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Analysis of the localization progress of the photoresist industry chain and monomers, resins, and supporting reagents

June 17, 2024

Latest company news about Analysis of the localization progress of the photoresist industry chain and monomers, resins, and supporting reagents

Analysis of the localization progress of the photoresist industry chain and monomers, resins, and supporting reagents

Summary

Photoresist is a crucial core material in the photolithography process. It is mainly composed of film-forming resins, sensitizers , monomers, solvents and additives. It is the core bottleneck material of the semiconductor industry. It has high technical barriers and is more dependent on imports. The photoresist industry chain involves multiple links, from raw materials such as monomers, resins, photosensitive materials to supporting reagents such as developers and strippers. China's semiconductor photoresist market relies on imports. The main components include KrF, ArF and EUV photoresist resins and photosensitive materials. Among them, monomers and post-processing technologies are the main factors restricting localization. Semiconductor photoresist supporting reagents are also bottleneck products that urgently need to be domestically produced, among which photosensitive materials and developers & strippers are the key.

Details

Photoresist is a crucial core material in the photolithography process. It can be divided into PCB, panel and semiconductor photoresist according to the downstream. It is mainly composed of film-forming resin, sensitizer, monomer, solvent and additive. It is also the core bottleneck material of the semiconductor industry. It has high technical barriers and is more dependent on imports. The photoresist industry chain involves multiple links, from raw materials such as monomers, resins, photosensitive materials to supporting reagents such as developers and stripping solutions. It is expected that the global photoresist market CAGR will reach 6.3% from 2019 to 2026, and will exceed US$12 billion by 2026.

1. Photoresist is a core material that is crucial in the photolithography process. It can be divided into PCB, panel and semiconductor photoresist according to the downstream . Among them, photoresist used in semiconductors is the core bottleneck material of China's semiconductor industry. It is estimated that the global photoresist market CAGR is expected to reach 6.3% from 2019 to 2026, and exceed US$12 billion by 2026. Combined with the factor of industrial transfer, the growth rate of China's photoresist market exceeds the global average.

2. The composition structure of photoresist is complex, mainly composed of film-forming resin, sensitizer, monomer, solvent and additive . The synthesis of semiconductor photoresist monomer is difficult, with high purity and metal ion requirements, and it relies on imports. Xuzhou Bokang reserves 80% of the world's photoresist monomer technology and is a stable supplier of well-known Japanese and Korean photoresist finished product companies. Wanrun shares also have photoresist monomer products. Resin is the most important component of photoresist, and domestic companies such as Shengquan Group, Xuzhou Bokang, Tongcheng New Materials, and Wanrun shares have layouts. The overall localization supply of photoresist solvents is high, and PMA's share is far ahead. Domestic listed companies Baichuan Shares and Yida Shares have layouts. The localization rate of photosensitive materials for photoresists is low, and domestic companies such as Qiangli New Materials and Jiuri New Materials have layouts. The supporting reagents are mainly developers and stripping solutions, and domestic companies such as Grinda have layouts.

3. Photoresist is a material with extremely high technical barriers. The production of high-quality photoresist is highly dependent on monomers with good performance and stable quality . Different photoresists have different performance requirements in terms of exposure light source, manufacturing process, film-forming characteristics, etc., and different requirements for material solubility, etching resistance and photosensitivity. Domestic companies need to improve their R&D strength and technical level to meet market demand.

4. The photoresist industry chain involves multiple links, from raw materials such as monomers, resins, photosensitive materials to supporting reagents such as developers and stripping solutions . Domestic companies need to find breakthroughs in different links to enhance their competitiveness. Xuzhou Bokang reserves 80% of the world's photoresist monomer technology, Shengquan Group is one of the major domestic photoresist manufacturers, Grinda has a layout in the developer field, and Qiangli New Materials and Jiuri New Materials have a layout in the photosensitive material field.

5. Photoresist has a wide range of applications, mainly in semiconductors, PCBs, panels and other fields. Among them, photoresist used in semiconductors is the core bottleneck material of China's semiconductor industry, accounting for 30% of the manufacturing cost of chips . With the rapid development of automobiles, AI, national defense and other fields, the market demand for photoresist continues to increase.

6. The global photoresist market is expanding, and the CAGR of the global photoresist market is expected to reach 6.3% from 2019 to 2026, exceeding US$12 billion by 2026. Combined with the factors of industrial transfer, the growth rate of China's photoresist market exceeds the global average. The demand for domestic photoresist market continues to increase, and domestic companies need to improve their competitiveness and strive for a larger market share.

Photoresist is the core material in the photolithography process and consists of film-forming agents, photosensitizers, solvents, additives and other chemical components and other additives. According to the application field, photoresist is divided into PCB, panel and semiconductor photoresist. PCB photoresist includes dry film photoresist, wet film photoresist and solder mask ink. Semiconductor photoresists are divided into G/I line photoresists, KrF photoresists, ArF photoresists and EUV photoresists according to the exposure wavelength. Display panel photoresist is mainly divided into TFT-LCD photoresist, color photoresist, black photoresist and touch screen photoresist. Other photoresists include electron beam photoresist, photosensitive polyimide, photosensitive polybenzoxazole resin, etc.

1. Photoresist is the core material in the photolithography process, which is composed of chemical components such as film formers, photosensitizers, solvents, additives and other additives. Photoresist is a light-sensitive mixed liquid used to transfer fine patterns from the mask to the substrate to be processed. Depending on the processing requirements, the film formers, photosensitizers, solvents and additives of photoresists will be different, thus deriving different types.

2. PCB photoresist is mainly used to transfer the circuit image to the substrate board. PCB photoresist includes dry film photoresist, wet film photoresist and photoimageable solder mask ink. The processing principles of dry film photoresist and wet film photoresist are the same, and the main difference lies in the process flow and usage requirements. Photoimageable solder mask ink is a special photoresist, which is mainly used to make solder mask layer and has two functions of solder mask and photolithography.

3. Semiconductor photoresist is mainly used to process fine electronic circuit patterns. According to the different exposure wavelengths, semiconductor photoresists can be divided into G/I line photoresists, KrF photoresists, ArF photoresists and EUV photoresists. As the line width of integrated circuits continues to shrink, the exposure wavelength of photoresists is also constantly developing towards the short-wave band to improve resolution. At the same time, the resolution level of photoresists is also improved through resolution enhancement technology.

4. Display panel photoresist is mainly used to manufacture fine patterns of liquid crystal panels. According to different uses, display panel photoresist can be divided into TFT-LCD photoresist, color photoresist, black photoresist and touch screen photoresist . Among them, TFT-LCD photoresist is used to process fine pattern electrodes in the front-end array process of liquid crystal panels; color photoresist and black photoresist are used to manufacture color filters; touch screen photoresist is used to make touch electrodes.

5. Photoresist supporting reagents are materials that directly interact with photoresist, including developers, stripping solutions , etc. The developer is a reagent that separates the exposed and unexposed parts of the photoresist, and the stripper is used to remove the photoresist and its residues. Photoresist supporting reagents are an indispensable part of the photolithography process and have an important impact on photolithography quality and processing efficiency.

6. Other photoresists mainly include special process photoresists such as electron beam photoresist, photosensitive polyimide and photosensitive polybenzoxazole resin. These photoresists are inferior to semiconductor photoresists in terms of number of manufacturers, supply volume and unit price. Electron beam photoresist is a high-resolution photoresist that can achieve submicron resolution. Photosensitive polyimide and photosensitive polybenzoxazole resin are optical materials mainly used to make micro circuit boards.

7. As a key material for micro-processing technology, the market size and application areas of photoresist are constantly expanding. With the continuous development of industries such as consumer electronics, communications, and medical care, the requirements for micro-processing technology are becoming higher and higher, which will further promote the development of the photoresist market. At present, the domestic photoresist market is mainly dominated by imported products, but with the technological progress and production capacity improvement of domestic enterprises, the market share of domestic photoresists will gradually increase.

Photoresist is one of the most important processes in the manufacture of integrated circuits. It is composed of resin, sensitizer, monomer, solvent and other additives. The quality stability of photoresist is crucial to manufacturing accuracy and cost control. Different types of photoresists require different raw materials and supporting reagents. Photoresist resin is the main component of photoresist, and monomer is the raw material of synthetic resin. The resin system and monomer type of different types of photoresists are also different.

1. Photoresist and its supporting functional materials are used in the lithography and etching process. In the manufacturing process of large-scale integrated circuits, lithography and etching technology is the most important process in the processing of fine circuit patterns, which determines the minimum feature size of the chip, accounts for 40-50% of the chip manufacturing time, and accounts for 30% of the manufacturing cost. In the process of pattern transfer, the silicon wafer is generally lithographically processed more than ten times.

2. The composition and structure of photoresists are complex, and product barriers are high. Photoresists are mainly composed of resins, sensitizers (photoinitiators/photosensitizers/photoacid generators), monomers, solvents and other additives. Photoresists for different purposes have different performance requirements in terms of exposure light sources, manufacturing processes, film-forming characteristics, etc., and different requirements for material solubility, etching resistance and photosensitivity. The proportion of different raw materials will vary greatly, among which photoresist resin is the main component of photoresist.

3. Resin is the most important component of photoresist. Resin accounts for 50% of the total cost of photoresist, the largest proportion among photoresist raw materials, followed by monomers accounting for 35% and photoinitiators accounting for 15%. The proportions of different types of photoresists will vary. For example, ArF resin is mainly propylene glycol methyl ether acetate, which accounts for only 5%-10% by mass, but its cost accounts for more than 97% of the total cost of photoresist raw materials.

4. Photoresist resin is the main component of photoresist, which is used to polymerize different materials in photoresist to form the skeleton of photoresist and determine the basic properties of photoresist such as hardness, flexibility, adhesion, etc. Different types of photoresists have different resin systems and monomer types. For example, the resin system of UV photoresist (G line, I line) is phenolic resin and diazonaphthoquinone compound, and the resin system of deep ultraviolet photoresist (KrF, ArF photoresist) is poly(p-hydroxystyrene) and its derivatives and photoacid generators, poly(alicyclic acrylate) and its copolymers and photoacid generators. The raw material system used in deep ultraviolet photoresist (EUV photoresist) is often polyester derivative molecular glass single component material and photoacid generator.

5. Photoresist monomers are the raw materials for synthetic resins, and different types of photoresists have corresponding photoresist monomers. Traditional I-line monomers are mainly methylphenol and formaldehyde, which are bulk chemicals; KrF monomers are mainly styrene monomers, which are liquid in nature; ArF monomers are mainly methacrylate monomers, which are both solid and liquid in nature. The performance and quality stability of the monomers determine the performance and quality stability of the resin , and the resin is polymerized from monomers. The best quality batches of filaments have different lengths, such as long, medium, and short. High-quality resins require that the length and number of filaments of each length be consistent or similar, which is an important factor in ensuring the stability and consistency of the final photoresist performance .

6. The sensitizers in photoresist include photosensitizers and photoacid generators, which are the key components of photoresist and play a decisive role in the sensitivity and resolution of photoresist. The types and proportions of sensitizers in different types of photoresists will vary.

7. Solvents are the largest component in photoresists. Their purpose is to keep the photoresist in a liquid state, but they themselves have almost no effect on the chemical properties of the photoresist. Additives include monomers and other auxiliary agents. Monomers have a regulating effect on the photochemical reaction of photoinitiators, and auxiliary agents are mainly used to change the specific chemical properties of photoresists.

8. The quality stability of photoresist is crucial to manufacturing precision and cost control. Different types of photoresists require different raw materials and supporting reagents. The resin, the core component of photoresist, determines its photolithography performance and etching resistance, while the monomer is the raw material for synthetic resin. The resin system and monomer type of different types of photoresist are also different . To produce high-quality photoresist, you must have monomers with good performance and stable quality.

The yield of photoresist monomers and synthetic resins varies greatly. Semiconductor-grade photoresist monomers require higher quality, less metal ion content, and higher prices. The industrialization of photoresist monomers is difficult and relies on imports. Domestic companies such as Xuzhou Bokang are rising. The resin of photoresist is the most important component of photoresist, and IC-grade resin relies on imports.

1. The yield of photoresist monomers to synthesize resins varies. The performance indicators of photoresist monomers include purity, moisture, acid value, impurities, metal ion content and other indicators. At the same time, the yield of different photoresist monomers to make resins is different. The yield of KrF monomer to make KrF resin is higher, and 1 ton of monomer will produce about 0.8-0.9 tons of resin; the yield of ArF will be lower, about 1 ton of monomer will produce 0.5-0.6 tons of ArF resin, and ArF resin is polymerized from several monomers, and the performance and price of each monomer are also different.

2. The barriers to entry for semiconductor photoresist monomers are extremely high. The synthesis of semiconductor-grade photoresist monomers has certain particularities, requiring more stable quality and fewer metal ion impurities. For example, the purity of semiconductor-grade monomers is required to reach 99.5%, and the metal ion content is less than 1ppb; while the panel-grade monomer structure is ethylene oxide, the purity requirement is only 99.0%, and the metal ion content is at least less than 100ppb. The price of semiconductor-grade photoresist monomers is much higher than that of general monomers.

3. The industrialization of photoresist monomers faces many difficulties and relies on imports. Monomers are easy to polymerize, experience has poor replicability, monomer purity is high, metal ion control is difficult, process amplification is difficult, and the verification cycle is long. It takes a long certification process for domestic companies to enter the supplier system of downstream customers. Generally, downstream customers will not easily change the original monomer supplier unless there are special reasons, and they need to obtain the consent and certification of the terminal photoresist manufacturer before they can change .

4. Domestic enterprises are catching up. At present, a considerable part of the photoresist monomer market in my country is still mainly occupied by leading companies in the United States and Japan such as DuPont and Mitsubishi Chemical.

5. The resin of the photoresist is the most important component of the photoresist. The photoresist resin is a high molecular polymer with some physical properties of high molecules, such as film-forming properties and Tg (glass transition temperature). The resin of the photoresist also has certain chemical characteristics. It must be able to react with the acid generated by the photoacid generator under light, or undergo deprotection (chemically amplified photoresist), or combine with other components (traditional G/I line photoresist), or undergo cross-linking (negative photoresist), thereby causing a change in solubility in the developer. Taking chemically amplified photoresist as an example, there is a switch on the resin that controls its dissolution in the developer - an insoluble hanging group. When this switch is turned off, the resin does not dissolve in the developer; during the exposure process, the acid decomposed by the photoacid reacts with the insoluble hanging group, which is equivalent to turning on the switch, allowing the resin to dissolve in the developer and achieve pattern transfer.

6. Among photoresist resins, IC-grade resins rely on imports. G-line photoresists use cyclized rubber resins, and 1-line photoresists use phenolic resins . The phenolic resins must be linear phenolic resins, which are electronic grade and completely different from the phenolic resins commonly seen in life. The degree of localization is very low and they mainly rely on imports.

7. The chemical and physical properties of photoresist resin play a crucial role in the performance and quality of photoresist.

8. The characteristics of photoresist monomers include the large difference in the yield of photoresist monomer synthetic resins. Semiconductor-grade photoresist monomers require higher quality, less metal ion content, and higher prices. The industrialization of photoresist monomers is difficult and relies on imports . Domestic companies such as Xuzhou Bokang and Ningbo Microchip are rising. The resin of photoresist is the most important component of photoresist, and IC-grade resin relies on imports . The chemical and physical properties of the resin play a vital role in the performance and quality of photoresist.

China's semiconductor photoresist market relies on imports. The main components include KrF, ArF and EUV photoresist resins and photosensitive materials. Among them, monomers and post-processing technology are the main factors restricting localization. Companies such as Xuzhou Bokang, Tongcheng New Materials and Wanrun Co., Ltd. have achieved relevant research and development and mass production results, but their market shares are small . Solvents account for the highest proportion in photoresists, and PMA is the most commonly used. Photosensitive materials are mainly divided into PAG and PAC, which have a significant impact on the properties of photoresist.

1. KrF photoresist resin mainly relies on imports. The monomer is a derivative of p-hydroxystyrene, and domestic supply is small . The production process of KrF photoresist resin is also difficult, especially the post-processing process.

2. ArF photoresist resin is made of copolymers of several monomers and has a high degree of customization. Some common ArF resins can be bought on the international market, but high-end ArF resins are almost not sold. The main constraints on domestic production are monomer supply and production process .

3. EUV photoresist resin can be made of poly(p-hydroxystyrene) resin, molecular glass or metal oxide , but due to equipment limitations, there is basically no domestic production . High-end chip packaging photoresist uses PI and PSPI resins, which are also very difficult, and the technology is basically in the hands of several foreign manufacturers .

4. Solvents account for the highest proportion in the photoresist system, among which PMA is the most commonly used. According to statistical analysis, among semiconductor and display photoresists, the solvent content in ArF photoresist is approximately 94.4%, the solvent content in KrF photoresist is approximately 89.4%, and the solvent content in i/g line photoresist is approximately 80% . Among display photoresists, TFT positive resist contains roughly 82% solvent, color photoresist has about 56% solvent, and black photoresist has about 31% solvent.

5. Photosensitive materials include photoinitiators and photoacid generators, which are important additives in photoresist. Photosensitive materials are compounds that are truly light-sensitive in photoresist components and are an important component of photoresist. Photoinitiators and photoacid generators are used in novolac resin and polyparahydroxystyrene or polymethacrylate resin system photoresists respectively. Photosensitive materials have a significant impact on the properties of the photoresist, among which PAG has an impact on the sensitivity and resolution of the photoresist and the diffusion rate of acid in the exposed area.

6.PAG is mainly used in chemically amplified bulk photoresists, including KrF photoresist, ArF photoresist, and EUV photoresist, which are solid at room temperature. PAC is mainly used in novolac resin system photoresists, such as g-line/i-line photoresists. The photosensitive material has a significant impact on the properties of the photoresist.

7. PGMEA is one of the commonly used display photoresist solvents, accounting for 85%-90% of the total market demand . In addition to PGMEA, the market demand of 3MBA, EEP and EDM ranks among the top three, slightly larger than DBDG, DMDG, PGDA and PGME, while PM, cyclohexanone and EL are in the market. Photoinitiators and photoacid are relatively dependent on imports .

Semiconductor photoresist supporting reagents are stuck products in urgent need of localization, among which photosensitive materials and developers & strippers are the key. Domestic companies have made breakthroughs in the field of photosensitive materials, but further development is still needed. The developer and stripper markets are growing steadily, and domestic companies are making plans

1. Photosensitive materials for semiconductor photoresists are one of the key bottleneck products and are still dependent on overseas imports . The prices of photosensitive materials of different qualities vary greatly. The price of PAG for KrF photoresists is 6,000-15,000 yuan/kg , while the price of PAG for ArF photoresists is about 15,000-300,000 yuan/kg , with a price difference of up to 20 times. Domestic companies have made some layouts in the field of photosensitive materials, but further development is still needed.

2. The main function of the developer is to dissolve the photoresist in the photolithography process. According to the different types of developers, the developer can be divided into positive photoresist developers and negative photoresist developers. Almost every type of photoresist has a special developer to ensure high-quality development. For KrF positive photoresist, tetramethylammonium hydroxide (TMAH) with a concentration of 2.38% is generally used as the developer.

3. Positive photoresist developer is mainly used to dissolve the exposed area of positive photoresist. It has good contrast, and the generated graphics have good resolution, good step coverage and good contrast, but poor adhesion, poor etching resistance and high cost. Negative photoresist developer is mainly used to dissolve the unexposed area of negative photoresist. It has good adhesion and blocking effect, fast photosensitivity, but it is easy to deform and expand during development, and can only be used for a resolution of 2pm.

4. Grinda is the leading domestic TMAH developer. The company's core product is TMAH developer. In 2004, it achieved a technological breakthrough in the product and successfully achieved mass production. The relevant technical indicators have reached the SEMI G5 standard requirements, breaking the monopoly of foreign companies in this field. The products not only replace imports, but are also exported to South Korea, Japan, Taiwan and other regions.

5. Stripping solution refers to the supporting reagent used to remove the photoresist on the substrate after exposure, development and subsequent processes. Stripping solution is usually used after the etching process is completed to remove the photoresist and residual substances while preventing damage to the underlying substrate layer. With the development of high-precision photolithography technology, the etched patterns are becoming more and more miniaturized, and the etching conditions of metals and oxide films have become more harsh, resulting in greater damage to the photoresist and deterioration of the photoresist.

6. The stripping liquid market is growing steadily. In 2022, the global photoresist stripping liquid market sales reached US$773 million, and it is expected to reach US$1.583 billion in 2029, with a compound annual growth rate (CAGR) of 8.9% (2023-2029). From the perspective of product type and technology, it can be divided into positive photoresist stripping liquid and negative photoresist stripping liquid. Since positive photoresist has become the mainstream photoresist, the corresponding positive photoresist stripping liquid is also the dominant type in the global photoresist stripping liquid market, with a consumer market share of 71.9% in 2022 and a share of 75.3% in 2029.

7. Developer and stripping solution are supporting reagents for photoresists and are also wet electronic chemicals (ultrapure reagents) . Photoresist manufacturers and wet electronic chemical manufacturers have made some arrangements in this field.

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