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??Story of Cycloaliphatic Epoxy Resin Project for Arf Photoresist of Tetra New Materials


Eight-year Efforts with Great Success, High-end Materials for Dream Pursue

There is a (methyl) acrylic-type cycloaliphatic epoxy monomer with annual sales of less than 200t, but it has been listed in the category of “bottleneck” materials that need to be addressed urgently in Guidelines for Demonstration of First Batch Applications of Key New Materials (2019 Edition and 2021 Edition) by the Ministry of Industry and Information Technology, with the reason that it is one of the most widely used monomers in the global ArF photoresist industry chain.

Photoresist, also known as photosensitive resist, is a medium used for pattern transfer through photochemical reactions. It is a type of fine chemicals characterized with assorted varieties, diversified properties and wide applications. Mainly used in fine processing of integrated circuits and discrete semiconductor devices in the electronics industry, the photoresist is to transfer fine patterns required from the mask to the substrate to be processed through exposure and development under the photochemical reaction, then to undergo etching, diffusion, ion implantation and metallization process. Therefore, it is the key basic chemical material in the electronic industry.

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The progress of electronic industry is closely related to the development of photoresist. If there is no core technology of semiconductor photoresist in hand, the integrated circuit industry in China will still be limited even if any breakthrough is made in photoetching machine. At present, more than 90% market shares of semiconductor photoresist have been occupied by enterprises in Japan, Korea and the United States, with main manufacturers including JSR, TOK, Fuji Electronics, Shin-Etsu and Sumitomo Chemical in Japan as well as Dow Chemical in the United States. Although domestic photoresist has been developed in recent years, it can only strive for breakthroughs in high-end markets, especially in the field of Arf photoresist. As mostly core processes of raw material production are mastered by foreign enterprises, this barrier also makes it difficult for domestic manufacturers to develop high-standard products.

At the end of 2015, a well-known foreign photoresist enterprise put forward that “There is an acrylic-type cycloaliphatic epoxy monomer in the market accounting for a large proportion in their photoresist formula system, but only one Japanese enterprise can supply such product in bulk. Therefore, they may face the risk of running out of stock at any time., and the enterprise invited Tetra to provide such kind of products by virtue of the technical accumulation in the field of cycloaliphatic epoxy resin.” Faced with such new market opportunity, Tetra New Materials set up a special team for photoresist project (Internal Project Code PR-001) with the General Manager as the team lead, the Technical Director as the project manager. The project team was composed of talented professionals in process development, R&D analysis, process technology, engineering technology, production development and supply chain to jointly tackle problems in key technologies.

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Group Photo of Project Team

Based on the overall schedule of “two years for laboratory production, two years for pilot production and three years for mass production”, the process development team conducted more than 1000 trials in the laboratory in over 600 days, solved problems in process route selection, indices of raw and auxiliary materials and intermediates, catalyst screening, inhibitor screening, product polymerization during distillation process, product yellowing, analysis of polymer and other impurities (key impurity<0.1%; non-detected polymer is required), excessive inhibitor, excessive viscosity (≤15cps) and excessive metal ions (the content of 12 kinds of metal ions ≤50ppb) and finally provided five batches of laboratory expanded samples for customers in 2017 and passed the customer’s laboratory test in early 2018.

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