Resist overlayer film forming composition for lithography and method for producing semiconductor device using the same

Abstract

There is provided a resist overlayer film forming composition for use in a lithography process in semiconductor device production, which does not intermix with a resist, blocks undesirable exposure light particularly in EUV exposure, for example, UV and DUV and selectively transmits EUV alone, and which can be developed with a developer after exposure. A resist overlayer film forming composition comprising: a polymer including an organic group including a linear or branched saturated alkyl group having a carbon atom number of 1 to 10, in which some or all of hydrogen atoms thereof are substituted with fluorine atoms, and an optionally substituted C.sub.8-16 ether compound as a solvent.

Claims

1. A resist overlayer film forming composition comprising: a polymer including an organic group including a linear or branched saturated alkyl group having a carbon atom number of 1 to 10, in which some or all of hydrogen atoms thereof are substituted with fluorine atoms, and an optionally substituted C.sub.8-16 ether compound as a solvent, wherein the polymer includes a unit structure of any one of (Formula 1-1-1) to (Formula 1-4-1) below: ##STR00061## in (Formula 1-1-1) to (Formula 1-4-1), Ar.sup.1 is an organic group including a C.sub.6-18 aromatic ring; Ar.sup.2 is a methylene group, a tertiary carbon atom, or an organic group including a C.sub.6-18 aromatic ring optionally bonded with Ar.sup.1 through a methylene group or a tertiary carbon atom; the organic group including the aromatic ring included in Ar.sup.1 or Ar.sup.2 includes an organic group including a linear or branched saturated alkyl group having a carbon atom number of 1 to 10, in which some or all of hydrogen atoms thereof are substituted with fluorine atoms, where the number of the organic group including a linear or branched saturated alkyl group having a carbon atom number of 1 to 10 included in Ar1 or Ar.sup.2 is an integer of 1 to 10; and a hydrogen atom of the aromatic ring in Ar.sup.1 or Ar.sup.2 is optionally substituted with a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, a C.sub.1-9 alkoxy group, an amino group having a hydrogen atom optionally substituted with a C.sub.1-3 linear alkyl group, a linear, branched, or cyclic saturated alkyl group having a carbon atom number of 1 to 6 or a linear or branched alkyl halide group having a carbon atom number of 1 to 6 in which a hydrogen atom is optionally substituted with a hydroxy group, or a combination of these groups, where the number of substituents for the hydrogen atom of the aromatic ring in Ar.sup.1 or Ar.sup.2 is an integer of 0 to 10.

2. The resist overlayer film forming composition according to claim 1, wherein Ar.sup.1 is an organic group of (Formula 2-a) to (Formula 2-e) below or a combination thereof, the aromatic ring included in Ar.sup.1 is bonded with Ar.sup.2, and Ar.sup.2 is a methylene group, an organic group of (Formula 3) below or (Formula 3-1) below: ##STR00062## in (Formula 2-a) to (Formula 2-e), (Formula 3), and (Formula 3-1), R.sub.3 to R.sub.15 and R.sub.17 are independently an organic group including a linear or branched saturated alkyl group having a carbon atom number of 1 to 10, in which some or all of hydrogen atoms thereof are substituted with fluorine atoms; T.sub.3 to T.sub.17 are independently a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, a C.sub.1-9 alkoxy group, an amino group having a hydrogen atom optionally substituted with a C.sub.1-3 linear alkyl group, a linear, branched, or cyclic saturated alkyl group having a carbon atom number of 1 to 6 or a linear or branched alkyl halide group having a carbon atom number of 1 to 6 in which a hydrogen atom is optionally substituted with a hydroxy group, or a combination of these groups; Q.sub.1 and Q.sub.2 are a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, a C.sub.6-40 arylene group, a linear or branched alkylene group having a carbon atom number of 1 to 10 in which a hydrogen atom is optionally substituted with a halogen atom, or a combination of these groups; the alkylene group optionally forms a ring; m1, m2, m5, m6, r4, r5, r8 to r14, t4, t5, and t8 to t14 are independently an integer of 0 to 2; r3, r6, r7, r17, t3, t6, t7, and t17 are independently an integer of 0 to 8; r15 and t15 are independently an integer of 0 to 9; in (Formula 2-a), (Formula 2-b), and (Formula 2-e), the sum of r3 to r15 or r17 that are present in the polymer is an integer of 1 to 10, in which some or all of hydrogen atoms are substituted with fluorine atoms; and in (Formula 2-c) and (Formula 2-d), the sum of r3 to r15 or r17 that are present in the polymer is an integer of 0 to 10; and if the sum of r3 to r15 or r17 in (Formula 2-c) and (Formula 2-d) is 0, at least one of Q.sub.1 and Q.sub.2 includes at least one linear or branched alkylene group having a carbon atom number of 1 to 10, in which some or all of hydrogen atoms are substituted with fluorine atoms.

3. The resist overlayer film forming composition according to claim 2, wherein in the unit structures of the polymer, any one of T.sub.3 to T.sub.17 includes one or more hydroxy groups.

4. The resist overlayer film forming composition according to claim 2, wherein R.sub.3 to R.sub.15, and R.sub.17 are an organic group of (Formula 1-7) below: ##STR00063## (in (Formula 1-7), W.sub.1 and W.sub.2 are independently a hydrogen atom, a fluorine atom, a trifluoromethyl group, a difluoromethyl group, or a monofluoromethyl group; w.sub.3 is a hydrogen atom, a fluorine atom, or a combination thereof; at least one of W.sub.1, W.sub.2 and w.sub.3 is the organic group including fluorine or a fluorine atom; m4 is an integer of 0 to 9; and the largest value of the number of carbon atoms included in (Formula 1-7) is 10).

Description

EXAMPLES

(1) The weight average molecular weights (Mw) of the polymers shown in Synthesis Example 1 to Synthesis Example 59 below in the present description were measured by GPC (Gel Permeation Chromatography). In the measurement, a GPC apparatus manufactured by TOSOH CORPORATION was used under the measurement conditions below. The degree of distribution shown in each synthesis example below in the present description is calculated from the measured weight average molecular weight and number average molecular weight.

(2) Measurement device: HLC-8320GPC [trade name] (manufactured by TOSOH CORPORATION)

(3) GPC column: TSKge1 SuperMultipore HZ-N (P0009) [trade name] (manufactured by TOSOH CORPORATION),

(4) TSKge1 SuperMultipore HZ-N (P0010) [trade name] (manufactured by TOSOH CORPORATION)

(5) Column temperature: 40° C.

(6) Solvent: tetrahydrofuran (THF)

(7) Flow rate: 0.35 m1/min

(8) Standard sample: polystyrene (manufactured by TOSOH CORPORATION)

Synthesis Example 1

(9) In 28.0 g of propyleneglycol monomethyl ether, 3.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.9 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 2.7 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.37 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-1) and (Formula 10-2). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2680.

Synthesis Example 2

(10) In 28.9 g of propyleneglycol monomethyl ether, 3.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.68 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 3.1 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.37 g of p-toluenesulfonic acid monohydrate were added and dissolved. After nitrogen was introduced into the reactor, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-1) and (Formula 10-2). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2189.

Synthesis Example 3

(11) In 29.8 g of propyleneglycol monomethyl ether, 3.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.45 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.37 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-1) and (Formula 10-2). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2311.

Synthesis Example 4

(12) In 33.2 g of propyleneglycol monomethyl ether, 3.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.2 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.43 g of p-toluenesulfonic acid monohydrate were added and dissolved. After nitrogen was introduced into the reactor, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2257.

Synthesis Example 5

(13) In 35.0 g of propyleneglycol monomethyl ether, 3.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.6 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 4.2 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.43 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2273.

Synthesis Example 6

(14) In 33.8 g of propyleneglycol monomethyl ether, 3.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.3 g of 2,4,6-trihydroxybenzaldehyde (the compound of Formula 5-40), 3.2 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.43 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-4). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 1300.

Synthesis Example 7

(15) In 35.3 g of propyleneglycol monomethyl ether, 3.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.67 g of 2,4,6-trihydroxybenzaldehyde (the compound of Formula 5-40), 4.2 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.43 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-4). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 1303.

Synthesis Example 8

(16) In 31.6 g of propyleneglycol monomethyl ether, 3.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 4.5 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.37 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formula of the resulting polymer is shown as (Formula 10-2). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 2702.

Synthesis Example 9

(17) In 14.6 g of propyleneglycol monomethyl ether, 3.0 g of phloroglucinol (the compound of Formula 3-16), 5.7 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.94 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for six hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a brown polymer. The main structural formula of the resulting polymer is shown as (Formula 10-5). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 4463.

Synthesis Example 10

(18) In 16.5 g of propyleneglycol monomethyl ether, 2.5 g of 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (the compound of Formula 1-9-1), 1.43 g of 2-vinylnaphthalene (the compound of Formula 1-10-11), and 0.19 g of 2,2′-azodiisobutyronitrile were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 80° C. for six hours, yielding a polymer solution. The structural formula of the resulting polymer is shown as (Formula 11-1). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 10232.

Synthesis Example 11

(19) In 17.7 g of propyleneglycol monomethyl ether, 5.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 0.34 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.46 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.00 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-6) and (Formula 10-7). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 5052.

Synthesis Example 12

(20) In 19.3 g of propyleneglycol monomethyl ether, 6.0 g of α,α,α′,α′-tetrakis(4-hydroxyphenyl)-p-xylene (product name: TEP-TPA, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-22), 0.34 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.51 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.00 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a red polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-8) and (Formula 10-9). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 13315.

Synthesis Example 13

(21) In 22.66 g of propyleneglycol monomethyl ether, 7.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 0.41 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 6.51 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.19 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-6) and (Formula 10-7). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 4596.

Synthesis Example 14

(22) In 17.7 g of propyleneglycol monomethyl ether, 5.0 g of 4,4′,4″-trihydroxytriphenylmethane (the compound of Formula 4-25), 0.71 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 11.18 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 2.04 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a red polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-10) and (Formula 10-11). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 4597.

Synthesis Example 15

(23) In 28.72 g of propyleneglycol monomethyl ether, 5.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 12.15 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.99 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formula of the resulting polymer is shown as (Formula 10-12). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 19773.

Synthesis Example 16

(24) In 25.17 g of propyleneglycol monomethyl ether, 7.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 0.97 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 7.66 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.15 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-6) and (Formula 10-7). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 4866.

Synthesis Example 17

(25) In 22.90 g of propyleneglycol monomethyl ether, 7.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 0.437 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 6.89 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.94 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-6) and (Formula 10-7). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 4631.

Synthesis Example 18

(26) In 22.35 g of propyleneglycol monomethyl ether, 4.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 0.55 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 8.75 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.60 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-12) and (Formula 10-13). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 6695.

Synthesis Example 19

(27) In 26.20 g of propyleneglycol monomethyl ether, 8.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (product name: TEP-DF, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.) (the compound of Formula 4-21), 8.75 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.72 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a yellow polymer. The main structural formula of the resulting polymer is shown as (Formula 10-6). A GPC analysis was conducted to show that the resulting polymer had a weight average molecular weight of 3333.

Synthesis Example 20

(28) In 42.37 g of propyleneglycol monomethyl ether, 5.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 6.99 g of 3,5-dibromo-4-hydroxybenzaldehyde (the compound of Formula 5-37), 1.5 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.62 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-14). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 4759.

Synthesis Example 21

(29) In 41.66 g of propyleneglycol monomethyl ether, 5.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 5.24 g of 3,5-dibromo-4-hydroxybenzaldehyde (the compound of Formula 5-37), 3.02 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.62 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-14). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 4526.

Synthesis Example 22

(30) In 16.48 g of propyleneglycol monomethylether acetate, 5.0 g of 2,2′-biphenol (the compound of Formula 5-11), 1.31 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 3.9 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.774 g of methanesulfonic acid were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-15) and (Formula 10-16). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2449.

Synthesis Example 23

(31) In 16.35 g of propyleneglycol monomethyl ether, 3.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.9 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 2.7 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.37 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-1) and (Formula 10-2). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3431.

Synthesis Example 24

(32) In 41.58 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.58 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 6.8 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.93 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3186.

Synthesis Example 25

(33) In 17.82 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.58 g of 2,4-dihydroxybenzaldehyde (the compound of Formula 5-42), 6.8 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.93 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-19). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2163.

Synthesis Example 26

(34) In 11.69 g of propyleneglycol monomethyl ether, 2.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.58 g of 6-hydroxy-2-naphthaldehyde (the compound of Formula 5-43), 2.11 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.24 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-20). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 7209.

Synthesis Example 27

(35) In 22.50 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.52 g of vanillin (the compound of Formula 5-33), 3.62 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-21). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3216.

Synthesis Example 28

(36) In 22.45 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.50 g of 4-hydroxy-3,5-dimethylbenzaldehyde (the compound of Formula 5-35), 3.62 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-22). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2818.

Synthesis Example 29

(37) In 22.17 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.20 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.17 g of p-anisaldehyde (the compound of Formula 5-44), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-23). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3280.

Synthesis Example 30

(38) In 22.29 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.20 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.21 g of 4-diethylaminobenzaldehyde (the compound of Formula 5-29), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-24). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2373.

Synthesis Example 31

(39) In 22.40 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.20 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.44 g of 4-diethylaminobenzaldehyde (the compound of Formula 5-29), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-24). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1973.

Synthesis Example 32

(40) In 22.21 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.20 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.19 g of 4-dimethylaminobenzaldehyde (the compound of Formula 5-28), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-25). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2646.

Synthesis Example 33

(41) In 22.21 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.20 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.19 g of 2,3-(methylenedioxy)benzaldehyde (the compound of Formula 5-31), and 0.49 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-26). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3311.

Synthesis Example 34

(42) In 40.44 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 3.23 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.66 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.93 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2993.

Synthesis Example 35

(43) In 46.40 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 3.1 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 8.16 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.11 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 5684.

Synthesis Example 36

(44) In 48.81 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 3.36 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 8.84 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.21 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 6006.

Synthesis Example 37

(45) In 42.78 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.71 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 7.14 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.97 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3615.

Synthesis Example 38

(46) In 42.78 g of propyleneglycol monomethylether acetate, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.71 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 7.14 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.97 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 4923.

Synthesis Example 39

(47) In 42.78 g of 4-methyl-2-pentanol, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.71 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 7.14 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.97 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2958.

Synthesis Example 40

(48) In 10.31 g of propyleneglycol monomethylether acetate, 3.0 g of 2,2′-biphenol (the compound of Formula 5-11), 0.93 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 2.4 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.48 g of methanesulfonic acid were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-16) and (Formula 10-17). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2451.

Synthesis Example 41

(49) In 10.05 g of propyleneglycol monomethylether acetate, 3.0 g of 2,2′-biphenol (the compound of Formula 5-11), 1.16 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 2.04 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.48 g of methanesulfonic acid were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-16) and (Formula 10-17). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2395.

Synthesis Example 42

(50) In 41.01 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 2.91 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 6.23 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.93 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-3). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3238.

Synthesis Example 43

(51) In 19.59 g of propyleneglycol monomethyl ether, 2.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 0.64 g of 6-hydroxy-2-naphthaldehyde (the compound of Formula 5-43), 2.11 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.12 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-20). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3923.

Synthesis Example 44

(52) In 36.20 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.83 g of 4-hydroxybenzaldehyde (the compound of Formula 5-39), 5.44 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.74 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-1) and (Formula 10-2). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2120.

Synthesis Example 45

(53) In 19.28 g of propyleneglycol monomethyl ether, 2.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.12 g of 6-hydroxy-2-naphthaldehyde (the compound of Formula 5-43), 1.58 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.10 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-20). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3664.

Synthesis Example 46

(54) In 9.9 g of propyleneglycol monomethylether acetate, 3.0 g of 2,2′-biphenol (the compound of Formula 5-11), 1.11 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 1.95 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 0.54 g of methanesulfonic acid were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-16) and (Formula 10-17). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1145.

Synthesis Example 47

(55) In 31.05 g of propyleneglycol monomethyl ether, 7.5 g of phloroglucinol (the compound of Formula 3-16), 3.61 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 7.2 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 2.36 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5) and (Formula 10-29). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1636.

Synthesis Example 48

(56) In 27.96 g of propyleneglycol monomethyl ether, 7.5 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 3.61 g of 3,4,5-trihydroxybenzaldehyde (the compound of Formula 5-46), 5.66 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.81 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2) and (Formula 10-5-1). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2503.

Synthesis Example 49

(57) In 29.16 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.38 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.6 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.19 g of 4-(methylthio)benzaldehyde (the compound of Formula 5-45), and 0.52 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-27). The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3172.

Synthesis Example 50

(58) In 2882 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.38 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.32 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.38 g of 4-(methylthio)benzaldehyde (the compound of Formula 5-45), and 0.52 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-27). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3080.

Synthesis Example 51

(59) In 28.48 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.38 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.02 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.57 g of 4-(methylthio)benzaldehyde (the compound of Formula 5-45), and 0.52 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-27). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3286.

Synthesis Example 52

(60) In 29.13 g of propyleneglycol monomethyl ether, 4.0 g of 1,5-dihydroxynaphthalene (the compound of Formula 3-18), 1.38 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 3.02 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), 0.76 g of 4-(methylthio)benzaldehyde (the compound of Formula 5-45), and 0.54 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-2), (Formula 10-3), and (Formula 10-27). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3308.

Synthesis Example 53

(61) In 18.74 g of propyleneglycol monomethyl ether, 9.0 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (the compound of Formula 5-20), 2.91 g of 2,6-bis(hydroxymethyl)-p-cresol (the compound of Formula 7-2), and 0.52 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a white novolac polymer. The main structural formula of the resulting polymer is shown as (Formula 10-28). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 4073.

Synthesis Example 54

(62) In 17.47 g of propyleneglycol monomethyl ether, 9.0 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (the compound of Formula 5-20), 2.25 g of 2,6-bis(hydroxymethyl)-p-cresol (the compound of Formula 7-2), and 0.399 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a white novolac polymer. The main structural formula of the resulting polymer is shown as (Formula 10-28). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 3019.

Synthesis Example 55

(63) In 24.13 g of propyleneglycol monomethyl ether, 5.0 g of phloroglucinol (the compound of Formula 3-16), 0.96 g of bis(4-hydroxyphenyl)sulfide (the compound of Formula 5-15), 3.04 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.33 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.75 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5), (Formula 10-29), (Formula 10-30), and (Formula 10-31). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 2010.

Synthesis Example 56

(64) In 24.34 g of propyleneglycol monomethyl ether, 5.0 g of phloroglucinol (the compound of Formula 3-16), 1.13 g of bis(4-hydroxyphenyl)sulfone (the compound of Formula 5-14), 3.04 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.33 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.75 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5), (Formula 10-29), (Formula 10-32), and (Formula 10-33). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1992.

Synthesis Example 57

(65) In 22.67 g of propyleneglycol monomethyl ether, 5.0 g of phloroglucinol (the compound of Formula 3-16), 0.52 g of 2,2′,4,4′-tetrahydroxydiphenyl sulfide (the compound of Formula 5-21), 2.88 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.05 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.66 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5), (Formula 10-29), (Formula 10-34), and (Formula 10-35). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1855.

Synthesis Example 58

(66) In 24.34 g of propyleneglycol monomethyl ether, 5.0 g of phloroglucinol (the compound of Formula 3-16), 1.10 g of 2,2′,4,4′-tetrahydroxydiphenyl sulfide (the compound of Formula 5-21), 3.04 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.33 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.75 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5), (Formula 10-29), (Formula 10-34), and (Formula 10-35). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1831.

Synthesis Example 59

(67) In 24.34 g of propyleneglycol monomethyl ether, 5.0 g of phloroglucinol (the compound of Formula 3-16), 1.10 g of 2,4′-dihydroxydiphenyl sulfone (the compound of Formula 5-22), 3.04 g of 3,4-dihydroxybenzaldehyde (the compound of Formula 5-41), 5.33 g of 3,5-bis(trifluoromethyl)benzaldehyde (the compound of Formula 5-27), and 1.75 g of p-toluenesulfonic acid monohydrate were added and dissolved. After purging the reactor with nitrogen, the reaction was allowed to proceed at 140° C. for four hours, yielding a novolac polymer solution. The resulting solution was added into a solution of methanol:water=1:9, yielding a black novolac polymer. The main structural formulae of the resulting polymer are shown as (Formula 10-5), (Formula 10-29), (Formula 10-36), and (Formula 10-37). A GPC analysis was conducted to show that the resulting novolac polymer had a weight average molecular weight of 1758.

Example 1

(68) In 0.6 g of the polymer obtained in Synthesis Example 1, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 2

(69) In 0.6 g of the polymer obtained in Synthesis Example 1, 19.4 g of dibutyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 3

(70) In 0.6 g of the polymer obtained in Synthesis Example 2, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 4

(71) In 0.6 g of the polymer obtained in Synthesis Example 3, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 5

(72) In 0.6 g of the polymer obtained in Synthesis Example 4, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 6

(73) In 0.6 g of the polymer obtained in Synthesis Example 5, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 7

(74) In 0.6 g of the polymer obtained in Synthesis Example 6, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 8

(75) In 0.6 g of the polymer obtained in Synthesis Example 7, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 9

(76) In 0.6 g of the polymer obtained in Synthesis Example 8, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 10

(77) In 0.6 g of the polymer obtained in Synthesis Example 9, 19.4 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 11

(78) In 3.0 g of the polymer solution obtained in Synthesis Example 10, 27.0 g of dibutyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 12

(79) In 0.6 g of the polymer obtained in Synthesis Example 1, 18.4 g of diisoamyl ether and 0.97 g of 4-methyl-2-pentanol was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 13

(80) In 0.6 g of the polymer obtained in Synthesis Example 1, 17.4 g of diisoamyl ether and 1.97 g of 4-methyl-2-pentanol was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 14

(81) In 0.6 g of the polymer obtained in Synthesis Example 1, 19.4 g of diisobutyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 15

(82) In 0.6 g of the polymer obtained in Synthesis Example 1, 16.5 g of diisoamyl ether and 2.91 g of 4-methyl-2-pentanol was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 16

(83) In 3.0 g of the polymer obtained in Synthesis Example 11, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 17

(84) In 3.0 g of the polymer obtained in Synthesis Example 12, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 18

(85) In 3.0 g of the polymer obtained in Synthesis Example 13, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 19

(86) In 3.0 g of the polymer obtained in Synthesis Example 14, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 20

(87) In 3.0 g of the polymer obtained in Synthesis Example 15, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 21

(88) In 3.0 g of the polymer obtained in Synthesis Example 16, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 22

(89) In 3.0 g of the polymer obtained in Synthesis Example 17, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 23

(90) In 3.0 g of the polymer obtained in Synthesis Example 18, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 24

(91) In 3.0 g of the polymer obtained in Synthesis Example 19, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 25

(92) In 3.0 g of the polymer obtained in Synthesis Example 20, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 26

(93) In 3.0 g of the polymer obtained in Synthesis Example 21, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 27

(94) In 3.0 g of the polymer obtained in Synthesis Example 22, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 28

(95) In 3.0 g of the polymer obtained in Synthesis Example 23, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 29

(96) In 3.0 g of the polymer obtained in Synthesis Example 24, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 30

(97) In 3.0 g of the polymer obtained in Synthesis Example 25, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 31

(98) In 3.0 g of the polymer obtained in Synthesis Example 26, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 32

(99) In 3.0 g of the polymer obtained in Synthesis Example 27, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μM to prepare a resist overlayer film forming composition to be used for lithography.

Example 33

(100) In 3.0 g of the polymer obtained in Synthesis Example 28, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 34

(101) In 3.0 g of the polymer obtained in Synthesis Example 29, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 35

(102) In 3.0 g of the polymer obtained in Synthesis Example 30, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 36

(103) In 3.0 g of the polymer obtained in Synthesis Example 31, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 37

(104) In 3.0 g of the polymer obtained in Synthesis Example 32, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 38

(105) In 3.0 g of the polymer obtained in Synthesis Example 33, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 39

(106) In 3.0 g of the polymer obtained in Synthesis Example 34, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 40

(107) In 3.0 g of the polymer obtained in Synthesis Example 35, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 41

(108) In 3.0 g of the polymer obtained in Synthesis Example 36, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 42

(109) In 3.0 g of the polymer obtained in Synthesis Example 37, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 43

(110) In 3.0 g of the polymer obtained in Synthesis Example 38, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 44

(111) In 3.0 g of the polymer obtained in Synthesis Example 39, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 45

(112) In 3.0 g of the polymer obtained in Synthesis Example 40, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 46

(113) In 3.0 g of the polymer obtained in Synthesis Example 41, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 47

(114) In 3.0 g of the polymer obtained in Synthesis Example 42, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 48

(115) In 3.0 g of the polymer obtained in Synthesis Example 43, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 49

(116) In 3.0 g of the polymer obtained in Synthesis Example 44, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 50

(117) In 3.0 g of the polymer obtained in Synthesis Example 45, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 51

(118) In 3.0 g of the polymer obtained in Synthesis Example 46, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 52

(119) In 3.0 g of the polymer obtained in Synthesis Example 47, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 53

(120) In 3.0 g of the polymer obtained in Synthesis Example 48, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 54

(121) In 3.0 g of the polymer obtained in Synthesis Example 49, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 55

(122) In 3.0 g of the polymer obtained in Synthesis Example 50, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μM to prepare a resist overlayer film forming composition to be used for lithography.

Example 56

(123) In 3.0 g of the polymer obtained in Synthesis Example 51, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 57

(124) In 3.0 g of the polymer obtained in Synthesis Example 52, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 58

(125) In 3.0 g of the polymer obtained in Synthesis Example 53, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 59

(126) In 3.0 g of the polymer obtained in Synthesis Example 54, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 60

(127) In 3.0 g of the polymer obtained in Synthesis Example 55, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 61

(128) In 3.0 g of the polymer obtained in Synthesis Example 56, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 62

(129) In 3.0 g of the polymer obtained in Synthesis Example 57, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 63

(130) In 3.0 g of the polymer obtained in Synthesis Example 58, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Example 64

(131) In 3.0 g of the polymer obtained in Synthesis Example 59, 27.0 g of diisoamyl ether was added and dissolved. Then, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a resist overlayer film forming composition to be used for lithography.

Comparative Example 1

(132) A resist overlayer film forming composition solution was obtained by dissolving 1 g of polyhydroxystyrene resin (commercially available product, weight average molecular weight of 8,000) in 99 g of 4-methyl-2-pentanol.

(133) [Test for Confirming Insolubility of Resist in Ether-based Solvent]

(134) An EUV resist solution (hydroxystyrene (HS)-containing resist) was applied using a spinner. The solution was heated on a hot plate at 100° C. for one minute to form a resist film, and the film thickness was measured.

(135) After the solvents for the resist overlayer film forming compositions (dibutyl ether, diisoamyl ether, diisobutyl ether) and the resist overlayer film compositions of Example 1, Example 12, Example 13, and Example 15 were each applied on the resist film using a spinner and heated on a hot plate at 100° C. for one minute, a puddle of a commercially available alkaline developer (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was formed on the resist (in the case of the solvents for the resist overlayer film forming compositions) or on the resist overlayer film (in the case of Example 1, Example 12, Example 13, and Example 15) and left for 60 seconds, followed by rinsing with pure water for 30 seconds while being rotated at 3000 rpm. After rinsing, baking was performed at 100° C. for 60 seconds, and the film thickness was measured.

(136) The degree of film loss of the resist was determined as shown in Table 1. Almost no film loss is shown by ⊙, and the film loss that is slightly greater than ⊙ as the resist overlayer film but poses no problem in practice is shown by ◯.

(137) TABLE-US-00001 TABLE 1 Resist Insolubility Confirming Test Dibutyl ether ⊙ Diisoamyl ether ⊙ Diisobutyl ether ⊙ Example 1 ⊙ Example 12 ⊙ Example 13 ⊙ Example 15 ◯

(138) [Intermixing Test with Resist (Positive tone Development (PTD)]

(139) An EUV resist solution (methacrylic resist) was applied using a spinner. The solution was heated on a hot plate at 100° C. for one minute to form a resist film, and the film thickness was measured (film thickness A: resist film thickness).

(140) The resist overlayer film forming composition solutions prepared in Example 1 to Example 64 of the present invention and Comparative Example 1 were each applied on the resist film using a spinner and heated on a hot plate at 100° C. for one minute to form a resist overlayer film, and the film thickness was measured (film thickness B: the sum of the film thicknesses of the resist and the resist overlayer film).

(141) A puddle of a commercially available alkaline developer (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was formed on the resist overlayer film and left for 60 seconds, followed by rinsing with pure water for 30 seconds while being rotated at 3000 rpm. After rinsing, baking was performed at 100° C. for 60 seconds, and the film thickness was measured (film thickness C).

(142) If film thickness A is equal to film thickness C, it shows that there is no intermixing with the resist and the product is applicable as a resist overlayer film for a PTD process.

(143) TABLE-US-00002 TABLE 2 Film Thickness Measurement Film Film Film thickness thickness thickness A (nm) B (nm) C (nm) Example 1 56 86 56 Example 2 56 86 56 Example 3 56 86 56 Example 4 56 86 56 Example 5 56 86 56 Example 6 56 86 56 Example 7 56 86 56 Example 8 56 86 56 Example 9 56 86 86 Example 10 56 86 86 Example 11 56 86 86 Example 12 56 86 56 Example 13 56 86 56 Example 14 56 86 56 Example 15 56 86 56 Example 16 56 86 56 Example 17 56 86 56 Example 18 56 86 56 Example 19 56 86 56 Example 20 56 86 56 Example 21 56 86 56 Example 22 56 86 56 Example 23 56 86 56 Example 24 56 86 56 Example 25 56 86 56 Example 26 56 86 56 Example 27 56 86 56 Example 28 56 86 56 Example 29 56 86 56 Example 30 56 86 56 Example 31 56 86 56 Example 32 56 86 56 Example 33 56 86 56 Example 34 56 86 56 Example 35 56 86 56 Example 36 56 86 56 Example 37 56 86 56 Example 38 56 86 56 Example 39 56 86 56 Example 40 56 86 56 Example 41 56 86 56 Example 42 56 86 56 Example 43 56 86 56 Example 44 56 86 56 Example 45 56 86 56 Example 46 56 86 56 Example 47 56 86 56 Example 48 56 86 56 Example 49 56 86 56 Example 50 56 86 56 Example 51 56 86 56 Example 52 56 86 56 Example 53 56 86 56 Example 54 56 86 56 Example 55 56 86 56 Example 56 56 86 56 Example 57 56 86 56 Example 58 56 86 56 Example 59 56 86 56 Example 60 56 86 56 Example 61 56 86 56 Example 62 56 86 56 Example 63 56 86 56 Example 64 56 86 56 Comparative Example 1 56 86 56

(144) [Application Test to Negative tone Development (NTD) Process]

(145) The resist overlayer film forming composition solutions prepared in Example 1 to Example 64 of the present invention and Comparative Example 1 were each applied on a wafer using a spinner and heated on a hot plate at 100° C. for one minute to form a resist overlayer film, and the film thickness was measured (film thickness A: the film thickness of the resist overlayer film).

(146) A puddle of butyl acetate (solvent developer), which is often used in an NTD process, was formed on the resist overlayer film, left for 60 seconds, and rotated at 3000 rpm. After that, baking was performed at 100° C. for 60 seconds, and the film thickness was measured (film thickness B).

(147) If film thickness B is 0 nm, it can be said that the resist overlayer film was able to be removed by the developer. This suggests that the composition of the present invention is also applicable as a resist overlayer film for an NTD process.

(148) TABLE-US-00003 TABLE 3 Film Thickness Measurement Film Film thickness thickness A (nm) B (nm) Example 1 30 0 Example 2 30 0 Example 3 30 0 Example 4 30 0 Example 5 30 0 Example 6 30 0 Example 7 30 0 Example 8 30 0 Example 9 30 0 Example 10 30 0 Example 11 30 0 Example 12 30 0 Example 13 30 0 Example 14 30 0 Example 15 30 0 Example 16 30 0 Example 17 30 0 Example 18 30 0 Example 19 30 0 Example 20 30 0 Example 21 30 0 Example 22 30 0 Example 23 30 0 Example 24 30 0 Example 25 30 0 Example 26 30 0 Example 27 30 0 Example 28 30 0 Example 29 30 0 Example 30 30 0 Example 31 30 0 Example 32 30 0 Example 33 30 0 Example 34 30 0 Example 35 30 0 Example 36 30 0 Example 37 30 0 Example 38 30 0 Example 39 30 0 Example 40 30 0 Example 41 30 0 Example 42 30 0 Example 43 30 0 Example 44 30 0 Example 45 30 0 Example 46 30 0 Example 47 30 0 Example 48 30 0 Example 49 30 0 Example 50 30 0 Example 51 30 0 Example 52 30 0 Example 53 30 0 Example 54 30 0 Example 55 30 0 Example 56 30 0 Example 57 30 0 Example 58 30 0 Example 59 30 0 Example 60 30 0 Example 61 30 0 Example 62 30 0 Example 63 30 0 Example 64 30 0 Comparative Example 1 30 30

(149) [Optical Parameter Test]

(150) The resist overlayer film forming composition solutions prepared in Example 1 to Example 64 of the present invention and Comparative Example 1 were each applied on a quartz substrate using a spinner. The solution was heated on a hot plate at 100° C. for one minute to form a resist overlayer film (film thickness of 30 nm). For these 60 kinds of resist overlayer films, the absorptance at wavelengths of 190 nm to 260 nm was measured using a spectrophotometer.

(151) The transmissivity at 13.5 nm was calculated by simulation based on the relation between the element composition ratio and the film density.

(152) The property of blocking DUV light is considered to be good if the largest value of absorptance is 40% or higher and to be poor if lower than 40%, in a wavelength band of 220 nm to 260 nm. The transmissivity of EUV light (13.5 nm) is considered to be good if the transmittance is 80% or higher and to be poor if lower than 80%.

(153) The resist overlayer film obtained from the resist overlayer film forming composition in each Example is superior in blocking DUV light to the resist overlayer film obtained from the resist overlayer film forming composition of Comparative Example 1.

(154) TABLE-US-00004 TABLE 4 EUV Transmissivity and DUV Blocking Property Film EUV Light DUV thickness Trans- light (nm) missivity Blocking Example 1 30 good good Example 2 30 good good Example 3 30 good good Example 4 30 good good Example 5 30 good good Example 6 30 good good Example 7 30 good good Example 8 30 good good Example 9 30 good good Example 10 30 good good Example 11 30 good good Example 12 30 good good Example 13 30 good good Example 14 30 good good Example 15 30 good good Example 16 30 good good Example 17 30 good good Example 18 30 good good Example 19 30 good good Example 20 30 good good Example 21 30 good good Example 22 30 good good Example 23 30 good good Example 24 30 good good Example 25 30 good good Example 26 30 good good Example 27 30 good good Example 28 30 good good Example 29 30 good good Example 30 30 good good Example 31 30 good good Example 32 30 good good Example 33 30 good good Example 34 30 good good Example 35 30 good good Example 36 30 good good Example 37 30 good good Example 38 30 good good Example 39 30 good good Example 40 30 good good Example 41 30 good good Example 42 30 good good Example 43 30 good good Example 44 30 good good Example 45 30 good good Example 46 30 good good Example 47 30 good good Example 48 30 good good Example 49 30 good good Example 50 30 good good Example 51 30 good good Example 52 30 good good Example 53 30 good good Example 54 30 good good Example 55 30 good good Example 56 30 good good Example 57 30 good good Example 58 30 good good Example 59 30 good good Example 60 30 good good Example 61 30 good good Example 62 30 good good Example 63 30 good good Example 64 30 good good Comparative Example 1 30 30 poor

INDUSTRIAL APPLICABILITY

(155) The present invention provides a composition for forming an EUV resist overlayer film for use in an EUV lithography process or a resist overlayer film for a lithography process in other exposure wavelengths, which does not intermix with a resist, blocks undesirable exposure light, for example, UV and DUV and selectively transmits EUV alone, for example, in EUV exposure, and can be developed with a developer after exposure.