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US 2002/0197559 A1 Nishi Et Al US 2002O197559A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0197559 A1 Nishi et al. (43) Pub. Date: Dec. 26, 2002 (54) POLYMERS, RESIST COMPOSITIONS AND (57) ABSTRACT PATTERNING PROCESS, NOVEL TETRAHYDROFURAN COMPOUNDS AND THER PREPARATION A polymer comprising recurring units of formula (1-1) or (1-2) wherein R', R, R and Rare H or alkyl, or R and R, (75) Inventors: Tsunehiro Nishi, Nakakubiki-gun (JP); and RandR' taken together may form a ring with each pair Takeshi Kinsho, Nakakubiki-gun (JP); being alkylene, and k is 0 or 1 and having a MW of Seiichiro Tachibana, Nakakubiki-gun 1,000-500,000 is novel. A resist composition comprising the (JP); Takeru Watanabe, polymer as a base resin is Sensitive to high-energy radiation, Nakakubiki-gun (JP); Koji Hasegawa, has excellent Sensitivity, resolution, etching resistance, and Nakakubiki-gun (JP); Tomohiro minimized Swell and lends itself to micropatterning with Kobayashi, Nakakubiki-gun (JP) electron beams or deep-UV. Correspondence Address: MILLEN, WHITE, ZELANO & BRANIGAN, (1-1) P.C. 2200 CLARENDON BILVD. SUTE 1400 (...) ARLINGTON, VA 22201 (US) (73) Assignee: Shin-Etsu Chemical Co., Ltd., Tokyo (c), (JP) R R3 (21) Appl. No.: 10/126,877 R2 O R4 (22) Filed: Apr. 22, 2002 (30) Foreign Application Priority Data ( ) (1-2) O Apr. 23, 2001 (JP)...................................... 2001-1241.26 Apr. 23, 2001 (JP)...................................... 2001-1241.37 Publication Classification k (51) Int. Cl." .......................... G03F 7/038; CO8G 65/34; R R3 GO3F 7/38; G03F 7/40 (52) U.S. Cl. ...................... 430/270.1; 528/425; 528/271; R2 O R4 525/88; 525/165; 430/296; 430/330; 430/311 US 2002/0197559 A1 Dec. 26, 2002 POLYMERS, RESIST COMPOSITIONS AND account of Swelling are rejected. While a finer pattern rule is PATTERNING PROCESS, NOVEL being demanded, there is a need to have a resist material TETRAHYDROFURAN COMPOUNDS AND THEIR which is not only Satisfactory in Sensitivity, resolution, and PREPARATION etching resistance, but fully restrained from Swelling. 0001) This invention relates to (i) a polymer comprising Specific recurring units, (ii) a resist composition comprising SUMMARY OF THE INVENTION the polymer as a base resin, (iii) a patterning process using the resist composition, (iv) a novel tetrahydrofuran com 0006 Therefore, an object of the present invention is to pound useful as a monomer to form the polymer, and (v) a provide (i) a polymer having improved reactivity, robustness method for preparing the tetrahydrofuran compound. and Substrate adhesion as well as minimized Swell during development, (ii) a resist composition comprising the poly BACKGROUND OF THE INVENTION mer as a base resin, which has a higher resolution and etching resistance than conventional resist compositions, 0002 While a number of recent efforts are being made to (iii) a patterning process using the resist composition, (iv) a achieve a finer pattern rule in the drive for higher integration novel tetrahydrofuran compound useful as a monomer to and operating Speeds in LSI devices, deep-ultraViolet lithog form the polymer, and (v) a method for preparing the raphy is thought to hold particular promise as the next tetrahydrofuran compound. generation in microfabrication technology. In particular, photolithography using a Krf or Arf excimer laser as the 0007. It has been found that novel polymers comprising light Source is Strongly desired to reach the practical level as recurring units of the following general formula (1-1) or the micropatterning technique capable of achieving a feature (1-2) and having a weight average molecular weight of size of 0.3 um or less. 1,000 to 500,000, which are produced by the method to be 0.003 For resist materials for use with a Krf excimer described later, have improved reactivity, robustneSS or lasers, polyhydroxystyrene having a practical level of trans rigidity and Substrate adhesion as well as an appropriately mittance and etching resistance is, in fact, a Standard base high Solubility and minimized Swell in a developer, that a resin. For resist materials for use with Arf excimer lasers, resist composition comprising the polymer as the base resin polyacrylic or polymethacrylic acid derivatives and poly has a high resolution and etching resistance, and that this mers containing aliphatic cyclic compounds in the backbone resist composition lends itself to precise micropatterning. are under investigation. All these polymers have advantages 0008. In a first aspect, the invention provides a polymer and disadvantages, and none of them have been established comprising recurring units of the following general formula as the Standard base resin. (1-1) or (1-2) and having a weight average molecular weight 0004 More particularly, resist compositions using of 1,000 to 500,000. derivatives of polyacrylic or polymethacrylic acid have the advantages of high reactivity of acid-decomposable groups and good Substrate adhesion and give relatively Satisfactory ( ) (1-1) results with respect to Sensitivity and resolution, but have extremely low etching resistance and are impractical because the resin backbone is weak. On the other hand, resist compositions using polymers containing alicyclic com pounds in their backbone have a practically acceptable level of etching resistance because the resin backbone is robust, (C) k but are very low in Sensitivity and resolution because the R R3 reactivity of acid-decomposable protective groups is extremely low as compared with those on the (meth)acrylic R2 O R4 polymers. Since the backbone of the resin is too robust, Substrate adhesion is poor. These compositions are thus impractical as well. ( ) (1-2) O 0005 Both the (meth)acrylic and alicyclic backbone sys tems commonly have the problem of pattern disruption due to Swelling of resist film. Resist compositions based on these Systems have been designed So as to improve their resolution performance by increasing the difference in dissolution rate k before and after exposure, and as a consequence, they R R3 eventually become highly hydrophobic. Highly hydrophobic resist compositions, when applied as a film and processed R2 O R4 with a developer, can maintain the film tenaciously in unexposed regions and allow the film to be instantaneously dissolved in over-exposed regions, while relatively-broad 0009 Herein each of R', R, R and R' is hydrogen or a exposed regions therebetween allow penetration of the Straight, branched or cyclic alkyl group of 1 to 15 carbon developer, but are kept undissolved, that is, Swollen. At the atoms, or a pair of R' and R and a pair of R and R' taken very Small pattern size for which an Arf excimer laser is together may form a ring wherein each said pair is a Straight, actually used, those resist compositions which allow adja branched or cyclic alkylene group of 2 to 15 carbon atoms cent pattern Strips to be joined together and disrupted on and k is equal to 0 or 1. US 2002/0197559 A1 Dec. 26, 2002 0010. In one preferred embodiment, the polymer in combination with recurring units of the following general includes, in addition to the recurring units of formula (1-1), formula (2-1), and recurring units of the following general recurring units of the following general formula (2-1). formula (3). (2-1) (2-1) (3) 0011) Herein R is hydrogen, methyl or CHCOR"; R is hydrogen, methyl or COR"; R' which may be identical or O- Y A O different in R and R is a straight, branched or cyclic alkyl (4) group of 1 to carbon atoms; R is an acid labile group; R is R6 R5 Selected from the class consisting of a halogen atom, a hydroxyl group, a Straight, branched or cyclic alkoxy, acy ( ) loxy or alkylsulfonyloxy group of 1 to 15 carbon atoms, and H O a Straight, branched or cyclic alkoxycarbonyloxy or alkoxy alkoxy group of 2 to 15 carbon atoms, in which Some or all of the hydrogen atoms on constituent carbon atoms may be Substituted with halogen atoms, Z is a single bond or a 0.015. Herein k", p, R to R and Y are as defined above, Straight, branched or cyclic (p+2)-valent hydrocarbon group R is hydrogen, methyl or CH-Co.R, R is hydrogen, of 1 to 5 carbon atoms, in which at least one methylene may methyl or COR", R' which may be identical or different in be Substituted with oxygen to form a chain-like or cyclic R and R is a straight, branched or cyclic alkyl group of 1 ether or two hydrogen atoms on a common carbon may be to 15 carbon atoms, and R is an acid labile group. Substituted with oxygen to form a ketone, k" is 0 or 1; and p is 0, 1 or 2. 0016. In a still further preferred embodiment, the poly 0012. In another preferred embodiment, the polymer mer includes, in addition to the recurring units of formula includes, in addition to the recurring units of formula (1-1), (1-2), recurring units of the following general formula (2-2). recurring units of the following general formulae (2-1) and (2-2) (2-1) (3) 0.017. Herein k", p and R to R are as defined above. 0018. In a second aspect, the invention provides a resist composition comprising the polymer defined above. 0019. In a third aspect, the invention provides a process 0013 Hereink', p and R to Rare as defined above, Y is for forming a resist pattern comprising the Steps of applying -O- or -(NR') , and R' is hydrogen or a straight, the resist composition onto a Substrate to form a coating, branched or cyclic alkyl group of 1 to 15 carbon atoms. heat treating the coating and then exposing it to high-energy 0.014.
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