and resins with dual active groups;

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

[0009] The relative molecular mass of carboxylic acid monomers containing alkenyl groups is 50-1000.

[0010] In some embodiments of the present invention, optionally, the mass fraction of photoinitiator 1 can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, or any value range between two of these. When the mass fraction of photoinitiator 1 is greater than 2 parts, it will cause excessive chemical reaction, making the photoresist difficult to develop when the prepared composition containing active group resin is applied. When the mass fraction of photoinitiator 1 is less than 0.5 parts, it will lead to incomplete chemical reaction and insufficient cross-linking, making the photoresist easy to develop when the prepared composition containing active group resin is applied, 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 any value range between two of these. When the mass fraction of photoinitiator 2 is greater than 15 parts, it will cause excessive chemical reaction, making the photoresist difficult to develop when the prepared composition containing active group resin is applied. When the mass fraction of photoinitiator 2 is less than 1 part, it will lead to incomplete chemical reaction and insufficient cross-linking, making the photoresist easy to develop when the prepared composition containing active group resin is applied, but the morphology after development is easily damaged.

[0012] In some embodiments of the present invention, optionally, the acylphosphine oxide free radical photoinitiator includes one or more of photoinitiator TPO, photoinitiator BAPO, and photoinitiator TPO-L; the non-acylphosphine oxide 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 lines straight, the morphology upright and more regular when the composition containing the active group resin is applied to the photoresist, optionally, the mass ratio of acylphosphine oxide free radical photoinitiator and non-acylphosphine oxide free radical photoinitiator is 0.03-2:1.

[0014] In some embodiments of the present invention, in order to make the lines straight and the morphology upright and regular when the composition containing the active group resin is applied to the photoresist, the mass ratio of the acylphosphine oxide free radical photoinitiator and the non-acylphosphine oxide free radical photoinitiator is further optionally 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 any value range between two of these. When the mass fraction of the resin containing active groups is greater than 65 parts, the resulting composition of the resin containing active groups, when applied to photoresist, results in an excessively thick photoresist, leading to a product thickness that does not meet requirements. It also causes the pattern to be exposed for too long during development, resulting in poor morphology of the photoresist. Furthermore, it can cause the resin containing active groups to swell, preventing development within the resin containing active groups, which can lead to easy removal of the resin or partial failure to open the film. When the mass fraction of the resin containing active groups is less than 50 parts, the resulting composition of the resin containing active groups, when applied to photoresist, results in an excessively thin photoresist, leading to a product thickness that still does not meet requirements. It also causes the pattern to be exposed for too short a time during development, affecting the morphology 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 any two of these values. When the weight-average molecular weight of the resin containing active groups is less than 5000, although the activity is relatively high, the storage stability and application performance stability still need to be further improved. When the weight-average molecular weight of the resin containing active groups is greater than 15000, the viscosity of the resin containing active groups is high (viscosity greater than 10000 mPa·s at 25°C). When preparing photoresist with a high viscosity, the subsequent crosslinking reaction is not easy to proceed.

[0017] In some embodiments of the present invention, in order to make the photoresist containing active groups have a short development time after exposure, the active group resin includes one or more of single active group resins and dual active group resins.

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

[0019] In some embodiments of the present invention, the anhydride resins include, but are not limited to, one selected from Dow Chemical (Bynel 4104) and Arkema (Orevac 18300), and the alkenyl resins include, but are not limited to, one selected from Dacron (AD 032).

[0020] In some embodiments of the present invention, in order to shorten the development time after photoresist exposure when the photoresist containing active group resin is made into a photoresist, and to shorten the development speed even when the photoresist thickness is increased, 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 includes at least dual-active-group resin A, and more 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 described in Formula I-1:

[0023]

[0024] Where n1 and m1 are both integers, and * represents the connection point of a chemical bond.

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

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

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

[0028]

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

[0030] R represents

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

[0032] * indicates the connection point of a chemical bond.

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

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

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

[0036] In some embodiments of the present invention, in order to make the active group resin have a suitable acid value and to make the photoresist with the active group resin, the development time after exposure of the photoresist is shorter, and the development speed is relatively shorter even when the photoresist thickness is increased, while improving the chemical resistance and resolution of the photoresist, optionally, the dual active group resin includes at least dual active group resin B, and more preferably, the dual active group resin is dual active group resin B.

[0037] In some embodiments of the present invention, optionally, the dual-active-group resin comprises dual-active-group resin B and 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 formulas II-1 to II-3:

[0039]

[0040]

[0041] In some embodiments of the present invention, optionally, the R in the dual-active-group resin B is selected from one of the structures of formula 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 produce thick, straight lines and upright, regular morphology when the prepared composition containing active group resin is used as a photoresist, optionally, the mass ratio of acylphosphine oxide free radical photoinitiator and non-acylphosphine oxide free 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 n2:m2 ratio is 1.5-4:1.

[0044] In some embodiments of the present invention, the mass fraction of the alkenyl carboxylic acid monomer 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 any value range between two of these. When the mass fraction of the alkenyl carboxylic acid monomer is greater than 20 parts, the development speed will be too fast when the composition of the active group resin is applied to the photoresist. When the mass fraction of the alkenyl carboxylic acid monomer is less than 10 parts, the development speed will be too slow when the composition of the active group resin is applied to the photoresist.

[0045] In some embodiments of the present invention, in order to shorten the development time when the prepared composition of the active group resin is applied to the photoresist, and to significantly reduce the development time when the thickness of the photoresist sample film increases, the relative molecular mass of the alkenyl carboxylic acid monomer is 50-1000. Optionally, the alkenyl carboxylic acid monomer includes one or more of acrylic acid, methacrylic acid, and myristenoic 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 any value range between two of these. When the mass fraction of the crosslinking agent is greater than 15 parts, the composition containing the active group resin is over-crosslinked, resulting in a high hardness of the active group resin. When used to prepare photoresist, the photoresist is not easy to develop after exposure. When the mass fraction of the crosslinking agent is less than 5 parts, the composition containing the active group resin is under-crosslinked, resulting in a low hardness of the active group resin. When used to prepare photoresist, the photoresist is prone to collapse after development and is not easy to form.

[0047] In some embodiments of the present invention, the crosslinking agent optionally comprises one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethoxypentaerythritol 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 any value between two of these. When the mass fraction of the solvent is greater than 30 parts, the film thickness of the composition containing the active group resin will be relatively thin; when the mass fraction of the solvent is less than 5 parts, the film thickness of the composition containing the active group resin will be relatively thick.

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

[0050] In some embodiments of the present invention, the solvent may optionally include, but is not limited to, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, ethylene glycol butyl ether acetate, and diethylene glycol ethyl ether acetate.

[0051] In some embodiments of the present invention, the solvent may optionally include, but is not limited to, one, two, three or more other solvents, which may be added reasonably according to actual needs. At the same time, the proportions of two, three or more other solvents added may also be reasonably adjusted as needed.

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

[0053] The dual-active-group resin has the structure described in Formula I-2:

[0054]

[0055] Where 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 subalkyl, and R3 represents -H, hydroxyl, hydroxymethyl, or C1-C3 alkyl.

[0058] * indicates the connection point of a chemical bond.

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

[0060] In some embodiments of the present invention, optionally, in order to make the synthesized dual-active group resin have a more suitable acid value with higher activity and an acid value 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 dual-active group resin have a more suitable acid value with an acid value 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 any value between two of these. When the ratio of n2:m2 is greater than 4:1, the acid value of the synthesized dual-active-group resin will be lower. Compositions containing active-group resins prepared from dual-active-group resins with lower acid values ​​will have slower development rates after spin-coating, pre-baking, and exposure. When the ratio of n2:m2 is less than 1.5:1, the acid value of the synthesized highly reactive resin will be higher. Compositions containing active-group resins prepared from dual-active-group resins with higher acid values ​​will have slower development rates after spin-coating, pre-baking, and exposure.

[0062] In some embodiments of the present invention, in order to improve the activity of the dual-active-group resin, and at the same time improve the overall performance 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 structure of the following formulas II-1 to II-3:

[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 grafted monomer, the grafted monomer having the structure shown in Formula III:

[0067]

[0068] To facilitate 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 extensive experiments, this invention has found that when the weight-average molecular weight of the styrene-maleic anhydride copolymer is 1000-10000, the viscosity of the dual-active-group resin at 25°C can be kept in the range of 1000-10000 mPa·s. Optionally, the weight-average molecular weight of the styrene-maleic anhydride copolymer is 5000-10000, and more preferably, 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 1000, 2000, 3000, 4000, 5000, 6000, 6500, 7000, 8000, 9000, 10000, or any value between two of these. When the weight-average molecular weight of the styrene-maleic anhydride copolymer is less than 1000, the weight-average molecular weight of the dual-active-group resin generated by the reaction of the styrene-maleic anhydride copolymer and the grafted monomer is less than 5000, resulting in the viscosity of the dual-active-group resin not meeting the standard (the viscosity meets the standard when the temperature is 25°C and the viscosity is 1000-10000 mPa·s). When using the dual-active-group resin with the substandard viscosity to prepare photoresist, it is not easy for the subsequent crosslinking 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 reactive resin generated by the reaction of the styrene-maleic anhydride copolymer and the grafted 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 temperature is 25℃ and the viscosity is 1000-10000 mPa·s). When using the dual-active group resin with the substandard viscosity to prepare photoresist, it is not easy for the subsequent crosslinking reaction to proceed.

[0070] In some embodiments of the present invention, in order to ensure complete reaction between the dual-active group resin and the crosslinking agent and to achieve the required viscosity of the dual-active group resin (viscosity of 1000-10000 mPa·s at 25°C), optionally, the weight-average molecular weight of the dual-active group resin is 8000-15000, and more preferably, the weight-average molecular weight of the dual-active group resin is 10000-13000.

[0071] In some embodiments of the present invention, the weight-average molecular weight of the dual-active-group resin can be 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000 or any two of these values.

[0072] In some embodiments of the present invention, in order to further shorten the development time when the composition containing active group resin prepared by dual active group resin is used as a photoresist, and the shortening of the development time is more obvious even when the thickness of the photoresist sample increases, optionally, n2:m2 is 1.5-4:1, and the weight average molecular weight of the dual active group resin is 8000-15000; further optionally, n2:m2 is 2-4:1, and the weight average molecular weight of the dual active group resin is 8000-15000; even further optionally, n2:m2 is 2-3:1, and the weight average molecular weight of the dual active group resin is 8000-15000.

[0073] On the other hand, the present invention also provides the application of compositions containing resins with active groups.

[0074] On the other hand, the present invention also provides applications of resins with dual active groups.

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

[0076] The composition of the active group resin provided by the present invention, through the formulation system, especially the combination of photoinitiators and the combination of active group resins, can make the prepared photoresist have straight lines, upright and regular morphology, and excellent chemical resistance and clear resolution, which can meet the needs of actual production. 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 still be significantly shortened.

[0077] Furthermore, the dual-active-group resin provided by the present invention, especially dual-active-group resin B, can significantly improve the chemical resistance and resolution of photoresists and also make an important contribution to shortening the development time. When the resin composition containing the dual-active-group resin is used as a photoresist, the development time is shortened regardless of whether the thickness of the photoresist sample film is increased or not. Attached Figure Description

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

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

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

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

[0082] Figure 5 This is an HPLC chromatogram showing the residual amount of grafted monomers used in the dual-active-group resin B1 of this invention. Detailed Implementation

[0083] The present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. In the following examples and comparative examples, except for the dual-active-group resins B1, B2, B3, and B4, all the monomers and related reagents used can be purchased from the market. Specifically, dual-active-group resin A1 was purchased from Nanjing Yinxin Chemical Co., Ltd., model SMA2000; dual-active-group resin A2 was purchased from Nanjing Yinxin Chemical Co., Ltd., model SMA3000; dual-active-group resin A3 was purchased from Nanjing Yinxin Chemical Co., Ltd., model SMA1000; polyacrylic acid (CAS: 9003-01-4) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; styrene-maleic anhydride copolymer A was purchased from Polyscope's XIRAN 3000; styrene-maleic anhydride copolymer B was purchased from Polyscope's XIRAN 2000; and styrene-maleic anhydride copolymer C was purchased from Polyscope's XIBOND. 2025; Styrene-maleic anhydride copolymer D was purchased from Polyscope's SMAXIRANS Z30010; Inactive resin was purchased from Huayi Chemical Group's Huayi W4315; Scanning electron microscope was purchased from Thermofisher, model Apreo 2S; Potentiometric titrator was purchased from Metrohm, model 888Titrando; Spin coater was purchased from Mikasa, model MS-B150.

[0084] The preparation method of dual-active-group resin B1 includes the following steps: In a 500ml four-necked round-bottom flask equipped with a thermometer, reflux condenser, and stirrer, add 100.00g of propylene glycol methyl ether acetate, 74.69g of styrene-maleic anhydride copolymer A (n2:m2 ratio of 3:1, weight average molecular weight 10000), and 2.90g of triethylamine. After stirring to dissolve, add 22.11g of hydroxyethyl acrylate and 0.29g of hydroquinone to the flask, then heat to 90℃ and reflux for 12 hours. Cool and discharge to obtain dual-active-group resin B1. The average weight average molecular weight of dual-active-group resin B1 is 11000. When the anhydride in styrene-maleic anhydride copolymer A undergoes ring-opening and grafting reaction with hydroxyethyl acrylate, the infrared spectrum after the reaction is completed reaches 1779cm. -1 The characteristic absorption peak of the acid anhydride is relatively weak, and due to Figure 5 It can be seen that after the reaction of styrene-maleic anhydride copolymer A with hydroxyethyl acrylate to synthesize dual-active-group resin B1, the residual amount of hydroxyethyl acrylate in dual-active-group resin B1 is less than 5%.

[0085] The preparation method of dual-active-group resin B2 includes the following steps: 100.00g of propylene glycol methyl ether acetate, 69.41g of styrene-maleic anhydride copolymer B (n2:m2 ratio of 2:1, weight average molecular weight 6500) and 4.95g of triethylamine are added to a 500ml four-necked round-bottom flask equipped with a thermometer, reflux condenser, and stir until dissolved. Then, 27.40g of hydroxyethyl acrylate and 0.29g of hydroquinone are added to the flask, and the temperature is raised to 90℃ and stirred under reflux for 12h. The mixture is then cooled and discharged to obtain dual-active-group resin B2, wherein the average weight average molecular weight of dual-active-group resin B2 is 9000.

[0086] The preparation method of dual-active-group resin B3 includes the following steps: 120.00g of propylene glycol methyl ether acetate, 78.23g of styrene-maleic anhydride copolymer C (n2:m2 ratio of 4:1, weight average molecular weight 6500) and 4.95g of triethanolamine are added to a 500ml four-necked round-bottom flask equipped with a thermometer, reflux condenser, and stir until dissolved. Then, 20.81g of hydroxypropyl acrylate and 0.19g of hydroquinone are added to the flask, and the temperature is raised to 90℃ and stirred under reflux for 12h. The mixture is then cooled and discharged to obtain dual-active-group resin B3, wherein the average weight average molecular weight of dual-active-group resin B3 is 7000.

[0087] The preparation method of dual-active group resin B4 includes the following steps: 150.00g of propylene glycol methyl ether acetate, 60.80g of styrene-maleic anhydride copolymer D (n2:m2 in the styrene-maleic anhydride copolymer is 1:1, and the weight average molecular weight is 9000) and 1.90g of dimethylamine are added to a 500ml four-necked round-bottom flask equipped with a thermometer, reflux condenser, and stir until dissolved. Then, 44.07g of glyceryl methacrylate and 0.48g of p-hydroxyanisole are added to the flask, and the temperature is raised to 90℃ and stirred under reflux for 12h. The mixture is then cooled and discharged to obtain dual-active group resin B4, wherein the average weight average molecular weight of dual-active group resin B4 is 12000.

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

[0089] Activation time test: The test shall be conducted in accordance with the GB7193.4-87 standard;

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

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

[0092] Chemical resistance: Seal one end of a 50mm inner diameter glass tube with a sealing material that is not corroded by chemical reagents. Prepare a coating of the resin to be tested under certain conditions. Cut a piece of the same size that can fit into the glass tube and adhere it to the center of the seal to ensure good contact and sealing. Pour a 5% HCl solution into the tube to make the liquid level 20mm ± 2mm. Cover the tube tightly with a glass plate. After standing for 24 hours, remove the sample, wash and dry it. Continue to adhere the coating resin to the center of the seal to ensure good contact and sealing. Pour a 5% NaOH solution into the tube to make the liquid level 20mm ± 2mm. Cover the tube tightly with a glass plate. After standing for 24 hours, remove the sample, wash and dry it. Visually inspect the test area for any abnormal phenomena such as blistering, discoloration, or peeling.

[0093] Storage stability: Place 50g of the resin to be tested into a sealed bottle, first place it in a 50℃ oven for 15 days, then place it in a -10℃ refrigerator for 15 days, and then take it out to test the activity of the resin.

[0094] Application performance stability test: The resin to be tested was spin-coated on a 4-inch circular silicon wafer. During spin-coating, the spin coater speed was 1400 rpm and the spin-coating time was 30 s. After spin-coating, the smoothness and uniformity of the coating were observed.

[0095] Table 1

[0096]

[0097]

[0098] Compared with non-reactive resins, the dual-reactive group resin B provided in this application has higher activity, an acid value within a suitable range, and better chemical resistance, storage stability, and stable application performance.

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

[0100] Compared with dual-active group resin B4, when the n2:m2 ratio is within a suitable range, the activation time of dual-active group resins B1-B3 is shortened and the acid value is within a suitable range.

[0101] Compared with dual-active-group resins B1-B2, dual-active-group resins B, when their weight-average molecular weight is within a suitable range, can improve activation time, storage stability, and application performance stability to a certain extent. At the same time, dual-active-group resins B have a more suitable acid value range.

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

[0103] The components and their 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] The compositions obtained in Examples 1-9 and Comparative Examples 1-4 were subjected to development time, resolution, chemical resistance, and morphology tests. The specific test methods are as follows, wherein a homogenizer was used during spin coating:

[0110] Chemical resistance test: The compositions prepared in Examples 1-9 and Comparative Examples 1-4 were allowed to stand until the foam was eliminated before spin coating and pre-baking. After spin coating and pre-baking, the samples were immersed in a 3% (v / v) HCl solution for 24 hours, then washed with deionized water and dried. After immersion in a 3% (w / w) NaOH solution for 24 hours, the changes in the photoresist samples were observed, and their acid and alkali resistance were tested. The thickness of the photoresist sample was 15 μm. During spin coating, the spin coating time was 30 s and the rotation speed was 1400 rpm. During pre-baking, the drying temperature was 110℃ and the drying time was 90 s.

[0111] Development time test: The compositions prepared in Examples 1-9 and Comparative Examples 1-4 were allowed to stand until foam was eliminated, and then spin-coated, pre-baked, exposed, and developed. The exposed and unexposed portions of the photoresist were washed away. The time taken to obtain the desired pattern on the wafer was defined as the development time. The time from when the photoresist was applied to the developer after exposure to when the desired pattern was obtained was calculated. The photoresist film thickness was 15 μm. During spin-coating, the spin coating time was 30 s and the spin 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 / cm². 2 The developer used was a 2.38% (w / w) TMAH solution; the photoresist film thickness was 20 μm; during spin coating, the spin coating time was 30 s and the spin speed was 1000 rpm; during pre-baking, the drying temperature was 110℃ and the drying time was 90 s; during exposure, the ultraviolet energy was 210 mJ / cm². 2 The developer used was a 2.38% TMAH solution.

[0112] The resolution testing method is as follows: After the compositions prepared in Examples 1-9 and Comparative Examples 1-4 are allowed to stand until the foam is eliminated, they are spin-coated, pre-baked, exposed, and developed. Then, the exposed or unexposed parts of the photoresist are washed away to obtain the desired pattern on the wafer. The minimum resolution that can reproduce the pattern size under a scanning electron microscope is used to observe the resolution of the photoresist sample under a scanning electron microscope.

[0113] The morphology testing method is as follows: After the compositions obtained in Examples 1-9 and Comparative Examples 1-4 are allowed to stand until the foam is eliminated, they are spin-coated, pre-baked, exposed, and developed. Then, the exposed or unexposed parts of the photoresist are washed away, thereby obtaining the desired pattern on the wafer. The pattern is observed under a scanning electron microscope with the best magnification and clearest field of view. The requirements are met when the lines are straight and the morphology is upright and relatively regular, or when the lines are thick and straight and the morphology is upright and relatively regular. Optionally, the lines are straight and the morphology is upright and regular. Further optionally, the lines are thick and straight and the morphology is upright and regular.

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

[0115] Table 4

[0116]

[0117]

[0118]

[0119] As can be seen from the comparison between Examples 5 and Examples 8-9, when the mass ratio of photoinitiator 1 and photoinitiator 2 is within a suitable range, the resulting composition containing active group resin, when applied to photoresist, produces straight lines, upright and regular morphology, and excellent morphology.

[0120] As can be seen from the comparison between Example 5 and Comparative Examples 1-2, when photoinitiator 1 and photoinitiator 2 are used in combination and the mass fractions of photoinitiator 1 and photoinitiator 2 are within a suitable range, the resulting composition containing active group resin, when applied to photoresist, produces straight lines, upright and regular morphology, and excellent morphology.

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

[0122] As can be seen from the comparison between Example 5 and Comparative Example 4, when the carboxylic acid monomer containing alkenyl groups replaces the carboxylic acid polymer containing alkenyl groups, the development time can be shortened to a certain extent, and the development time is also reduced when the thickness of the photoresist sample increases.

[0123] As can be seen from the comparison between Examples 1-3 and Examples 4-9, when the composition of the active group resin prepared by using the dual active group resin B provided in this application is applied to the photoresist, the chemical resistance and resolution of the photoresist can be improved, the development time can be shortened, and even if 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] As can be seen from the comparison between Examples 1-2 and Examples 3-4, 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 lines are thick and 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 thickness of the photoresist sample increases, the shortening of the development time is more obvious, which meets the requirements of miniaturized electronic components with higher performance requirements.

[0125] As can be seen from the comparison of Examples 1-9, the composition of the active group resin prepared using the components and contents provided in this application has straight lines, upright and regular morphology, better chemical resistance and clearer resolution, and shortens the development time. Even when the thickness of the photoresist sample increases, the development time is appropriately shortened.

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

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

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

[0129] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the invention. The scope of the invention is defined by the appended claims and their equivalents. Obviously, the embodiments described in this invention are only a part of the embodiments of the invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A composition containing a resin with active groups, characterized in that: For use in photoresists, the composition containing active group resin comprises the following components in parts by weight: 50-65 parts of active group resin, 10-20 parts of alkenyl carboxylic acid monomer, 5-15 parts of crosslinking agent, 0.5-2 parts of photoinitiator 1, 1-15 parts of photoinitiator 2, and 5-30 parts of solvent. Wherein, photoinitiator 1 is an acylphosphine oxide-based free radical photoinitiator; photoinitiator 2 is a non-acylphosphine oxide-based free radical photoinitiator; 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; The resin containing active groups includes a resin with dual active groups; The weight-average molecular weight of the resin containing active groups is 5000-15000; The relative molecular mass of the carboxylic acid monomer containing an alkenyl group is 50-1000; The dual-active-group resin includes dual-active-group resin B, which has the structure described in formula I-2: Ⅰ-2； Where n2 and m2 are both integers, n2:m2 = 1.5-4:1; R is selected from one of the structures described in Formula II-1-1, Formula II-2-1 to Formula II-2-4, and Formula II-3-1: Indicates the bonding sites of chemical bonds; The dual-active-group resin B is prepared by reacting a styrene-maleic anhydride copolymer with a grafted monomer, wherein the weight-average molecular weight of the styrene-maleic anhydride copolymer is 6000-10000. The weight-average molecular weight of the dual-active-group resin B is 8000-15000.

2. The composition containing an active group resin according to claim 1, characterized in that: The acylphosphine oxide free radical photoinitiator comprises one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate. The non-acylphosphine oxide free radical photoinitiator comprises one or more of 2,2-dimethoxy-2-phenylacetophenone (benzoyladium dimethyl ketal), benzophenone, and 4-benzoylbiphenyl (4-phenylbenzophenone).

3. The composition containing an active group resin according to claim 1, characterized in that: The resin containing active groups also includes a single active group resin, which comprises one or more of acid anhydride resins and alkenyl resins.

4. The composition containing an active group resin according to claim 1, wherein the dual-active-group resin further comprises a dual-active-group resin A, the dual-active-group resin A having the structure described in Formula I-1: Ⅰ-1， in, n1 and m1 both represent integers, and n1:m1 = 2-4:1; Indicates the bonding sites of chemical bonds.

5. The composition containing an active group resin according to claim 4, characterized in that: n1:m1=2-3:

1.

6. The composition containing an active group resin according to claim 1, characterized in that, n2:m2=2-4:

1.

7. The composition containing an active group resin according to claim 6, characterized in that, n2:m2=2-3:

1.

8. The composition containing an active group resin according to claim 1, characterized in that: The alkenyl-containing carboxylic acid monomer comprises one or more of acrylic acid, methacrylic acid, and myristenoic acid.

9. The composition containing an active group resin according to claim 1, characterized in that, The crosslinking agent comprises one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethoxypentaerythritol tetraacrylate.

10. A resin with two active groups, characterized in that: The dual-active-group resin has the structure described in Formula I-2: Ⅰ-2； Where n2:m2=1.5-4:1, and both n2 and m2 represent integers; R is selected from one of the structures described in Formula II-1-1, Formula II-2-1 to Formula II-2-4, and Formula II-3-1: Indicates the bonding sites of chemical bonds; The dual-active-group resin is prepared by reacting a styrene-maleic anhydride copolymer with a grafted monomer, wherein the weight-average molecular weight of the styrene-maleic anhydride copolymer is 6000-10000. The weight-average molecular weight of the dual-active-group resin is 8000-15000.

11. The dual-active-group resin according to claim 10, characterized in that, n2:m2=2-4:

1.

12. The dual-active-group resin according to claim 11, characterized in that, n2:m2=2-3:

1.

13. Use of the composition of the resin containing active groups according to any one of claims 1-9.

14. The use of the dual-active-group resin according to any one of claims 10-12.

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