Monomer, polymer, resist composition, and patterning process

Abstract

A monomer of formula (1a) or (1b) is provided wherein A is a polymerizable group, R.sup.1-R.sup.6 are monovalent hydrocarbon groups, X.sup.1 is a divalent hydrocarbon, group, Z.sup.1 is an aliphatic group, Z.sup.2 forms an alicyclic group, k=0 or 1, m=1 or 2, n=1 to 4. A useful polymer is obtained by polymerizing the monomer. A resist composition comprising the polymer has improved development properties and is processed to form a negative pattern having high contrast, high resolution and etch resistance which is insoluble in alkaline developer. ##STR00001##

Claims

1. A monomer selected from among the following formulae: ##STR00371## ##STR00372##

2. A polymer comprising recurring units derived from the monomer of claim 1.

3. The polymer of claim 2, further comprising one or more recurring units selected from recurring units having the formulae (A) to (D): ##STR00373## wherein R.sup.b is hydrogen, methyl or trifluoromethyl, Z.sup.A is a C.sub.1-C.sub.20 fluoroalcohol-containing group, Z.sup.B is a C.sub.1-C.sub.20 phenolic hydroxyl-containing group, Z.sup.C is a C.sub.1-C.sub.20 carboxyl-containing group, Z.sup.D is a substituent group having a lactone structure, sultone structure, carbonate structure, cyclic ether structure, acid anhydride structure, alcoholic hydroxyl, alkoxycarbonyl, sulfonamide or carbamoyl moiety, X.sup.4 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, naphthylene, OR.sup.c, or C(O)Z.sup.ER.sup.c, Z.sup.E is oxygen or NH, and R.sup.c is a straight, branched or cyclic C.sub.1-C.sub.6 alkylene group, or a straight, branched or cyclic C.sub.2-C.sub.6 alkenylene group, phenylene group or naphthylene group, wherein the R.sup.c group may contain a carbonyl, ester, ether or hydroxyl moiety.

4. The polymer of claim 2, further comprising one or more recurring units selected from recurring units having the formulae (3a) to (3d): ##STR00374## ##STR00375## wherein R.sup.a is hydrogen, methyl or trifluoromethyl, R.sup.1 and R.sup.2 are each independently a straight C.sub.1-C.sub.10 or branched C.sub.3-C.sub.10 or cyclic C.sub.3-C.sub.10 monovalent hydrocarbon group in which any constituent CH.sub.2 moiety may be replaced by O or C(O), a pair of R.sup.1 and R.sup.2 may bond together to form an alicyclic group with the carbon atom to which they are attached, X.sup.1 is a straight, branched or cyclic C.sub.1-C.sub.15 divalent hydrocarbon group in which any constituent CH.sub.2 moiety may be replaced by O or C(O), X.sup.2 and X.sup.3 are each independently a single bond or a straight, branched or cyclic C.sub.1-C.sub.15 divalent hydrocarbon group in which any constituent CH.sub.2 moiety may be replaced by O or C(O), Z.sup.1 is a straight C.sub.1-C.sub.20 or branched C.sub.3-C.sub.10 or cyclic C.sub.3-C.sub.20, (n+1)-valent aliphatic hydrocarbon group in which any constituent CH.sub.2 moiety may be replaced by O or C(O), b is an integer meeting b5+2rc, c is an integer of 1 to 3, k is 0 or 1, n is an integer of 1 to 4, r is an integer of 0 to 2, Z.sup.2 is an atomic group necessary to form a C.sub.3-C.sub.10 alicyclic group with the carbon atom to which it is attached, in which any constituent CH.sub.2 moiety may be replaced by O or C(O), with the proviso that when the oxygen atom attached to Z.sup.1 or Z.sup.2 forms a bond with the carbonyl carbon bonded to a polymer main chain or the linker [OX.sup.1C(O)], a tertiary ester bond is not formed.

5. The polymer of claim 2, further comprising one or more recurring units selected from recurring units having the formulae (f1) to (f3): ##STR00376## wherein R.sup.11 is each independently hydrogen or methyl, R.sup.12 is a single bond, phenylene, OR.sup.21, or C(O)Z.sup.22R.sup.21, Z.sup.22 is oxygen or NH, R.sup.21 is a straight, branched or cyclic C.sub.1-C.sub.6 alkylene group, straight, branched or cyclic C.sub.2-C.sub.6 alkenylene group or phenylene group, and R.sup.21 may contain a carbonyl (CO), ester (COO), ether (O) or hydroxyl moiety, L is a single bond or Z.sup.33C(O)O, Z.sup.33 is a straight, branched or cyclic C.sub.1-C.sub.20 divalent hydrocarbon group which may be substituted with a heteroatom, is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, OR.sup.22, or C(O)Z.sup.44R.sup.22, Z.sup.44 is oxygen or NH, R.sup.22 is a straight, branched or cyclic C.sub.1-C.sub.6 alkylene group, straight, branched or cyclic C.sub.2-C.sub.6 alkenylene group or phenylene group, and R.sup.22 may contain a carbonyl, ester, ether or hydroxyl moiety, R.sup.13 to R.sup.20 are each independently a straight, branched or cyclic C.sub.1-C.sub.20 monovalent hydrocarbon group in which at least one hydrogen atom may be substituted by a heteroatom, and M.sup. is a non-nucleophilic counter ion.

6. A resist composition comprising a base resin, an acid generator, and an organic solvent, the base resin comprising the polymer of claim 2.

7. A pattern forming process comprising the steps of applying the resist composition of claim 6 onto a substrate, baking to form a resist film, exposing the resist film to high-energy radiation to define exposed and unexposed regions, baking, and developing the exposed resist film in a developer to form a pattern.

8. The pattern forming process of claim 7 wherein the developing step uses an alkaline developer in which the unexposed region of resist film is dissolved and the exposed region of resist film is not dissolved, for forming a negative tone pattern.

Description

EXAMPLE

(1) Examples of the Invention are given below by way of illustration and not by way of limitation. The abbreviation pbw is parts by weight, THF stands for tetrahydrofuran, and DMF for dimethylformamide. For all polymers, Mw and Mn are determined versus polystyrene standards by GPC using THF solvent, and dispersity Mw/Mn is computed therefrom.

[1] Synthesis of Monomers

Example 1

Synthesis of Monomer 1

(2) ##STR00326##

Example 1-1

Synthesis of Intermediate 1

(3) In nitrogen atmosphere, 285 g of triethylsilyl chloride was added dropwise to a solution of 290 g of Hydroxy-ester 1 in 157 g of pyridine and 1,125 g of DMF which was cooled in an ice bath. At the end of dropwise addition, the contents were stirred at room temperature for 7 hours. The reaction solution was again cooled in an ice bath, to which 1,200 g of water was added dropwise to quench the reaction. This was followed by ordinary aqueous workup, solvent distillation, and vacuum distillation, obtaining 392 g of Intermediate 1 as colorless clear oil (yield 80%). The product was measured for boiling point and infrared (IR) spectrum and the main isomer analyzed by nuclear magnetic resonance (.sup.1H-NMR) spectroscopy, with the results shown below.

(4) b.p.: 90 C./4 Pa

(5) IR (D-ATR):

(6) =3592, 2912, 2876, 1738, 1458, 1435, 1415, 1356, 1310, 1235, 1196, 1167, 1117, 1095, 1050, 1016, 894, 871, 851, 834, 812, 795, 742, 727, 619, 596 cm.sup.1

(7) .sup.1H-NMR (600 MHz, in DMSO-d.sub.6):

(8) =3.85 (1H, m), 3.57 (3H, s), 2.32 (1H, m), 1.80 (4H, m), 1.51 (4H, m), 0.90 (9H, t), 0.53 (6H, q) ppm

Example 1-2

Synthesis of Intermediate 2

(9) In nitrogen atmosphere, a dilute solution of 342 g of Intermediate 1 (isomer mixture) in 400 mL of THF was added dropwise to a THF solution of methylmagnesium chloride which had been prepared from 73 g of magnesium, chloromethane and 1,200 mL of THF, at 25-45 C. The contents were stirred at 50 C. for 10 hours. Then the reaction solution was ice cooled, to which a mixture of 300 g of ammonium chloride and 1,800 g of 3.0 wt % hydrochloric acid aqueous solution was added dropwise to quench the reaction. This was followed by ordinary aqueous workup, solvent distillation, and vacuum distillation, obtaining 295 g of Intermediate 2 as colorless clear oil (yield 90%). The product was measured for boiling point and IR spectrum and the main isomer analyzed by .sup.1H-NMR spectroscopy, with the results shown below.

(10) b.p.: 90 C./5 Pa

(11) IR (D-ATR):

(12) =3379, 2952, 2938, 2912, 2876, 1460, 1444, 1414, 1378, 1296, 1237, 1196, 1146, 1102, 1051, 1016, 956, 930, 913, 871, 833, 310, 757, 742, 726, 694, 627 cm.sup.1

(13) .sup.1H-NMR (600 MHz in DMSO-d.sub.6):

(14) =3.96 (1H, m), 3.93 (1H, s), 1.63 (2H, m), 1.46 (2H, m), 1.35 (4H, m), 1.14 (1H, m), 0.99 (6H, s), 0.90 (9H, t), 0.52 (6H, q) ppm

Example 1-3

Synthesis of Intermediate 3

(15) In nitrogen atmosphere, a solution of 55 g of Intermediate 2 (isomer mixture) in 100 mL of THF was added dropwise to 9.6 g of sodium hydride in 100 ml of THF at 50 C. The contents were stirred at 80 C. for 6 hours. Then the reaction solution was cooled at 25 C., to which 44 g of 2,2-bistrifluoromethyloxirane was added dropwise. Stirring was continued at 40 C. for 36 hours. The reaction solution was cooled, to which 100 g of saturated ammonium chloride aqueous solution was added to quench the reaction. This was followed by ordinary aqueous workup, solvent distillation, and vacuum; distillation, obtaining 70 g of Intermediate 3 as colorless clear oil (yield 78%). The product was measured for boiling point and IR spectrum and the main isomer analyzed by .sup.1H-NMR spectroscopy, with the results shown below.

(16) b.p.: 105 C./7 Pa

(17) IR (D-ATR):

(18) =3462, 2953, 2915, 2878, 1461, 1445, 1415, 1373, 1324, 1266, 1213, 1166, 1140, 1095, 1052, 1030, 1004, 931, 907, 889, 861, 833, 808, 772, 758, 743, 727, 714, 680, 599, 567 cm.sup.1

(19) .sup.1H-NMR (600 MHz in DMSO-d.sub.6):

(20) =7.72 (1H, brs), 3.96 (1H, m), 3.64 (2H, s), 1.62 (2H, m), 1.43-1.30 (7H, m), 1.04 (6H, s), 0.90 (9H, t), 0.52 (6H, q) ppm

Example 1-4

Synthesis of Intermediate 4

(21) In nitrogen atmosphere, a solution containing 70 g of Intermediate 3 (isomer mixture), 70 mL of acetic acid, 70 mL of THF and 17.5 mL of water was stirred at 60 C. for 12 hours. Then the reaction solution was cooled, to which 100 mL of water was added to quench the reaction. The reaction solution was extracted with 200 mL of toluene. This was followed by ordinary aqueous workup, solvent distillation, and vacuum distillation, obtaining 46 g of Intermediate 4 as colorless clear oil (yield 87%). The product was measured for boiling point and IR spectrum and the main isomer analyzed by .sup.1H-NMR spectroscopy, with the results shown below.

(22) b.p.: 90 C./4 Pa

(23) IR (D-ATR):

(24) =3489, 3307, 3083, 2946, 1481, 1465, 1448, 1413, 1369, 1321, 1289, 1257, 1212, 1162, 1114, 1097, 1074, 1039, 1027, 1018, 990, 980, 954, 941, 907, 880, 825, 787, 762, 721, 710, 683, 669, 610, 589, 574, 566 cm.sup.1

(25) .sup.1H-NMR (600 MHz in DMSO-d.sub.6):

(26) 7.62 (1H, brs), 4.11 (1H, d), 3.80 (1H, m), 3.62 (2H, s), 1.67 (2H, m), 1.45-1.24 (7H, dm), 1.02 (6H, s) ppm

Example 1-5

Synthesis of Monomer 1

(27) In nitrogen atmosphere, 11 g of methacrylic anhydride was added dropwise to a solution containing 18 g of Intermediate 4 (isomer mixture), 13 g of triethylamine, 0.06 g of dimethylaminopyridine, and 45 g of toluene at 40 C. The contents were stirred at 50 C. for 12 hours. Then the reaction solution was ice cooled, to which 15 g of water was added dropwise to quench the reaction. This was followed by ordinary aqueous workup, solvent distillation, and purification by silica gel column chromatography, obtaining 12 g of Monomer 1 as colorless clear oil (5 step yield 28%, isomer ratio 87/13). The product was measured for boiling point and IR spectrum and the main isomer analyzed by .sup.1H-NMR spectroscopy, with the results shown below.

(28) b.p.: 90 C./4 Pa

(29) IR (D-ATR):

(30) =3446, 2947, 2875, 1712, 1637, 1450, 1386, 1369, 1322, 1298, 1260, 1213, 1168, 1093, 1069, 1027, 991, 935, 919, 876, 816, 763, 716, 702, 684, 601, 573, 561 cm.sup.1

(31) .sup.1H-NMR (600 MHz in DMSO-d.sub.6):

(32) =7.76 (1H, brs), 6.01 (1H, s), 5.62 (1H, s), 4.94 (1H, m), 3.65 (2H, s), 1.95-1.75 (5H, m), 1.56-1.46 (4H, m), 1.39-1.31 (3H, m), 1.08 (6H, s) ppm

Example 2

Synthesis of Monomer 2

(33) ##STR00327## ##STR00328##

Example 2-1

Synthesis of Intermediate 5

(34) In nitrogen atmosphere, 83 g of triethylsilyl chloride was added dropwise to a solution containing 83 g of Hydroxy-ketone 1, 41 g of imidazole and 160 g of DMF which was cooled in an ice bath. At the end of dropwise addition, the contents were stirred at room temperature for 6 hours. The reaction solution was again cooled in an ice bath, to which 200 g of water was added dropwise to quench the reaction. This was followed by ordinary aqueous workup and solvent distillation, obtaining 143 g of Intermediate 5 as oil (crude yield 97%). Without further purification, Intermediate 5 was used in the subsequent reaction.

Example 2-2

Synthesis of Intermediate 6

(35) In nitrogen atmosphere, a dilute solution of 341 g of Intermediate 5 in 100 mL of THF was added dropwise to a 3.0 M methylmagnesium chloride THF solution (conventionally prepared) at 25-45 C. The contents were stirred at 50 C. for 5 hours. Then the reaction solution was ice cooled, to which a mixture of 142 g of ammonium chloride and 800 g of 3.0 wt % hydrochloric acid aqueous solution was added dropwise to quench the reaction. This was followed by ordinary aqueous workup, solvent distillation, and vacuum distillation, obtaining 327 g of Intermediate 6 as colorless clear oil (yield 90%).

Example 2-3

Synthesis of Intermediate 7

(36) In nitrogen atmosphere, a solution of 138 g of Intermediate 6 (isomer mixture) in 250 mL of THF was added dropwise to 22 g of sodium hydride in 140 ml of THF at 50 C. The contents were stirred at 80 C. for 6 hours. Then the reaction solution was cooled at 25 C., to which 99 g of 2,2-bistrifluoromethyloxirane was added dropwise. Stirring was continued at 40 C. for 46 hours. The reaction solution was cooled, to which 400 g of saturated ammonium chloride aqueous solution was added to quench the reaction. This was followed, by ordinary aqueous workup, solvent distillation, and vacuum distillation, obtaining 217 g of Intermediate 7 as colorless clear oil (yield 98%).

2-4

Synthesis of Intermediate 8

(37) In nitrogen atmosphere, a solution containing 211 g of Intermediate 7 (isomer mixture), 420 mL of acetic acid, 210 mL of THF and 210 mL of water was stirred at 60 C. for 16 hours. Then the reaction solution was cooled, to which 250 mL of water was added to quench the reaction. The reaction solution was extracted with 1,000 mL of toluene. This was followed by ordinary aqueous workup, solvent distillation, and purification by silica gel column chromatography, obtaining 140 g of Intermediate 8 as colorless clear oil (yield 98%).

Example 2-5

Synthesis of Intermediate 9

(38) In nitrogen atmosphere, 113 g of methacrylic acid chloride was added dropwise to a solution containing 157 g of Intermediate 8 (isomer mixture), 175 g of triethylamine, 5.3 g of 4-dimethylaminopyridine and 450 mL of acetonitrile at 40 C. The contents were stirred at 60 C. for 3 hours. The reaction solution was ice cooled, to which 500 g of water was added dropwise to quench the reaction. This was followed by ordinary aqueous workup and solvent distillation, obtaining 181 g of Intermediate 9 as oil (yield 83%). Without further purification, Intermediate 9 was used in the subsequent reaction.

Example 2-6

Synthesis of Monomer 2

(39) In nitrogen atmosphere, 363 g of 8% sodium hydroxide aqueous solution was added dropwise to a solution of 181 g of Intermediate 9 (isomer mixture) in 900 g of t-butanol at room temperature. The contents were stirred at room temperature for 3 hours. Then the reaction solution was ice cooled, to which 133 g of 20 wt % hydrochloric acid aqueous solution was added dropwise to quench the reaction. The reaction solution was extracted with 1,000 mL of toluene. This was followed by ordinary aqueous workup, solvent distillation, and crystallization, obtaining 147 g of Monomer 2 as white crystal (6 step yield 60%, isomer ratio 66/34).

(40) The product was measured for IR spectrum and the main isomer analyzed by .sup.1H-NMR spectroscopy, with the results shown below.

(41) IR (D-ATR):

(42) =3278, 3012, 2960, 2925, 2306, 2873, 1681, 1628, 1485, 1448, 1408, 1380, 1345, 1329, 1312, 1293, 1275, 1259, 1215, 1189, 1156, 1121, 1103, 1091, 1061, 1041, 1032, 1010, 985, 947, 934, 921, 897, 881, 868, 817, 736, 715, 700, 680, 640, 589 cm.sup.1

(43) .sup.1H-NMR (600 MHz in DMSO-d.sub.6):

(44) =7.85 (1H, s), 5.91 (1H, s), 5.58 (1H, s), 3.70 (2H, s), 2.29 (2H, m), 2.09-1.89 (9H, m), 1.81 (3H, s), 1.38 (2H, m), 1.35 (3H, s) ppm

Example 3

Synthesis of Monomer 2

(45) Monomers 3 to 12, shown below, were similarly synthesized using the corresponding reactants.

(46) ##STR00329## ##STR00330## ##STR00331##

[2] Synthesis of Polymers

(47) Each of polymers (Polymers 1 to 23 and Comparative Polymers 1 to 12) for use in resist compositions was prepared by combining monomers in cyclopentanone solvent, effecting copolymerization reaction, crystallizing from hexane, washing with hexane several times, isolation and drying. The polymer was analyzed for composition by .sup.1H-NMR and .sup.13C-NMR spectroscopy.

Example 4

(48) Polymer 1 Mw=8,600 Mw/Mn1.67

(49) ##STR00332##

Example 5

(50) Polymer 2 Mw=8,400 Mw/Mn=1.65

(51) ##STR00333##

Example 6

(52) Polymer 3 Mw=8,300 Mw/Mn=1.67

(53) ##STR00334##

Example 7

(54) Polymer 4 Mw=8,300 Mw/Mn=1.66

(55) ##STR00335##

Example 8

(56) Polymer 5 Mw=8,500 Mw/Mn=1.66

(57) ##STR00336##

Example 9

(58) Polymer 6 Mw=8,900 Mw/Mn=1.71

(59) ##STR00337##

Example 10

(60) Polymer 7 Mw=8,800 Mw/Mn=1.72

(61) ##STR00338##

Example 11

(62) Polymer 8 Mw=8,500 Mw/Mn=1.68

(63) ##STR00339##

Example 12

(64) Polymer 9 Mw=8,700 Mw/Mn=1.70

(65) ##STR00340##

Example 13

(66) Polymer 10 Mw=8,800 Mw/Mn=1.69

(67) ##STR00341##

Example 14

(68) Polymer 11 Mw=9,000 Mw/Mn=1.76

(69) ##STR00342##

Example 15

(70) Polymer 12 Mw=8,700 Mw/Mn=1.70

(71) ##STR00343##

Example 16

(72) Polymer 13 Mw=8,300 Mw/Mn=1.66

(73) ##STR00344##

Example 17

(74) Polymer 14 Mw=8,500 Mw/Mn=1.65

(75) ##STR00345##

Example 18

(76) Polymer 15 Mw=8,800 Mw/Mn=1.71

(77) ##STR00346##

Example 19

(78) Polymer 16 Mw=8,700 Mw/Mn=1.69

(79) ##STR00347##

Example 20

(80) Polymer 17 Mw=8,600 Mw/Mn=1.70

(81) ##STR00348##

Example 21

(82) Polymer 18 Mw=8,700 Mw/Mn=1.68

(83) ##STR00349##

Example 22

(84) Polymer 19 Mw=9,000 Mw/Mn=1.72

(85) ##STR00350##

Example 23

(86) Polymer 20 Mw=8,500 Mw/Mn=1.67

(87) ##STR00351##

Example 24

(88) Polymer 21 Mw=8,400 Mw/Mn=1.66

(89) ##STR00352##

Example 25

(90) Polymer 22 Mw=8,300 Mw/Mn=1.62

(91) ##STR00353##

Example 26

(92) Polymer 23 Mw=8,700 Mw/Mn=1.64

(93) ##STR00354##

Comparative Example 1

(94) Comparative Polymer 1 Mw=8,400 Mw/Mn=1.65

(95) ##STR00355##

Comparative Example 2

(96) Comparative Polymer 2 Mw=8,500 Mw/Mn=1.63

(97) ##STR00356##

Comparative Example 3

(98) Comparative Polymer 3 Mw=8,700 Mw/Mn=1.65

(99) ##STR00357##

Comparative Example 4

(100) Comparative Polymer 4 Mw=8,600 Mw/Mn=1.62

(101) ##STR00358##

Comparative Example 5

(102) Comparative Polymer 5 Mw=8,400 Mw/Mn=1.66

(103) ##STR00359##

Comparative Example 6

(104) Comparative Polymer 6 Mw=8,600 Mw/Mn=1.63

(105) ##STR00360##

Comparative Example 7

(106) Comparative Polymer 7 Mw=8,600 Mw/Mn=1.63

(107) ##STR00361##

Comparative Example 8

(108) Comparative Polymer 8 Mw=8,500 Mw/Mn=1.61

(109) ##STR00362##

Comparative Example 9

(110) Comparative Polymer 9 Mw=8,400 Mw/Mn=1.65

(111) ##STR00363##

Comparative Example 10

(112) Comparative Polymer 10 Mw=8,400 Mw/Mn=1.65

(113) ##STR00364##

Comparative Example 11

(114) Comparative Polymer 11 Mw=9,800 Mw/Mn=2.53

(115) ##STR00365##

Comparative Example 12

(116) Comparative Polymer 12 Mw=12,000 Mw/Mn=2.01

(117) ##STR00366##

[3] Preparation of Resist Compositions

Examples 27 to 49 & Comparative Examples 13 to 24

(118) Resist compositions R-01 to R-35 were prepared by using inventive Polymers 1 to 23 or Comparative Polymers 1 to 12 as the base resin, dissolving the polymer and other components in a solvent in accordance with the recipe shown in Tables 1 and 2, and filtering through a Teflon filter having a pore size of 0.2 m.

(119) In Tables 1 and 2, acid generator (PAG-1 to 4), water-repellent polymer (SF-1), sensitivity regulator (Q-1 to 4), crosslinker (XL-1), and solvent are as identified below.

(120) Photoacid Generator: PAG-1 to PAG-4

(121) ##STR00367##
Sensitivity Regulator: Q-1 to Q-4

(122) ##STR00368##
Water-Repellent Polymer: SF-1

(123) Mw=8,700

(124) Mw/Mn=1.85

(125) ##STR00369##
Crosslinker: XL-1

(126) ##STR00370##
Solvent

(127) PGEE: propylene glycol monoethyl ether

(128) DAA: diacetone alcohol

(129) GBL: -butyrolactone

(130) TABLE-US-00001 TABLE 1 Water- Sensitivity repellent Resist Resin PAG regulator polymer Crosslinker Solvent Composition (pbw) (pbw) (pbw) (pbw) (pbw) (pbw) Example 27 R-01 Polymer 1 PAG-4 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 28 R-02 Polymer 2 PAG-4 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 29 R-03 Polymer 3 PAG-1 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 30 R-04 Polymer 4 PAG-3 Q-1 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 31 R-05 Polymer 5 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 32 R-06 Polymer 6 PAG-2 Q-3 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 33 R-07 Polymer 7 PAG-4 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 34 R-08 Polymer 8 PAG-4 Q-3 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 35 R-09 Polymer 9 PAG-3 Q-4 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 36 R-10 Polymer 10 PAG-2 Q-3 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 37 R-11 Polymer 11 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 38 R-12 Polymer 12 PAG-1 Q-4 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 39 R-13 Polymer 13 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 40 R-14 Polymer 14 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 41 R-15 Polymer 15 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 42 R-16 Polymer 16 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 43 R-17 Polymer 17 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 44 R-18 Polymer 18 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100)

(131) TABLE-US-00002 TABLE 2 Water- Sensitivity repellent Resist Resin PAG regulator polymer Crosslinker Solvent Composition (pbw) (pbw) (pbw) (pbw) (pbw) (pbw) Example 45 R-19 Polymer 19 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 46 R-20 Polymer 20 PAG-3 Q-4 SF-1 XL-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) (5.0) DAA (400) GBL (100) 47 R-21 Polymer 21 PAG-3 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 48 R-22 Polymer 22 PAG-4 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GBL (100) 49 R-23 Polymer 23 PAG-4 Q-2 SF-1 PGEE (2,000) (100) (5.0) (3.5) (5.0) DAA (400) GB L(100) Comparative 13 R-24 Comparative PAG-1 Q-2 SF-1 PGEE (2,000) Example Polymer 1 (5.0) (3.5) (5.0) DAA (400) (100) GBL (100) 14 R-25 Comparative PAG-2 Q-1 SF-1 XL-1 PGEE (2,000) Polymer 2 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 15 R-26 Comparative PAG-3 Q-3 SF-1 XL-1 PGEE (2,000) Polymer 3 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 16 R-27 Comparative PAG-4 Q-3 SF-1 XL-1 PGEE (2,000) Polymer 4 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 17 R-28 Comparative PAG-3 Q-3 SF-1 XL-1 PGEE (2,000) Polymer 5 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 18 R-29 Comparative PAG-3 Q-3 SF-1 PGEE (2,000) Polymer 6 (5.0) (3.5) (5.0) DAA (400) (100) GBL (100) 19 R-30 Comparative PAG-4 Q-4 SF-1 PGEE (2,000) Polymer 7 (5.0) (3.5) (5.0) DAA (400) (100) GBL (100) 20 R-31 Comparative PAG-3 Q-3 SF-1 XL-1 PGEE (2,000) Polymer 8 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 21 R-32 Comparative PAG-4 Q-4 SF-1 XL-1 PGEE (2,000) Polymer 9 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 22 R-33 Comparative PAG-3 Q-3 SF-1 PGEE (2,000) Polymer 10 (5.0) (3.5) (5.0) DAA (400) (100) GBL (100) 23 R-34 Comparative PAG-4 Q-4 SF-1 XL-1 PGEE (2,000) Polymer 11 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100) 24 R-35 Comparative PAG-4 Q-3 SF-1 XL-1 PGEE (2,000) Polymer 12 (5.0) (3.5) (5.0) (5.0) DAA (400) (100) GBL (100)

[4] Evaluation of Swell Quantity of Resist During Development, by the QCM (Quartz Crystal Microbalance) Technique

Examples 50 to 53 & Comparative Example 25

(132) The above-prepared resist solution (in Tables 1 and 2) was spin coated on a QCM substrate and baked on a hot plate at 100 C. for 60 seconds to form a resist film of 100 nm thick. The resist film was exposed by means of an ArF open-frame exposure system in a dose varying stepwise from 1 mJ/cm.sup.2 to 13 mJ/cm.sup.2 by an increment of 1 mJ/cm.sup.2 and baked (PEB) on a hot plate at the temperature shown in Table 3 for 60 seconds. The QCM substrate was set on a quartz oscillator microbalance instrument RDA-Qz3 for resist development analysis (Litho Tech Japan Co., Ltd.). Development in a 2.38 wt % TMAH aqueous solution was carried out, during which a variation of thickness of resist film was observed as a function of development time. From graphs in which a film thickness variation was plotted relative to development time for each dose, the exposure dose corresponding to the maximum swell quantity and the maximum swell ratio (maximum, swell quantity standardized per initial film thickness) are determined, with the results shown in Table 3. A smaller value of maximum swell ratio indicates that the swell of resist film is suppressed.

(133) TABLE-US-00003 TABLE 3 Maximum PEB temp. Dose swell ratio Resist ( C.) (mJ/cm.sup.2) (%) Example 50 R-01 100 9 109 51 R-02 100 8 112 52 R-03 120 10 140 53 R-04 120 9 132 Comparative 25 R-22 100 7 191 Example

(134) As is evident from Table 3, the resist compositions within the scope of the invention show lower maximum swell ratios than the comparative resist compositions.

[5] ArF Lithography Patterning Test 1

Examples 54 to 67 & Comparative Examples 26 to 37

(135) On a silicon wafer which had been coated with antireflective coating ARC29A (Nissan Chemical Industries, Ltd.) to a thickness of 78 nm, the resist composition (in Tables 1 and 2) was spin coated, then baked on a hot plate at 100 C. for 60 seconds to form a resist film of 100 nm thick. Using an ArF excimer laser scanner NSR-S307E (Nikon Corp., NA 0.85, 0.93/0.74, annular illumination), exposure was performed through a 6% halftone phase shift mask bearing a line-and-space pattern with a space width of 90 nm and a pitch of 180 nm, a space width of 80 nm and a pitch of 160 nm or a space width of 70 nm and a pitch of 140 nm (on-safer size) or a trench pattern with a space width of 90 nm and a pitch of 1,650 nm (on-wafer size) while varying the dose and focus (dose pitch: 1 mJ/cm.sup.2, focus pitch: 0.025 m). After the exposure, the wafer was baked (PEB) at the temperature shown in Table 4 for 60 seconds and puddle developed in 2.38 wt % TMAH aqueous solution for 30 seconds. The wafer was rinsed with deionized water and spin dried, forming a negative pattern. The L/S patterns and trench pattern after development were observed under TD-SEM S-9380 (Hitachi Kitechnologies, Ltd.).

(136) Evaluation of Sensitivity

(137) As an index of sensitivity, the optimum dose (Eop, mJ/cm.sup.2) which provided an L/S pattern with a space width of 90 nm and a pitch of 180 nm was determined. A smaller dose value indicates a higher sensitivity.

(138) Evaluation of Exposure Latitude (EL)

(139) The exposure dose which provided an L/S pattern with a space width of 90 nm10% (i.e., 81 nm to 99 nm) was determined. EL (%) is calculated from the exposure doses according to the following equation:
EL(%)=(|E1E2|/Eop)100
wherein E1 is an exposure dose which provides an L/S pattern with a space width of 81 nm and a pitch of 180 nm, E2 is an exposure dose which provides an L/S pattern with a space width of 99 nm and a pitch of 180 nm, and Eop is the optimum exposure dose which provides an L/S pattern with a space width of 90 nm and a pitch of 180 nm.
Evaluation of Line Width Rough ness (LWR)

(140) The L/S pattern formed by exposure in the optimum dose (determined in the sensitivity evaluation) was observed under TD-SEM. The space width was measured at longitudinally spaced apart 10 points, from which a 3-fold value (3) of standard deviation () was determined and reported as LWR. A smaller value of 3 indicates a pattern having a lower roughness and more uniform space width.

(141) Evaluation of Depth of Focus (DOF)

(142) As an index of DOF, a range of focus which provided a trench pattern with a space width of 90 nm10% (i.e., 81 to 99 nm) was determined. A greater value indicates a wider DOF.

(143) Evaluation of Resolution

(144) Resolution is the minimum size that can be resolved among the L/S patterns with a size from 70 nm to 90 nm (pitch 140 to 180 nm). A smaller value indicates better resolution.

(145) The results are shown in Table 4.

(146) TABLE-US-00004 TABLE 4 PEB Eop Re- temp. (mJ/ EL LWR DOF solution Resist ( C.) cm.sup.2) (%) (nm) (m) (nm) Example 54 R-01 100 38.5 15.3 6.5 0.18 70 55 R-02 100 36.5 10 6.7 0.18 70 56 R-03 120 40.5 14.5 7.3 0.18 70 57 R-04 120 38.4 16.3 7.1 0.18 70 58 R-10 120 50.5 9.8 7.6 0.16 80 59 R-11 100 43.5 12.3 8.3 0.14 70 60 R-12 105 33.5 14.5 6.9 0.16 80 61 R-13 95 40.5 16.3 7.1 0.18 80 62 R-14 100 45.8 15.8 6.6 0.14 70 63 R-19 90 50.6 12.3 6.9 0.14 70 64 R-20 95 31.2 12.5 7.5 0.14 80 65 R-21 100 35.2 16.3 8.1 0.16 70 66 R-22 100 36.1 15.9 7.9 0.16 70 67 R-23 100 25.4 15.2 7.5 0.18 70 Comparative 26 R-24 100 36.3 9.5 10.3 0.1 90 Example 27 R-25 95 25.3 10.5 9.8 0.08 90 28 R-26 110 28.3 8.3 11.5 0.1 90 29 R-27 100 38.5 5.6 15.2 0.12 90 30 R-28 100 35.6 7.5 9.5 0.08 90 31 R-29 110 30.5 6 16.3 0.1 90 32 R-30 100 45.3 10.1 13.2 0.1 90 33 R-31 100 33.3 6.6 10.7 0.08 90 34 R-32 100 35.6 5.6 9.8 0.08 90 35 R-33 100 33.2 4.3 10.2 0.08 90 36 R-34 105 45.6 3.2 16.3 0.07 100 37 R-35 100 38.9 4.1 16.8 0.06 100

(147) As is evident from Table 4, the resist compositions within the scope of the invention have practically acceptable sensitivity. Both EL and DOF have a wide margin. LWR is low as compared with the resists of Comparative Examples. Resolution is also excellent.

[6] ArF Lithography Patterning Test 2

Examples 68 to 73 & Comparative Examples 38 to 40

(148) On a substrate, a spin-on carbon film ODL-180 (Shin-Etsu Chemical Co., Ltd.) having a carbon content of 80 wt % was deposited to a thickness of 180 nm and a silicon-containing spin-on hard mask SHB-A940 having a silicon content of 43 wt % was deposited thereon to a thickness of 35 nm. On this substrate for trilayer process, the resist composition (in Tables 1 and 2) was spin coated, then baked on a hot plate at 100 C. for 60 seconds to form a resist film of 60 nm thick.

(149) Using an ArF excimer laser immersion lithography scanner NSR-S610C (Nikon Corp., NA 1.30, 0.90/0.72, cross-pole opening 35 deg., cross-pole illumination, azimuthally polarized illumination), exposure was performed through a 6% halftone phase shift mask bearing a contact hole (CH) pattern with a hole size of 55 nm and a pitch of 110 nm (on-wafer size) while varying the dose and focus (dose pitch: 1 mJ/cm.sup.2, focus pitch: 0.025 m). After the exposure, the wafer was baked (PEB) at the temperature shown in Table 5 for 60 seconds and puddle developed, in 2.38 wt % TMAH aqueous solution for 30 seconds. The wafer was rinsed with deionized water and spin dried, obtaining a negative pattern. The CH pattern after development was observed under TD-SEM CG4000 (Hitachi Hitechnologies, Ltd.).

(150) Evaluation of Sensitivity

(151) As an index of sensitivity, the optimum dose (Eop, mJ/cm.sup.2) which provided a CH pattern with a hole size of 55 nm and a pitch of 110 nm was determined. A smaller dose value indicates a higher sensitivity.

(152) Evaluation of Exposure Latitude (EL)

(153) The exposure dose which provided a CH pattern with a hole size of 55 nm10% (i.e., 49.5 nm to 60.5 nm) was determined. EL (%) is calculated from the exposure doses according to the following equation:
EL(%)=(|E1E2|/Eop)100
wherein E1 is an exposure dose which provides a CH pattern with a hole size of 49.5 nm and a pitch of 110 nm, E2 is an exposure dose which provides a CH pattern with a hole size of 60.5 nm and a pitch of 110 nm, and Eop is the optimum exposure dose which provides a CH pattern with a hole size of 55 nm and a pitch of 110 nm.
Evaluation of Critical Dimension Uniformity (CDU)

(154) For the CH pattern formed by exposure in the optimum dose (determined in the sensitivity evaluation), the hole size was measured at 10 areas subject to an identical dose of shot (9 contact holes per area), from which a 3-fold value (3) of standard deviation () was determined and reported as CDU. A smaller value of 3 indicates a CH pattern having improved CDU.

(155) The results are shown in Table 5.

(156) TABLE-US-00005 TABLE 5 PEB temp. Eop EL CDU 3 Resist ( C.) (mJ/cm.sup.2) (%) (nm) Example 68 R-01 100 35.9 13.5 7.1 69 R-02 100 33.6 11.1 6.8 70 R-03 120 39.6 13 6.5 71 R-04 120 36.3 13.8 6.7 72 R-22 100 36.8 14 7 73 R-23 120 35.8 13.7 6.9 Comparative 38 R-24 100 34.1 7.2 10.1 Example 39 R-34 105 37.9 6.3 11.8 40 R-35 100 37.8 5.9 12.1

(157) As is evident from Table 5, the resist compositions within the scope of the invention show practically acceptable sensitivity, a wide margin of EL, and excellent CDU.

[7] EB Writing Test

Examples 74 to 79 & Comparative Examples 41 to 44

(158) On a silicon wafer which had been surface treated in HMDS gas phase at 90 C. for 60 seconds, each of the inventive resist compositions or comparative resist compositions in Tables 1 and 2 was spin coated and prebaked on a hot plate at 100 C. for 60 seconds to form a resist film of 60 nm thick. Using an EB lithography system JBX-9000 (JEOL, Ltd.) at an accelerating voltage of 50 kV, a L/S pattern having a space width of 100 nm and a pitch of 200 nm (on-wafer size) was written while varying the dose (dose variation pitch 2 C/cm.sup.2). After the imagewise exposure, the resist film was baked (PEB) at the temperature shown in Table 6 for 60 seconds, puddle developed in 2.38 wt % TMAH aqueous solution for 30 seconds, rinsed with deionized water, and dried, obtaining a negative pattern. The L/S pattern after development was observed under TD-SEM S-9380 (Hitachi Hitechnologies, Ltd.).

(159) Evaluation of Sensitivity

(160) As an index of sensitivity, the optimum dose (Eop, C/cm.sup.2) which provided an L/S pattern with a space width of 100 nm and a pitch of 200 nm was determined. A smaller dose value indicates a higher sensitivity.

(161) Evaluation of Exposure Latitude (EL)

(162) The exposure dose which provided an L/S pattern with a space width of 100 nm10% (i.e., 90 nm to 110 nm) was determined. EL (%) is calculated from the exposure doses according to the following equation:
EL(%)=(|E1E2|/Eop)100
wherein E1 is an exposure dose which provides an L/S pattern with a space width of 90 nm and a pitch of 200 nm, E2 is an exposure dose which provides an L/S pattern with a space width of 110 nm and a pitch of 200 nm, and Eop is the optimum exposure dose which provides an L/S pattern with a space width of 100 nm and a pitch of 200 nm.
Evaluation of Line Width Roughness (LWR)

(163) The L/S pattern formed by exposure in the optimum dose (determined in the sensitivity evaluation) was observed under TD-SEM. The space width was measured at longitudinally spaced apart 10 points, from which a 3-fold value (3) of standard deviation () was determined and reported as LWR. A smaller value of 3 indicates a pattern having a lower roughness and more uniform space width.

(164) The results are shown in Table 6.

(165) TABLE-US-00006 TABLE 6 PEB temp. Eop EL LWR Resist ( C.) (C/cm.sup.2) (%) (nm) Example 74 R-01 100 41.2 13.5 4.6 75 R-02 100 39.6 12.3 4.5 76 R-03 120 45.3 15.6 5.1 77 R-04 120 40 16.3 5.5 78 R-22 105 41.2 15.8 5.5 79 R-23 120 42.1 15.3 5.1 Comparative 41 R-24 100 42.2 8.6 8.9 Example 42 R-25 105 53.5 7.2 9.5 43 R-34 100 55.6 6.9 10.8 44 R-35 105 56.8 6.3 11.4

(166) As is evident from Table 6, the resist compositions within the scope of the invention show practically acceptable sensitivity, a wide margin of EL, and low LWR.

(167) It is noted that the invention is not limited to the aforementioned embodiments. While the embodiments are merely exemplary, any embodiments having substantially the same construction as the technical concept set forth in the following claims and exerting equivalent functions and results are believed to be within the spirit, and scope of the invention.

(168) Japanese Patent Application No. 2015-220175 is incorporated herein by reference.

(169) Although, some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.