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At present, the core technology of high-end integrated circuit materials is in the hands of foreign companies such as Europe, America and Japan. Many key materials used in integrated circuit manufacturing have become the key to the development of my country’s independent semiconductor industry, just like semiconductor manufacturing equipment and EDA software. field. Even if it is as powerful as South Korea’s Samsung Electronics, during the Japan-South Korea trade war in July 2019, after Japan restricted the export of key raw materials such as photoresist, fluorinated polyimide and high-purity hydrogen fluoride to South Korea, the neck was stuck a little. There is no way.

Taking photoresist as an example, together with the supporting reagents, it accounts for about 12% of the wafer manufacturing materials, which is the fourth largest wafer manufacturing material, which determines the precision and yield of the semiconductor patterning process, and its quality and performance affect the integration. A key factor in circuit performance, yield and reliability. However, the production process of high-end photoresist is complex and the technical barriers are high. It has been monopolized by American and Japanese companies for many years. At present, Japan’s Japan Synthetic Rubber (JSR), Tokyo Yoshika, Shin-Etsu Chemical and Fuji Electronic Materials have occupied 70% of the global market share. % of the market share, the industry concentration is high. In addition to Japanese manufacturers, other photoresist manufacturers mainly include DowDuPont (the photoresist business is now spun off to New DuPont) and Dongjin Smeiken.

Especially ArF, KrF photoresist and high-end photoresist for EUV process in the future are of great significance to the development of integrated circuits in my country. At present, the demand of the semiconductor industry is growing, and the domestic growth rate is significantly higher than that of overseas. However, the global EUV and ArF photoresists are mainly supplied by JSR, Dow and Shin-Etsu Chemical and other suppliers. Localization in this field should be realized as soon as possible, otherwise it will be paid in the future. greater price.

　　A news of purchasing a lithography machine is a daily limit

On the evening of January 19, Jingrui, a domestic photoresist manufacturer, announced that the company successfully purchased an ASMLXT 1900 Gi type ArF immersion (DUV) lithography machine after multiple negotiations and active operation, and it arrived on the same day. Suzhou, moved into the company’s high-end photoresist R&D laboratory. In the next step, the company will actively organize relevant resources to complete the installation and commissioning of the equipment as soon as possible.

It is reported that Jingrui shares reviewed and approved the “Proposal on the Purchase of Equipment” at the twenty-eighth meeting of the second board of directors on September 28, 2020. In order to carry out high-end photoresist research and development projects for integrated circuit manufacturing, the company plans to import second-hand ASML lithography equipment from South Korea’s SK Hynix through Singtest Technology PTE. LTD. After disclosing the news of the purchase of the lithography machine, the company’s stock price rose strongly to the daily limit after opening higher in early trading on September 29, closing up 19.99%.

“Immersion lithography machine is the key equipment for high-end photoresist research and development. Despite the huge investment, Jingrui Co., Ltd. is determined to buy it.” Regarding the purchase of this lithography machine, Wu Tianshu, chairman of Jingrui Co., Ltd., introduced in his speech at the scene, in order to solve the problem In the field of integrated circuit manufacturing, the key material “stuck neck” problem, accelerate the research and development of high-end ArF photoresist, and establish a research and development platform.

　Millions of dollars in equipment is just the beginning

Judging from the on-site photos, when the ASML XT 1900 Gi lithography machine was moved into the venue, an air-cushion vehicle was also used, and its importance can be imagined.

How much did Jingrui Co., Ltd. spend on purchasing this lithography machine? According to a report disclosed on September 29, 2020, this ASML XT 1900 Gi-type ArF immersion lithography machine is worth US$11.025 million (equivalent to RMB 75.08 million) and can be used to develop high-end photoresists with a maximum resolution of 28nm.

There are also industry insiders who analyzed that more than 10 million US dollars can only buy a lithography machine host, but also a series of related auxiliary equipment such as coating and developing machines, defect inspection equipment, film thickness inspection machines, and a clean room… …The research and development of ArF photoresist requires a large investment of several hundred million yuan.

“With the continuous development of China’s integrated circuit industry and the continuous improvement of manufacturing processes, Jingrui’s deployment of ArF photoresist is both a responsibility and a challenge.” Jingrui said that although the overall strength of China’s integrated circuit industry has improved significantly, it is subject to According to the development level of photoresist technology in my country, the current self-sufficiency rate of g-line and i-line photoresist suitable for 6-inch silicon wafers is about 10%, and the self-sufficiency rate of KrF photoresist suitable for 8-inch silicon wafers is less than 5%. The ArF photoresist used for 12-inch silicon wafers is basically imported, and the localization of photoresist still has a long way to go.

　　The use and composition of each grade of photoresist

According to reports, as the chip enters the nanoscale, the wavelength of semiconductor photoresist is also constantly shortening, and it has gradually developed from ultraviolet broadband to g-line (436nm), i-line (365nm), KrF (248nm), ArF (193nm) ), ArF Immersion, and state-of-the-art EUV (

The main components of photoresist are divided into additives such as resin, sensitizer, solvent and surfactant. The solvent mainly disperses the components of the photoresist, so that the photoresist has fluidity. The solvent used in the current semiconductor and panel photoresist is mainly PGMEA (propylene glycol methyl ether acetate, also referred to as PMA); resin and sensitizer are used together , is the main functional component of photoresist to play a photosensitive effect. Different types of photoresist have very different compositions of resin and sensitizer. According to the photosensitive wavelength from long to short, it is mainly phenolic resin-diazonaphthoquinone system ( g line/i line), p-hydroxystyrene-photoacid generator system (KrF), acrylate-photoacid generator system (ArF), molecular glass or metal oxide system (EUV). Other additives include surfactants, stabilizers, and the like.

Although there are differences in the content of each component in various photoresists, the resin content is generally below 20%. Generally, the shorter the wavelength of the photoresist, the lower the resin content and the higher the solvent content: g line/i line The resin content of the glue is about 10-20%, the resin content of KrF glue is below 10%, and the resin content of ArF glue and EUV photoresist is usually below 5%.

Another important component of photoresist is sensitizer. G-line/i-line glue and panel glue will use photoinitiators including DNQ (diazonaphthoquinone) as sensitizer. Semiconductor photoresists (KrF, ArF, EUV) all use photoacid generators as the main photosensitive components.

In addition to resins and sensitizers, solvents and other additives such as leveling agents, surfactants, etc., are mainly used to form a uniformly dispersed solution system for the photoresist. Among them, most of the solvents used in various types of photoresists are propylene glycol methyl ether. Acetate, referred to as PGMEA overseas, and referred to as PMA in China.

　　ArF photoresist market accounted for the largest

Semiconductor photoresist continues to grow, and domestic manufacturers continue to make efforts. With the rapid development of the global semiconductor industry, the global semiconductor photoresist market continues to grow. According to SEMI, the global semiconductor photoresist market size in 2018 was US$2.029 billion, a year-on-year increase of 15.83%. Among them, China, America, Asia Pacific, Europe and Japan accounted for 32%, 21%, 20%, 9% and 9% respectively.

From a global perspective, KrF and ArF have the largest market share, and EUV photoresist has not yet begun to be involved in China. In terms of products, ArF/liquid immersion ArF corresponds to advanced integrated circuit technology, and the market share is the highest, reaching 41%, but KrF glue and i-line/g-line glue still have a considerable market size. In the future, with the use of multiple exposure technology, the market demand for ArF photoresist will continue to expand.

It can be seen from the downstream distribution of various types of semiconductor photoresists that g-line/i-line glue is currently mainly used in power semiconductors and sensors, while KrF glue is mainly used in memory chips, and ArF is mainly used in logic chips and Manufacturing of high-end memory chips. From the perspective of market geographical distribution, the photoresist market distribution is more consistent with the global wafer manufacturing capacity distribution. Taiwan, South Korea, North America, mainland China, and Japan occupy the main markets.

　Japanese companies have strong control in the high-end photoresist market

From the perspective of the competitive landscape, the global photoresist market is basically controlled by Japanese companies, and Japanese manufacturers account for 70% of the market share in all types of semiconductor photoresists. In terms of categories, Japanese manufacturers have a market share of 93%, 80%, and 61% in the ArF, KrF, and g-line/i-line adhesive markets, respectively, showing strong control in the high-end market.

Although the disadvantage of Chinese photoresist companies is not obvious from the perspective of gross profit margin, in terms of revenue volume, domestic companies such as Jingrui and Hengkun are nearly 2 orders of magnitude worse than Japanese companies. From the perspective of R&D expenditure, the proportion of R&D investment in domestic photoresist-related listed companies in operating income is not significantly behind that of Japanese leading companies, but from the absolute value of R&D investment, domestic companies are 1-2 different from Japan’s leading companies. Magnitude. No matter from the perspective of industry status, company size, technical strength, and R&D investment, domestic photoresist companies have a long way to go to catch up with Japan’s leading companies.

Although the ASML XT 1900 Gi lithography machine purchased this time is not an advanced process lithography machine, it is of great significance for the localization of core integrated circuit materials.

“The installation project is expected to be completed in the first half of the year. We expect to complete the technical parameters and product finalization of the new process of ArF photoresist products within three years, and achieve large-scale production.” Looking forward to the future, Wu Tianshu believes that to realize the industrialization of ArF photoresist, China’s Photoresist can basically meet the requirements of 45nm to 28nm technology and process, and finally realize the strategic layout applied to 12-inch chip manufacturing.

　　The key companies in the domestic semiconductor photoresist industry chain are as follows:

Jingrui Co., Ltd.: Subsidiary Suzhou Ruihong has undertaken and completed the national 02 special “i-line photoresist product development and industrialization” project. The i-line photoresist has been supplied to well-known large-size semiconductor manufacturers in China. The photoresist has completed the pilot test, and the product resolution has reached the technical requirements of 0.25-0.13μm, and a pilot test demonstration line has been built. On January 19, the ASML XT 1900Gi ArF immersion lithography machine purchased by Jingrui Co., Ltd. successfully entered the factory, which can be used to develop high-end photoresists with a maximum resolution of 28nm.

Shanghai Xinyang: mainly focuses on KrF and dry ArF photoresist, and has entered the stage of production capacity construction. According to the fixed increase plan on November 3, 2020, the company plans to raise no more than 1.45 billion yuan, of which 815 million yuan is planned to be invested in high-end photoresist research and development and industrialization projects for integrated circuit manufacturing. The main goal is to achieve ArF dry method The industrialization of the photoresist used in the process and the KrF thick film photoresist for 3D NAND step etching, and strive to realize the industrialization of the above products before 2023, filling the domestic gap. On January 5, the company announced that since the establishment of the R&D and industrialization project of 193nm ArF dry photoresist, according to the progress of the project, it has planned to purchase core equipment such as ASML-1400 lithography machine. It is expected that the lithography machine will enter the market. The on-site time of the partner is before the end of March 2021.

Beijing Kehua (not listed): The product types cover KrF (248nm), G/I line (including broad spectrum), KrF (248nm) photoresist has passed the certification of some customers including SMIC, and has achieved batch supply Goods, G-line, i-line photoresist has achieved mass production supply.

NTU Optoelectronics: In 2017, it undertook the R&D and industrialization project of ArF (193nm) photoresist material, one of the key core materials for integrated circuit chip manufacturing. On December 17, 2020, it was announced that the self-developed ArF photoresist product has successfully passed the customer use certification and can be used in the integrated circuit manufacturing process of the 90nm~14nm technology node. According to the plan, Nanda Optoelectronics plans to build an annual production capacity in Ningbo Economic Development Zone. 25 tons of 193nm (ArF dry and immersion) photoresist production line, the lithography machine purchased and installed by the company is also ASML’s 1900 model immersion lithography machine.

According to Hu Jian, a researcher at Huatai Securities, on the one hand, my country has issued a number of relevant policies, which provide good policy support for the development of the photoresist industry. In the domestic semiconductor material industry chain in China, the research and development and mass production of domestic photoresist may be accelerated. Domestic manufacturers plan to expand investment in the field of semiconductor photoresist monopolized by Japan and the United States, and develop and mass production in the field of high-end ArF photoresist. Continue to break through.

According to the forecast of Zhiyan Consulting, the market space of semiconductor photoresist in mainland China will be close to 5.5 billion yuan in 2022, twice that of 2019. Hu Jian further pointed out that, taking the development history of photoresist in Japan as a mirror, he believes that in China, which has the world’s largest electronics industry and semiconductor market, the continuous expansion of local semiconductor production capacity, national policies and determination and the support of the integrated circuit fund will all contribute to China. Domestic photoresist provides unprecedented new opportunities for development.