Central Glass Company, Limited

International Business Machines Corporation

Takehisa Ishimaru

Rudy J Wojtecki

Ratnam Sooriyakumaran

Daniel Sanders

Satoru Narizuka

Hoa D Truong

Akihiro Ishii

Manabu Yasumoto

Takashi Ootsuka

Takako Yamazaki

Mari Imamura

Non-ionic photo-acid generating (PAG) compounds were prepared that contain an aryl ketone group having a perfluorinated substituent alpha to the ketone carbonyl. The non-polymeric PAGs release a sulfonic acid when exposed to high energy radiation such as deep UV or extreme UV light. The photo-generated sulfonic acid has a low diffusion rate in an exposed resist layer subjected to a post-exposure bake (PEB) at 100&#xb0; C. to 150&#xb0; C., resulting in formation of good line patterns after development. At higher temperatures, the PAGs can also undergo a thermal reaction to form a sulfonic acid. The perfluorinated substituent provides improved thermal stability and hydrolytic/nucleophilic stability.

Fluorinated sulfonate esters of aryl ketones for non-ionic photo-acid generators

Non-ionic photo-acid generating (PAG) polymerizable monomers were prepared that contain a side chain sulfonate ester of an alpha-hydroxy aryl ketone. The aryl ketone group has a perfluorinated substituent alpha to the ketone carbonyl. The sulfur of the sulfonate ester is also directly linked to a fluorinated group. PAG polymers prepared from the PAG monomers release a strong sulfonic acid when exposed to high energy radiation such as deep UV or extreme UV light. The photo-generated sulfonic acid has a low diffusion rate in an exposed resist layer subjected to a post-exposure bake (PEB) at 100&#xb0; C. to 150&#xb0; C., resulting in formation of good line patterns after development.

Non-ionic aryl ketone based polymeric photo-acid generators

Non-ionic photo-acid generating (PAG) compounds were prepared that contain an aryl ketone group. The disclosed non-polymeric PAGs release a strong sulfonic acid when exposed to high energy radiation such as deep UV or extreme UV light. The photo-generated sulfonic acid has a low diffusion rate in an exposed resist layer subjected to a post-exposure bake (PEB) at 100&#xb0; C. to 150&#xb0; C., resulting in formation of good line patterns after development. At higher temperatures, the PAGs undergo a thermal reaction to form a sulfonic acid.

Non-ionic low diffusing photo-acid generators

Photo-acid generating vinyl polymerizable monomers (PAG monomers) were prepared comprising sulfonate ester groups of N-hydroxide imides. The photo-acid generating portion of the PAG monomer is linked to a polymerizable portion of the monomer by an amide linking group. Photo-acid generating polymers (PAG polymers) of the PAG monomers show high sensitivity to extreme ultraviolet radiation (13.5 nm) and much less sensitivity to far ultraviolet wavelengths (193 nm, 248 nm). The PAG polymers also exhibit thermal and chemical amplification properties useful for forming high resolution positive tone or negative tone lithographic resist patterns.

Non-ionic photo-acid generating polymers for resist applications

A production process of a fluorosulfuric acid aromatic-ring ester according to the present invention includes reaction of an aromatic-ring hydroxyl compound with sulfuryl fluoride (SOF) in the presence of a tertiary amine except pyridine and methylpyridine. The sulfuryl fluoride, used as the reactant in the production process according to the present invention, is widely adapted as a fumigant and is easily available on a large scale. Further, the target compound can be obtained rapidly with a high yield under moderate reaction conditions in the production process according to the present invention. In this way, all of the prior art problems can be solved in the production process according to the present invention. The production process according to the present invention is thus particularly useful for industrial production of the fluorosulfuric acid aromatic-ring ester.

Process for producing fluorosulfuric acid aromatic-ring esters

A production method of a &#x3b2;-fluoroalcohol includes performing a reaction of an &#x3b1;-fluoroester with hydrogen gas (H) in the presence of a specific ruthenium complex (i.e. a ruthenium complex of the general formula [2], preferably a ruthenium complex of the general formula [4]). This production method can employ a suitable hydrogen pressure of 1 MPa or less by the use of such a specific ruthenium complex and does not require a high-pressure gas production facility when put in industrial practice. In addition, this production method can remarkably reduce the amount of catalyst used therein (to e.g. a substrate/catalyst ratio of 20,000) in comparison to the substrate/catalyst ratio conventional reduction of &#x3b1;-fluoroalcohol. It is possible by these reduction in hydrogen pressure and catalyst amount to largely reduce the production cost of the &#x3b2;-fluoroalcohol. 

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Tokyo, Japan

Takehisa Ishimaru