Preparation and Characterization of p-Styrenesulfonates ofIsopropylidene Dicyclohexanol as Acid Amplifiers to Enhance the Photosensitivity of Positive-Working Photoresists p-
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(5) ) †. Preparation and Characterization of p-Styrenesulfonates of Isopropylidene Dicyclohexanol as Acid Amplifiers to Enhance the Photosensitivity of Positive-Working Photoresists Eunju Lee, Kyongil Hong, Kwontaek Lim, Yongseok Jeong, Sungsu Hong†, and Yeontae Jeong * Division of Image and Information Engineering, Pukyong National University, Pusan 608-739, Korea † School of Chemical Engineering, Pukyong National University, Pusan 608-739, Korea (Received July 10, 2002). . !" # $ %&'()$* +,-" . / 01 # 2*34 5 67 89. : ;<#=" >?@ ABC DEF GH p-I JKL MN/ . OPQR S PT7 U*QV9. >WX . OPX 4-hydroxy-4'-pstyrenesulfonyloxy isopropylidene dicyclohexane(1), 4,4'-di-p-styrenesulfonyloxy isopropylidene dicyclohexane(2). SBR 4-p-styrene-sulfonyloxy-4'-tosyloxy isopropylidene dicyclohexane(3)" Y# QZ [)X \] ^ P7 -_`a9. bX >WX . / cdX e# f cdX poly(tert-butyl methacrylate) film# gQZ 2h#= 12h > +,- i# jd]4 kdl 8m7 noQV9. : . , , 01 ABSTRACT. The photosensitivity enhancement of photoresist achieved by the addition of acid amplifiers stems from the autocatalytic decomposition of the acid amplifiers triggered by acidic species generated from a photoacid generator. In this research we synthesized and evaluated 4-hydroxy-4'-p-styrenesulfonyloxy isopropylidene dicyclohexane(1), 4,4'-di-p-styrenesulfonyloxy isopropylidene dicyclohexane(2) and 4-p-styrenesulfonyloxy-4'-tosyloxy isopropylidene dicyclohexane(3) as novel acid amplifiers. These acid amplifiers(1-3) showed reasonable thermal stability for resist processing temperature. As estimated by the sensitivity curve, 1-3 were 2X-12X sensitive than poly(tert-butyl methacrylate) film in the presence of a photoacid generator and, therefore, provides practical applicability for photoimaging. Keywords: Acid Amplifier, Photoacid Generator, Chemically Amplified Photoresist. 437.
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(8) . 438. . . (photoacid generator: PAG)p qk P(acid-labile) R)% <P!" 01 " PAG P!" r # $ s t9. u7 Ev" PAG/ c dQR, PAG 3w7 xZ / Evy" E * 8af, 5 wt% > 2*Ez e PAGc> {O | ) } ~ 4 X> 8a 9. > ~ 7 $sQ $ .1 * !a9. .1 " (photosensitivity)p 1 (pattern shape) PT7 Ev QZ 0 1 (chemically amplified photoresist: CAP)# . (Acid Amplifier, AA)/ 2*QZ f9. . " > '( l7 Q Z g 1](non-linear)4 7 PEz 8" 7 Q" 01 # . / 2*Q postexposurebake(PEB) &^# AA *]o > P!, .1 * t9. .1 PAG Pt > AA/ )$Ev" '( l7 QZ AA > (secondary acid)7 PEv" dark reaction> PEB&^# +, - , 01 # 8,= # QZ PAG P!" r 9 r > .1 #= P! 01 #= 9 .1 #= (sensitivity)* t9. >WX AA* , l i E#" E *$" \# X ^ P> 8, Q )$E# " u7 9w PEz 8, X9. >WX . EF GDH >?@ AB C DEF GH p-¡¢£KL MN¤# QZ ¥t ¦* 89. : ;<#=" p-¡¢£ KL 9 * F§4 !" p-¨JK L7 '( )$E# Pl 87 ©f ª« ¬ R)% # Ez 8" IJ ®d/ R 8" ¯ ° . > ?@ ABC DEF GH p-IJKL M N/ OPQR% QV4 -ª*= . 5 PT7 U*QR% EQV9.. OP#cdtE± 4,4'-isopropylidene dicyclohexanol, p-styrenesulfonyl chloride" Aldrichc#= <$ ²> cdQVR, 4-hydroxy-4'-tosyloxy isopropylidene dicyclohexane ~³# ´¬ OPQV4, µ ¶ d( cdX ·B¸ Junsei chemicalc#= <$ S cdQV9. DTSOTf(diphenyl-4-thiophenoxyphenyl sulfonium triflate)" (¹)º»M4 ¼ ª > ²> cdQV9. H-NMR spectrum JEOL JNM-ECP 400 MHz/ cdQZ ½ QVR, d(" CDCl / cdQV9. ¾?)» Carlo Erbac ¿À CHNS/O 1108 ¾?)»/ cdQZ helium ÁQ#= )»QV9. Â" Fisherc model IA9100 ý / >dQZ ½ QV4 S Ä . ²> ÅQV9. FT-IR spectrum BOMEM MB100 )Æ ½ QVR, DSC/TGA ½ Perkin Elmer 77 cdQZ ÇYÈ 10 C/min4 N Á Q#= ½ É9. Ê Ë " (¹) EÌHÌCc SC1007 cdQZ ÍÎ ËÏ7 QVR, 200 W RÐÑ Ò@ Karl suss MJB 3 7 ¹a4, Í Î ÓÔ" Perkin Elmerc Lamda 40 UV/Vis spectrophotometer ÕÖ×7 >dQZ ½ QV9.
(9) . 1-3. 4-5. 6-9. 8-11. 12-13. 12. 1. 3. o. 2. 4-Hydroxy-4'-p-styrenesulfonyloxy isopropylidene. dicyclohexane(1). 250 ml Ø< ÙÚ ¦Û ܬÝ# ·B¸ 81 mlp 4,4'-isopropylidene dicyclohexanol(IPDH) (0.05 mol, 12.01 g)7 ÞR q Ev= Âo ß à Yi/ 0 C áâEã9. 0 C >Q áâ> ! Ü ¬Ý# p-styrenesulfonyl chloride(p-SSC) (0.05 mol, 10.13 g)/ 2*QR 0 C#= 24EÕ &^ qQ= qkEã9. qk> ä- Pt µ7 A QZ å QR {æ 70 C#= Ð çèQZ ·B¸7 åX9. 100 ml ém7 ÞR 80 ml CH Cl 2ê ëX ß, 10% µ dì 100 ml 3ê í,= î ª8" ·B¸7 åX9. Á 100 ml ZWê í , 7 åEã9. ï* äð Mñ7 ò MgSO iEã 9m MgSO / åQR, Ð çèQZ d(/ óo ß ethyl acetate : hexane=5:1(v/v) ôO d (/ >d$ jBõö ÷ Ý øSù· )BQV 9. úû#= 24EÕ iQZ ü ýþ ) o. o. o. o. 2. 2. 4. 4. Journal of the Korean Chemical Society.
(10) !"# p-$%&'( )$*+# ,- . /-01. 1ÿ P7 6a9. yield: 36%; mp: 152 C; IR o. 439. mp: 135 oC; IR(KBr, cm−1): 2941(-CH3), 1596(CH2=CH-),. (KBr, cm ): 3436(-OH), 2940(-CH3), 1597(CH3=CH-),. 1171(-SO2); 1H-NMR(CDCl3, δ): 0.62-2.16(m, 24H),. 1175(-SO2); 1H-NMR(CDCl3, δ): 0.64-1.98(m, 24H),. 2.43(s, 3H), 4.31-4.33(m, 2H), 5.44-5.46(d, 1H), 5.87-. 3.46-3.48(m, 1H), 4.01(s, 1H), 4.33-4.35(m, 1H), 5.42-. 5.91(d, 1H), 6.71-6.75(m, 1H), 7.25-7.32(d, 2H), 7.52-. 5.44(d, 1H), 5.86-5.90(d, 1H), 6.69-6.74(m, 1H), 7.52(d,. 7.54(d, 2H), 7.77(d, 2H), 7.83(d, 2H); Found: C, 64.50;. 2H), 7.85(d, 2H); Found: C, 68.11; H, 8.98; S, 7.63.. H, 7.67; S, 11.08. Calc. for C30H40S2O6: C, 64.26; H,. Calc. for C23H34SO4: C, 67.95; H, 8.43; S, 7.89.. 7.19; S, 11.43.. −1. 4,4'-Di-p-styrenesulfonyloxy isopropylidene dicyclo-. Ø< ÙÚ ¦Û ܬÝ# ·B¸ 81 mlp IPDH(0.05 mol, 12.01 g)7 ÞR q Ev = Âo ß àYi/ 0 C áâEã9. 0 C >Q áâ> ! ܬÝ# p-SSC(0.10 mol, 20.26 g)/ 2*QR 0 C#= 48EÕ &^ q Q= qkEã 9. qk> ä- p &+X ×4 )BQZ ýþ ) 1ÿ P7 6a9. yield: 42%; mp:. . hexane(2). 250 ml. o. o. o. 133 oC; IR(KBr, cm−1): 2942(-CH3), 1594(CH2=CH-),. 1163(-SO2); 1H-NMR(CDCl3, δ): 0.62-2.03(m, 24H), 4.324.34(m, 2H), 5.43-5.45(d, 2H), 5.86-5.91(d, 2H), 6.706.74(m, 2H), 7.52(d, 4H), 7.83(d, 4H); Found: C, 65.20; H, 7.51; S, 10.85. Calc. for C31H40S2O6: C, 65.00; H, 7.04; S, 11.19. 4-p-Styrenesulfonyloxy-4'-tosyloxy isopropylidene dicyclohexane(3). 250 ml. Ø< ÙÚ ¦Û ܬÝ#. ·B¸ 81 mlp 4-hydroxy-4'-tosyloxy isopropylidene dicyclohexane (0.05 mol, 19.73 g)7 ÞR q Ev = Âo ß àYi/ 0 C áâEã9. 0 C >Q áâ> ! ܬÝ# p-SSC(0.05 mol, 10.13 g)/ 2*QR 0 C#= 24EÕ &^ q Q= qkEã 9. qk> ä- p &+X ×4 )BQZ X ýþ ) 1ÿ P7 6a9. yield: 48%;. / ># ËÏl ÍÎ7 1PQ $ +X dì ÿ cdt9. ´¬= / 6 $ # 2*!," . d(# d$P7 * > Õ Q t9. . OPX 1, 2 SB R 3 ââ ¤7 Md(/ >dQZ 3 wt% d ì7 f¤, d$P7 j QV4
(11) æ Â" e , )]4 Â" e , æ  " e/ ¥QZ S s/ Table 1# -_`a9. 1 G 7 X ¿ Md(# ª d$P> e Q f 2, 3 G, H, #H d(#  " d$P7 -_9. 1 d(. 12. o. o. o. Table 1. Solubility properties of prepared acid amplifiers in a various kind of solvents AA Solvent Hexane Ethyl acetate Chloroform Benzene Toluene Ethyl ether Methylene chloride THF Methanol Ethanol Acetone PGME PGMEA EL a. 2002, Vol. 46, No. 5. . . 2. . 3. . . . . . . propylene glycol monomethyl ether propylene glycol monomethyl ether acetate c ethyl lactate b. Scheme 1. Structures of acid amplifiers.. 1. .
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(14) . 440. Fig. 2. FT-IR spectra of of PtBMA film containing 5 wt% of 1 in the presence of 5 wt% DTSOTf stored for (1) 0, (2) 5 and (3) 20 min at 140 oC. Fig. 1. TGA thermograms of acid amplifiers.. ¹ cdQ" PGME, PGMEA SBR EL# d$P7 -_`R 8f 2, 3 d$P7 -_ 7 nol 8a9. . 1, 2p 37 E¹c\w)» )»X  " ââ 152 C, 132 C SBR 134 CV4 \ w)» s" Fig. 1# -_`a9. 1, 2p 3 ¿Ó  E®Q= 1)$* +,-R Y* xª # ´ ¬ )$* +,-" S )$Y/ 1 175 C#= 1)$* +,-R 2, 3 152 C#= 1 )$* +,- 1 \] ^ P> ±Õ e 37 n ol 8a9. . 1, 2p 3 ¿Ó" )$Y * 150 C/ ~# ¥ @ ï#= " ªò ~ * ²7 f \]o ^ P7 * 7 nol 8a4- >p O <ip \] ^ P ÷Æ# ;<* !!, X9 R âX9. PtBMA Film ÍÎ \ ^ P (e "X f ± * PEB #= \]4 #^ Q 9 PEB &^ p g ¿Ó \# X ) $* +,- ? $ % 1Pt &¬* 'Qt9. ´¬=, . / 3Q" ÍÎ ÿ \] ^ P7 ½. Q QZ jB& ># ËÏ7 QZ \] P 7 () *9. ÁX THF d(# PtBMA(Mw=20500, Mw/Mn=1.78)/ ÂZ 10 wt% dì7 f¤R Z# o DTSOTf(diphenyl-4-thiophenoxyphenyl sulfonium triflate)/ 5 wt%p OPX . / ââ o. o. o. o. o. o. r 5 wt%/ 2*E+
(15) æ Âo 9m Ê Ë (2500 rpm#= 7,, 1500 rpm#= 7,) jB & ># ÍÎ(0.35 µm)4 ËÏX9. jB& > # ËÏX ÍÎ \] ^ P FT-IR spectrophotometer/ >d$ 120 C, 130 C, 140 C ââ Y #= EÕ# ´- P ·Ý ./ ½ QZ s. QV9. . * \# QZ )$Q 1174 cm sulfonic acid sulfonyl group ¯ ° ·Ý* P! = 1139 cm . sulfonate ester# 8" sulfonyl group ν symmetric /0* ?Q t9 (Fig. 2). bX \)$# $ Pt > R)% protecting groupo tert-butyl group7 )$Q" g º qk7 34 5 2970 cm #= -_-" tert-butyl group P ·Ý* ó,¤ t9. Qf g º qk# X ·Ý ?" 2]o §4 , Pt > ¹ 1 úµ# $ ,2 3j> 4 ! . sulfonyl group# oX ·Ý(b)* ó ,0" $ 7 >dQZ jB& > %N P / 0o 611 cm ·Ý(a)/ 4 QZ . \] ^ P7 s QV9. 1 2/ 5 wt% 3X PtBMA film 120 C#=" (e ^ QR 130 C# =" 15) " l fX )$* ²> ^ QV 9. SW- 3 120 C#= 10) >%#" \)$* +,- 1, 2# g$=" \] ^ P> 5, 7 Fig. 3, Fig. 4 Fig. 5 6 8a9. >WX s . 1, 2p 37 3Q" PtBMA film #= +q]4 cdQ" 120 C >Q soft bake b" PEB Y#=" \] ^ P# ªò ~ * ²m7 nol 8a9. PtBMA. o. o. o. −1. −1. s=0. −1. −1. o. o. o. o. Journal of the Korean Chemical Society.
(16) !"# p-$%&'( )$*+# ,- . /-01. 441. Fig. 3. Time course of the consumption of the sulfonyl group of PtBMA film containing 5 wt% of 1 in the presence of 5 wt% DTSOTf at various temperatures.. Fig. 4. Time course of the consumption of the sulfonyl group of PtBMA film containing 5 wt% of 2 in the presence of 5 wt% DTSOTf at various temperatures.. Fig. 5. Time course of the consumption of the sulfonyl group of PtBMA film containing 5 wt% of 3 in the presence of 5 wt% DTSOTf at various temperatures. 2002, Vol. 46, No. 5.
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(19) . I7 #= " $ # QZ /
(20) æ åQ" A"X 8? w w4 t9. PtBMA A9 / s. X × 9m 9. ÁX THF d(# PtBMA / ÂZ 10 wt% dì7 f¤R Z# o DTSOTf/ 5 wt%p OPX . / ââ PtBMA r 5 wt%/ 2*E+
(21) æ Âo 9m Ê Ë (2500 rpm#= 7,, 1500 rpm#= 7,) jB& > # 0.35 µm ÍÎ4 ËÏX % 70 C #= 20) &^ soft bake/ QV9. 200 W RÐÑ Ò@ Karr suss MJB 3 / >dQZ 7 ¹R, 120 C #= 2) &^ PEB QV9. 2.38 wt% tetramethylamonium hydroxide(TMAH) dì4 30, &^ $ QR Á # 30, &^ ïX % 24EÕ &^ 40 C úû#= iQV9. $ %# :;Q" ÍÎ ÓÔ / Perkin Elmerc Lamda 40 UV/Vis spectrophotometer ÕÖ×7 >dQZ ½ QV9. . / 3Q " PtBMA A9 / . / cdQ PtBMA A9 # gQZ Fig. 6# -_`a9. . 17 5 wt% cdX PtBMA A9 " . / cdQ A9# g$ 12h > +,<4, . 2, 37 5 wt% cdX e#" ââ 2h > +,î7 = 8a9. ´¬= . / 2*Ev" e# * !" / nol 8aR hydroxy group7 X ># * 1> hydroxy group> ²" 2, 3# g$ ]?7 6 8a9. > @ > . sulfonate group7 o. '( )$E+ *]o > P! +,-" §4 R!, 89. bX, >?@ ABC DEF GDH p-¡¢£KL MN/ . cdX e" 2h#= 4h > 8a f, : ;<#= OPX . ¤ | A/ æ%B"o gC D1Q 5 '( )$E# P!" * !, +," §4 QR 89. ´¬=, nX / EFQ QZ . D1 # QZ G4 ;<* "<t9. 8. 12. . o. o. I7 7 X . >?@ ABC DEF GH p-IJKL MN 4-hydroxy-4'-p-styrenesulfonyloxy isopropylidene dicyclohexane(1), 4,4'-di-p-styrenesulfonyloxy isopropylidene. SBR 4-p-styrenesulfonyloxy-4'-tosyloxy isopropylidene dicyclohexane(3)/ OPQR H-NMR, FT-IR ¶ ¾?)»4 S <i/ noQV9. 1 G 7 X ¿ Md(# ª d$P> e Q R d( ¹ cdQ" PGME, PGMEA SBR EL# d$P7 -_`aR 2, 3 ±Õ d$P> 5,H9. >WX . ¤ %N )$Y* 150 C/ ~# ¥ #=" ªò ~ * ²7 f \]o ^. P7 * 7 DSC/TGA thermograms4 nol 8 aR jB& ># ËÏX ÍÎ \] ^ P FTIR spectrophotometer/ >d$ 120 C, 130 C, 140 C â dicyclohexane(2). 1. o. o. o. o. Fig. 6. Photosensitivity curves of PtBMA film doped with 5 wt% of acid amplifiers in the presence of 5 wt% DTSOTf as a photoacid generator (film thickness: 0.35 µm). Journal of the Korean Chemical Society.
(22) !"# p-$%&'( )$*+# ,- . /-01. â Y#= EÕ# ´- P ·Ý ./ ½ Q Z s QV9. 1 2/ 5 wt% 3X PtBMA film 120 C#=" (e ^ QR 130 C#=" 15) " l fX )$* ²> ^ QV9. SW- 3 120 C#= 10) >%#" \)$* +,- 1, 2 # g$=" \] ^ P> 5, 7 6 8a9. ø Î4 / () , . 17 5 wt% cd X PtBMA A9 " . / cdQ A9# g$ 12h > +,<4, . 2, 37 5 wt% cdX e#" ââ 2h > +,î7 = 8a9. ´¬= . / 2*Ev" e# * !" / n ol 8aR 1> 2, 3# g$ ]?7 6 8a9. o. o. o. 1. Kaur, S.; Crivello, J. V.; Pascuzzi, N. J.polym. Sci. 1998, 37, 199. 2. Bukofsky, S. J.; Feke, G. D.; Wu, Q.; Grober, R. D.; Dentinger, P. M.; Taylor, J. W. Appl. Phys. Lett. 1998,. 2002, Vol. 46, No. 5. 443. 73, 408. 3. Park, S. W.; Arimitsu, K.; Ichimura, K.; Ofugi, J. Y. Photopolym. Sci. Tecnol. 1999, 12, 293. 4. Park, S. W.; Arimitsu, K.; Lee, S. G.; Ichimura, K. Chem Lett. 2000, 1036. 5. Huang, W. S.; Kwong, R.; Moreau, W. Proc. SPIE. 2000, 3999, 591. 6. Willson, C.; R, G.; Dammel, A.; Reiser, A. Proc. SPIE. 1997, 3049, 28. 7. Ito, H.; Arimitsu, K.; Ichimura. K. Macromol. Chem. Phys. 2000, 201, 132. 8. Ohfuji, T.; Takahashi, M.; Kuhara, Ogawa, K.; Ohtsuka, H.; Sasago, M.; Ichimura. K. Proc. SPIE. 1999, 3049, 76. 9. Choi, S. J.; Kim, H. W.; Woo, S. G.; Moon, J. T. Proc. SPIE. 2000, 3999, 54. 10. Park, S. W.; Arimitsu, K.; Ichimura, K. Macromol. Rapid Commun. 2000, 1050. 11. Arimitsu, K.; Ichimura, K. Macromol. Chem. Phys. 2001, 453. 12. Jeong, Y. T.; Lee, E. J.; Park, J. Y. J. Kor. Soc. Imaging Sci. Technol. 2001, 7, 110. 13. Jeong, Y. T.; Lee, E. J.; Kuen, K. A. J. Kor. Printing. Soc. 2002, 20, 91..
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