TW200832057A - Resist composition for use in lithography method utilizing electron beam, x-ray or EUV light - Google Patents

Abstract

Disclosed is a resist composition for use in a lithography method utilizing electron beam, X-ray or EUV light. Specifically disclosed is a resist composition for use in a lithography method utilizing electron beam, X-ray or EUV light, comprising: a fluorinated polymer (F) which has a repeating unit (F) having a fluorinated aromatic ring structure in a side chain and whose alkali solubility can be increased by the action of an acid; and a compound capable of generating an acid. For example, the repeating unit (F) is a repeating unit (FV) [wherein RF represents a hydrogen atom, a halogen atom, a methyl group, or a halomethyl group (provided that three pieces of RF's may be the same as or different from one another); YF represents an acid-degradable group having 1 to 20 carbon atoms or a hydrogen atom; and p, q and r independently represent an integer of 0 to 5, provided that the sum total of p, q and r is 1 to 5].

Description

200832057 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a photoresist composition used in lithography using electron beam, X-ray and EUV light, and a photoresist formation containing the photoresist composition and an organic solvent Composition. [Prior Art] In the manufacture of an integrated circuit such as a semiconductor, lithography is used, in which a light ray pattern obtained by irradiating light from an exposure light source onto a reticle is projected onto a photosensitive resist film on a substrate, and the pattern is transferred. Printed to a photosensitive photoresist film. The transferred pattern was made fine by a short wavelength of the exposure light source, and an ArF collimated laser light (wavelength 193 nm) and F2 excimer laser light (wavelength 157 nm) were used as an exposure light source. Therefore, it is known that a photoresist composition for increasing alkali solubility by the action of an acid used in lithography using F2 excimer laser light includes the following repeating unit (F, 1) and contains the following repeating unit (Gh1) A photoresist composition of a fluoropolymer (see Patent Document 1). [Chemical 1]

(FV11)

{Gv2') On the other hand, as a next-generation lithography for forming finer patterns, lithography using electron beams, X-rays, and EUV light as exposure light sources has attracted attention in recent years. -4- 200832057 In the aforementioned lithography, a photoresist composition containing a polymer which increases alkali solubility by an action of an acid and a compound (acid generator) which produces an acid is usually used.

As the polymer, a polymer of a repeating styrene of a fluorine atom is known (refer to the repeating unit of the structure of the patent document (refer to Patent Document 3 below). [Chemical Formula 2] contains a non-acid-decomposable group. A polymer having a fluorine-containing aliphatic ring element (FANb) or the like (for repeating unit (PV1) or the like 2)

(FANb) c(cf3) 2oh Further, in Non-Patent Documents 1 and 2, a photoresist composition containing a polymer of a repeating unit of a styrene having a chlorine atom or a bromine atom is indicated, and a polymerization containing no repeating unit is included. Compared with the photoresist composition of the object, the sensitivity to the electron beam is high. However, in Non-Patent Documents 1 and 2, there is no description of a fluorine-containing polymer containing a repeating unit of a styrene having a fluorine atom. Patent Document 1: JP-A-2005-002925 (Patent Document 2) JP-A-2005-275283 (Patent Document 3) JP-A-2005-275283 Non-Patent Document 1: Japanese Journal of Applied Physics (Jpn·J·Appl·

Phys. ),43 ( 6B),2 0 0 4,3 9 7 1-3 9 7 3 Page 200832057 Non-Patent Document 2: Japanese Journal of Applied Physics (jpn. Phys. ) , 44 ( 26 ), 2 0 0 5 , L 8 4 2 - L 8 4 4 pages [Summary of the Invention] [Problems to be Solved by the Invention] The photoresist composition used in the above-mentioned lithography is intended to be an electron beam, an X-ray, and the like from the viewpoint of forming a polar lake shape. EUV light is narrow. In order to modulate such a photoresist composition, a polymer which is easily ionized by an electron beam or X EUV light or which easily generates secondary electrons and which has an alkali solubility by an acid is used as a photo-enhancing composition. The method of producing acid is useful. Further, the photoresist film formed of the photoreceptor on the substrate forms a very fine pattern from the substrate; $ is expected to be excellent in etching resistance. However, photoresist compositions that satisfy these characteristics are not known. The present invention is aimed at forming an extremely fine pattern, and the etching resistance is excellent for white light, X-ray, and EUV light. [Means for Solving the Problem] That is, the present invention has the following gist.光] — A photoresist composition for use in electron beam, X-ray, and EUV light, which is characterized by containing an acid having a repeating unit (F) having a side chain having an aromatic ring structure, so that the alkali is contained Fluoropolymer (F); and a compound which produces an acid.

Appl.

Micro-pattern high-sensitivity ray and the effect of acid resistance in the action of electron-resistance group fluorination aryl cyclization increase -6-200832057 [2] as described in [1], the repeating unit (F ), a repeating unit represented by the following formula (Fv), [Chemical 3] rf rf

The symbol in the formula indicates the following meaning, RF: hydrogen atom, halogen atom, methyl group or halomethyl group, three 1^ may be the same or different, YF: hydrogen atom or acid decomposition of 1 to 20 carbon atoms The radicals, p, q and r are each independent, representing an integer from 0 to 5, and the sum of p, q and r is an integer from 1 to 5.

[3] The photoresist composition according to [1] or [2] wherein the repeating unit (F) is at least one selected from the group consisting of the following formula (FV1), the following formula (Fv2), and the following formula (Fv 3 ) The repeating unit (Fvn) of the group, he 4]

(FV3) The symbol in the formula indicates the following meanings: Π, τ2 and ql: each is an integer of 1 to 3 independently, -7-200832057 YF2: an acid-decomposable group having 1 to 20 carbon atoms. [4] The photoresist composition according to any one of [1] to [3] wherein the fluoropolymer (F) has a weight average molecular weight of 1,000 to 1,000,000. [5] The photoresist composition according to any one of [1] to [4] wherein the ratio of the weight average molecular weight to the number average molecular weight of the fluoropolymer (F) is 2.2 or less. [6] The photoresist composition according to any one of [1] to [5] wherein the ratio of the weight average molecular weight to the number average molecular weight of the fluoropolymer (F) is 1.5 or less. [7] The photoresist composition according to any one of [1] to [6] wherein the fluoropolymer (F) further contains at least one selected from the group consisting of the following formula (Gv 1 ), the following formula (Gv 2 ), and a repeating unit (Gv η) of a group of repeating units represented by the following formula (Gv 3 ), [Chemical 5]

(Gv1) (Gv2) (Gv3) The symbol in the formula indicates the following meaning, RC}: hydrogen atom, halogen atom, methyl group or halomethyl group, three RGs may be the same or different, T(}: hydrogen atom , halogen atom, methyl or halomethyl group Z6 and WG •• are each independently an acid decomposition of a carbon number of 1 to 2 -8-8 - 200832057, g: an integer of 1 to 4. [8] as [1] The photoresist composition according to any one of [7], wherein the fluoropolymer (F) further contains at least one selected from the group consisting of the following formula (Qvl), the following formula (QV2), the following formula (QV3), and the following formula (Qv4) The repeating unit (QVn) in which the repeating unit is grouped [[6]

The symbol in the formula indicates the following meaning, RQ: represents a hydrogen atom, a halogen atom, a methyl group or a halomethyl group, and the three RQs may be the same or different, TQ: a hydrogen atom, a halogen atom, a methyl group or a halomethyl group, q : An integer from 1 to 4. [9] The photoresist composition according to any one of [1] to [8] wherein the compound which produces an acid is a diazonium or a phosphonium 'sulfonium, _ key salt (iodonium), iidosulfonate, oximesulfonate, diazodisulfone, disulfone or o-nitrobenzyl sulfonate, relative to The total mass of the fluoropolymer (F), the compound which produces the acid contains 0.1 to 20% by mass. -9-200832057 [10] A photoresist forming composition for use in lithography using electron beam, X-ray, and EUV light, characterized by containing the photoresist composition as described in any one of [1] to [9] And organic solvents. [11] The photoresist forming composition according to [1], wherein the organic solvent is an alcohol compound, a ketone compound, an ester compound, an aromatic hydrocarbon compound, an ether compound or a guanamine compound. Advantageous Effects of Invention According to the present invention, there is provided a photoresist composition which is excellent in etching resistance to electron beams, X-rays, and EUV light, and which is used in lithography using electron beams, X-rays, and EUV light. [Embodiment] In the present specification, the symbols in the base are the same as the above unless otherwise specified. In the present specification, the compound represented by the formula (f) is referred to as the compound (f), and the repeating element represented by the formula (F) is represented by a repeating unit (F) represented by the formula -C(CF3)2(〇Y). The base is _c(CF3)2(OY). Other compounds and other groups are also referred to in the same manner. Further, the term "exposure" as used in the present invention refers to the commemoration of irradiation including electron beams.

The present invention provides a fluoropolymer (F) comprising: an acid-producing compound which comprises an acid having a repeating unit (F) having a fluorine-containing aromatic ring structure in a side chain; The photoresist composition used in the electron beam, X•10-200832057 ray and EUV light lithography (hereinafter referred to as lithography only). The fluoropolymer (F) of the present invention is considered to be easily ionized or easily released by electron beams, X-rays, and EUV light because it has a fluorine atom having a large absorption cross-sectional area for electron beams, X-rays, and EUV light. Secondary electrons. In particular, the fluorine-containing polymer (F) has a fluorine-containing aromatic ring structure having a π-electron, and is considered to be easier to emit secondary electrons than a fluorine-containing polymer having a fluorine-containing aliphatic ring structure. Therefore, in the photoresist composition of the present invention, it is considered that the fluoropolymer (F) is easily activated by electron beams, X-rays, and EUV light to promote the generation of an acid of the acid generator. Therefore, it is considered that the acid-producing agent of the present invention has high acid generation efficiency and high sensitivity to electron beams, X-rays, and EUV light. Further, the fluoropolymer (F) contains a repeating unit (F) having a fluorine-containing aromatic ring structure, and has excellent etching resistance as compared with a fluorine-containing polymer containing a repeating unit having a fluorine-containing aliphatic ring structure. Therefore, by using the photoresist composition of the present invention, it is possible to form a very fine pattern by lithography using electron rays, X-rays, and EUV light. The repeating unit (F) of the fluoropolymer (F) may be composed of only one type or two or more types. The fluorine-containing aromatic ring structure of the repeating unit (F) is not particularly limited as long as it has a fluorine atom-containing aromatic ring structure, and may be a monocyclic fluorine-containing aromatic ring structure or a polycyclic fluorine-containing aromatic ring. The ring structure is preferably one having the following fluorine-containing aromatic ring structure (and the position of the carbon atom of the benzene ring to which -CF3, -F, -C(CF3)2〇Yf is bonded, and is not particularly limited). -11 - 200832057 [化7] ycF^pj^F)q VC<CF3>2°YF)r Moreover, the fluorine-containing aromatic ring structure can be directly bonded to the main chain of the fluoropolymer (F), The side chain of the fluoropolymer (F) may be bonded via a linking group (-C(O)O-, -〇-, etc.). The repeating unit (F) is preferably a repeating unit (Fv) described below (and the position of the carbon atom of the benzene ring to which -CF3, -F, -C(CF3)2OYf is bonded, and is not particularly limited). [r8] rf rf

It is preferable that the three Rf of the repeating unit (Fv) is a hydrogen atom. The YF of the acid-decomposable group having 1 to 20 carbon atoms is not particularly limited, and is preferably a YF2 to be described later, and a group (YF21) to be described later, a group (YF22) to be described later, and a group (YF23) to be described later are particularly preferable. It is preferable that the sum of p, q and r is an integer of 1 to 3. Among p, q, and r, one is an integer of 1 to 3, and the other two are 0. The fluoropolymer (F) containing a repeating unit (Fv) is preferably a polymerization product of the following compound -12-200832057 (fv). Rf rf

(fv) rf repeating unit (F) is at least one repeating unit selected from the group consisting of F n

The repeating unit (Fv2) of the repeating unit represented by the following repeating unit (Fv2) and the repeating unit (Fv3) described below is preferable (and 'in each repeating unit, -CF3, -F, -C (CF3) The position of the carbon atom of the benzene ring to which 2OYf is bonded is not particularly limited). [化10]

CH2-CH*^— -^ch2-ch|- · -|ch2^ch|- |^JfC(CF3)2〇H)rl |^^C(CF3)2〇YF2)r2 ό为(Fv1) ( FV2) (FV3) YF2 is not particularly limited, and is represented by the formula -C ( YA ) ( ΥΒ ) Ο ( Yc ): base (YF21 ), formula -(〇)c(yd)3: base The group represented by (YF22) or the formula -C(YD)3: the group (γΡ23) is preferred. The symbols in the formula indicate the following meanings (the same applies hereinafter). ΥΑ and ΥΒ: independently hydrogen atoms or hydrocarbon groups having 1 to 8 carbon atoms 〇 YC: a hydrocarbon group having 1 to 16 carbon atoms. -13- 200832057 YD: a hydrocarbon group having 1 to 16 carbon atoms, and 3 YDs on the same carbon atom may be the same or different. Further, carbon atoms in the two YDs may form a cyclic hydrocarbon group. Specific examples of the group (YF21) are, for example, the following groups. [化11]

A ch2och3 — ch(ch3)och3 a ch2och2ch3 - ch(ch3)och2ch3 a ch2och2ch2ch3 — ch(ch2ch3)〇ch2ch3 —ch2och2ch2ch2ch3 —ch(ch3)och2ch2ch3 a ch2och(ch3)2 - ch(ch3)och2ch2ch2ch3 a CH2〇C( CH3)3 -CH(CH2CH3)〇CH2CH2CH3-ch(ch2ch3)och2ch2ch2ch3-ch(ch2ch2ch3)och2ch2ch3-C(CH3)2〇CH3-c(ch3)2och2ch3

-CH(CH3)0 -CH(CH3)0 - ch(ch3)och2ch2 —

-CH(CH3)OCH2CH2 - CH{CH3)0

-CH(CH3)OCH2

Specific examples of the group (YF22) are, for example, the following groups. [2 (2)

Specific examples of the group (YF23) are, for example, the following groups. -14- 200832057 [化13] ch3 a c(ch3)3 a c

Ch3 ch3—QxrD ch3 ch3 CH0CH3 ch3C〇-i9-i0^

CH

Ch3 ch3 c-ch3 - c-ch2ch3 element As a specific example of the repeating unit (Fv 1 ), for example, the following repeating sheet [Chemistry 14] • ch2 -CH^-

-CH2 - CH 4

Ch2~ch C(CF3)2(OH) C(CF3)2(OH)

C(CF3)2(〇H)

lCH2-CH|- -fCH2-CH|- _LCH2^CHA_

〇(CF3)2(OH) V i^C(CF3)2(OH) "C(CF3)2(OH) ^^^〇(〇Ρ3)2(〇Η) C(CF3)2( OH) 0{CF3)2(0H) -ch2-ch

-|ch2-chV (H〇)(CF3)2CnJ^C(CF3)2(OH) (HO)(CF3)2C^ C(CF3)2(OH) C(CF3)2(OH)

V C(CF3) 2 (OH) is a specific example of the repeating unit (Fv2 ), for example, the repeating unit -15-200832057 [Chemical 15] -ch2-chh

-ch2-ch^ C(CF3)2(OYF2) C(CF3)2(〇YF2)

C(CF3)2(OYF2) -CH2-CHV -f〇H2-CH|- -fcH2-CH4- .C(CF3)2(〇YF2} ^J〇c(cf3)2(〇yF2)

€(CF3)2(OYF2> C(CF3)2(OYF2) C(CF3)2(OYF2)

C(CF3)2(OYF2) :ch2-ch^- -fcH2-CHb(YF20)(CF3)2C>i^C(CF3)2(OYF2) C(CF3)2(OYF2) (yF2〇Kcf3) 2c^Y^c(cf3)2(oyF2> C(CF3)2(OYF2) is a specific example of the repeating unit (Fv3), for example, the repeating unit described below [Chemical 16] -ch2-ch^- -^ch2- Ch^- ~^ch2-ch^ -CH2—CH”

F -0Η2~0Η^-

F 丫, F F

F -ch2-ch F, 丄 F

The fluoropolymer (F) preferably contains 1 mol% or more of repeating units (Fvn) for all repeating units. The upper limit of the above repeating unit (Fvn) is not particularly limited, and is preferably 80 mol% or less. The repeating unit (Fvn) is particularly desirable for all repeating units to contain 1 to 50 mol%. The fluoropolymer (F) increases the alkali solubility by the action of an acid - fluoropolymer of -16-200832057. The fluoropolymer (F) preferably contains a repeating unit having an acid-decomposable group, and contains at least one repeating unit (Gv 1 ) selected from the group consisting of the following repeating unit (Gv2) and the following repeating unit (Gv3). The repeating unit (Gvn) in which the repeating units are grouped is particularly desirable. [:ization 17]

It is preferable that the three RGs of the repeating units (GV1) and (Gv2) are hydrogen atoms. The repeating unit (Gv3) is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. The WG of the repeating unit (GV1) and (Gv2) and the WG of the repeating unit (Gv3) are preferably independent YF2, and the base (YF21), the base (YF22) and the base (YF23) are particularly preferable. It is preferable that the repeating unit (GV1) and (Gv2) have a g of 1. Specific examples of the repeating unit (Gv 1 ) are, for example, the following repeating units. -17- 200832057 [化 18]

As a specific example of the repeating unit (Gv2), for example, the following repeating order [Chemistry 19]: ch2-〒h^——^ch2-ch^- -^ch2-ch^ -|ch2-ch cooyF2

COOYF2

COOYp COOY F2 rCH2-CH^-

COOYr

COOY F2

COOYF2 CH2"~CH

~^ch2-chVirC00YF2 Λ cooyF2 YF2oocy^:psco〇yF2 COOYF2 CH2 - CHj YF20,0C.丄 COOYF2

COOY*· As a specific example of the repeating unit (Gv3), for example, the following repeating unit. -18- 200832057 [化 20]

H CH3 F

I I I ch2==c ch2=c ch2=c ch2= C(CH3)3 C(CH3)3 C(CH3)3

The fluoropolymer (F) preferably contains 1 mol% or more of repeating units (Gvn) for all repeating units. The upper limit of the above repeating unit (Gvn) is not particularly limited, and is preferably 80% or less. The repeating unit (Gvn) having an acid-decomposable group is particularly preferably contained in an amount of 10 to 50 mol% for all repeating units. The fluoropolymer (F) may further contain at least one repeating unit selected from the group consisting of the following repeating unit (QV1), the following repeating unit (QV2), the following repeating unit (QV3), and the following repeating unit (Qv4); Cluster of repeating units (QVn). [chemical 21] rq rq R° R° Rq Rq

TQ :ch2+ o in (Qv4) (QV1) (Qv2) (Qv3)

The three RQs of the H repeat unit (Qvl) (Qv3) are hydrogen atoms. -19- 200832057 Imagine. The repeating unit (Qv4) is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. It is preferable that the repeating unit (Qvl) and (Qv2) have a q of 1. As a specific example of the repeating unit (QV 1 ), for example, the following compounds [Chemical 23⁄4]

Specific examples of the repeating unit (QV2), for example, the following compounds [Chem. 23]

As a specific example of the repeating unit (QV3), for example, the following compound W 匕 24]

-20- 200832057 As a specific example of the repeating unit (Qv4), for example, the following compound [Chem. 25] H CH3 F I I I ch2 = c ch2 = c ch2 = c

t I OH ch2=

OH

OH

=c I C=c I OH The fluoropolymer (F ) is preferably one unit of a repeating unit (Qvn) of 1 mol% or more for all repeating units. The upper limit of the above-mentioned repeating unit (QV η ) is not particularly limited to 80% by volume or less. The repeating unit (QVn) is particularly desirable for all repeating units to contain 10 to 50 mol%. The weight average molecular weight of the fluoropolymer (F) is preferably from 1 〇〇〇 to looooo, and more preferably from 1000 to 20,000. In this case, the photosensitive portion of the photoresist film in the developing step is easily removed. The fluoropolymer (F) is preferably a polymer having a narrow molecular weight distribution. The ratio of the weight average molecular weight (weight average molecular weight / number average molecular weight) to the number average molecular weight of the fluoropolymer (F) is preferably 2.2 or less, and particularly preferably 1.5 or less. The aforementioned lower limit is not particularly limited and is 1.0 or more. In this case, the fluoropolymer (F) is particularly easy to modulate high resolution and pattern due to its transparency and sensitivity to electron beams, X-rays, and EUV light, uranium resistance, and solubility in a developing solution. A well-formed photoresist composition. The fluoropolymer (F) having a narrow molecular weight distribution is preferably produced by living radical polymerization in which a monomer of repeating mono-21 - 200832057 (F) is formed. However, the living radical polymerization of the present invention not only refers to the activity of the polymerization terminal which maintains the polymerization of the monomer but undergoes radical polymerization, and refers to a species in which the polymerization terminal is inactivated and the polymerization terminal is activated. , while performing similar living polymerization. The living radical polymerization is carried out by a method using a reversible addition-cleavage chain transfer agent such as a thiocarbonylthio compound (for example, the method described in International Publication No. 9 9 8 / 0 0 1 4 8 8); A method of a radical scavenger such as a cobalt complex or an oxynitride; and an atom transfer radical polymerization method using a transition metal complex as a catalyst using an organic halide as an initiator is preferable. Preferred examples of the fluoropolymer (F) include, for example, a repeating unit (Fvn) and a repeating unit (Gvn), and include 5 to 50 mol% of repeating units (Fvn) for all repeating units. A fluoropolymer (F) comprising 10 to 80 mol% of repeating units (Gvn). The above-mentioned fluorine-containing polymer may further contain 5 to 50 mol% of the repeating unit (QVn) for all the repeating units. The repeating unit (Gvn) of the above fluoropolymer is preferably a repeating unit (GV1). In the case where the fluoropolymer contains a repeating unit (Qvn), the repeating unit (QVn) is preferably a repeating unit (Qv3) and/or a repeating unit (Qvl) having q of 1. Further, the weight average molecular weight of the fluoropolymer (F) is preferably from 10,000 to 3,000. The ratio of the weight average molecular weight (weight average molecular weight / number average molecular weight -22 - 200832057) to the number average molecular weight of the fluoropolymer (F) is preferably 2 or less, more preferably 1.5 or less. The acid generator of the present invention is a compound which generates an acid by an action of an electron beam, an X-ray, and an EUV light (hereinafter also referred to as a photoacid generator), and is usually irradiated by electron rays, X-rays, and EUV light. A compound that produces an acid due to chemical bond cleavage. The above compound may be a non-polymeric compound or a polymer compound j. The acid generator is not limited, such as dia ζ ο nium, phosphonium, suifonium, iodonium, imido sulfonate. ), oximesulfonate, diazodisulfone, disiilfone or o-nitrobenzyl sulfonate. The photoacid generator is preferably a compound which generates a sulfonic acid by irradiation with active light. As the above compounds, for example, a phosphonium salt, an iodine salt, an iminosulfonate, an anthracenesulfonate, a diazodiazine or a dioxime. Specific examples of the photoacid generator include, for example, diphenyl iodide mesylate, diphenyl iodine sulfonate, diphenyl iodine hexafluoroantimonate, diphenyl iodide dodecyl Benzene sulfonate, bis(4-butylphenyl) iodine mesylate, bis(4-butylphenyl)iodonium dodecylbenzenesulfonate, triphenylguanidine Sulfonate, triphenyl decanoate, triphenylsulfonium perfluorooctane sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium trifluoromethane Sulfonate, triphenyl-brain cerium salt, 1-(naphthylacetomethyl) thiolaniumtriflate, cyclohexylmethyl (2-oxocyclohexyl) Methanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium methanesulfonate, dimethyl-23- 200832057 (4-hydroxynaphthyl) anthracene tosylate, dimethyl (4-hydroxynaphthalene)鎏) Dodecylbenzenesulfonate, dimethyl (4-hydroxynaphthyl) anthracene naphthalenesulfonate, triphenyl camphorsulfonate, (4-hydroxyphenyl)benzylmethylhydrazine Tosylate, (4-methoxy) Phenyl iodide trifluoromethanesulfonate, bis(4-butylphenyl)iodotrifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine (triazine) , methoxyphenyl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-three-d, 1,1-bis(4-chlorophenyl)- 2,2,2 - trichloroethane, 4-13 benzopyrene, 2,4,6-trimethyltribenzamide, bis(phenylsulfonyl)methane, benzoin toluenesulfonic acid Salt, 1,8-naphthalene dicarboxylic acid imino methanesulfonate, and the like. The photoresist composition of the present invention preferably contains 0.1 to 20% by mass of an acid generator, and particularly preferably 0.1 to 10% by mass, based on the total mass of the fluoropolymer (F). When the photoresist composition of the present invention is used for lithography of electron beams, X-rays, and EUV light, it is usually used for coating on the surface of a substrate and drying to form a film, and it is preferably prepared into a liquid composition. The present invention provides a photoresist forming composition comprising the photoresist composition of the present invention and an organic solvent. The photoresist-forming composition of the present invention preferably contains an organic solvent of 1 〇 〇 1 1 〇 〇 〇 〇 by mass based on the total mass of the fluoropolymer (F). The organic solvent is not particularly limited as long as it is a solvent having high compatibility with the fluoropolymer (F) and the acid generator. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent containing no fluorine atom. -24- 200832057 Specific examples of organic solvents, such as alcohols such as methanol, ethanol, and diacetone alcohol; acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and N-methyl Ketones such as pyrrolidone and γ-butyrolactone; propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, carbitol acetate, methyl 3-methoxypropionate , 3-ethoxypropionic acid ethyl ester, β-methoxyisobutyric acid methyl ester, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, acetic acid 2-ethoxy B Ester, isoamyl acetate, methyl lactate, ethyl lactate and other esters; aromatic hydrocarbons such as toluene and xylene; propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoisopropyl Ethers such as ether, diethylene glycol monomethyl ether, diethylene glycol dicarboxylic acid, propylene glycol monomethyl ether; hydrazine, hydrazine, dimethyl carbamide, hydrazine, hydrazine, dimethyl acetamide, etc. . The method for forming a photoresist pattern in a lithography using electron beam, X-ray, and EUV light using the photoresist forming composition of the present invention is not particularly limited as a method of forming a photoresist pattern, for example, by sequentially After coating the photoresist forming composition of the present invention on the substrate, removing the organic solvent, forming a photoresist film formed by the photoresist composition of the present invention on the substrate; and performing electron lines on the photoresist film on the substrate, X a step of exposing the ray and the EUV light; and a step of removing the development of the photosensitive portion of the photoresist film; and a method of forming the photoresist pattern of the substrate on which the photoresist pattern is formed. In the above-described formation method, the heating step, the washing step, and the drying step can be further appropriately combined.

Moreover, the term "exposure" refers to the illusion of illuminating electron beams, X-rays, and ElJV-25-200832057 light. The substrate is not particularly limited, and examples thereof include a ruthenium-doped ruthenium-based substrate, a glass substrate, an ITO substrate, and a quartz substrate coated with chromium oxide. The developing step 'contacts the alkaline solution from the side of the photoresist film to the exposed portion of the photoresist film. Specific examples of the alkaline solution include, for example, an aqueous test solution selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine. EXAMPLES The present invention will be specifically described by way of examples, but the invention is not limited thereto. In the examples, the weight average molecular weight is denoted by Mw, the number average molecular weight is denoted by Μη, and the ratio of Μη to Mw is denoted by Mw/Mn. Azobisisobutyronitrile is referred to as AIBN, propylene glycol methyl ether acetate is referred to as PGMEA, tetrahydrofuran is referred to as THF, and polystyrene is referred to as PSt. A triphenyl sulfonium nonaflate which is a photoacid generator is used as an acid generator. For the production of a polymer, any of the following compounds is used. -26- 200832057 [化26]

OH 〇Si(CH3)2(C(CH3)3) (qv31) (qv11) (pqvH) - cleavage chain Further, as a reversible transfer agent using living radical polymerization, the following compound (X 1 ) was used. [化27]

The Mw and Μ of the polymer were measured using a gel permeation chromatography layer separation solvent: ΤΉ F, internal standard: p s t ). Specifically, a column for SEC (TSKgel SuperHZ-2000, 3 000 and 4 制 manufactured by TORAY Co., Ltd.) was used as 12 kinds of Mw495 to 1 1 1 000 of Mw/Mn having a different Mw of 1.15 or less. The internal phase (developing solvent: THF) for molecular weight measurement had a flow rate of 3535 ml/min and a degree of 40 °C. Analysis method (Exhibition. Trade name column, make PSt (from the standard. Move the column of temperature -27-200832057 [Example 1] fluoropolymer (F) manufacturing example [Example 1-1] polymer (1) The production example is a compound (fvu) (7.1 g), a compound (gvll) (3.00), a compound (qv31) (l.〇g), and a pressure-resistant reaction vessel (100 ml internal volume, made of glass). Toluene (25.8 g), followed by aIBN (〇_8g) as a polymerization initiator. After freezing and degassing in the reactor, the reactor was sealed, and the temperature in the reactor was 60 ° C for 18 hours. Then, the solution in the reactor was dropped into a house, and the obtained solid component was taken out and vacuum-dried at 8 Torr for 24 hours to obtain a white powdery amorphous polymer at 25 ° C ( 1) (8.1 g). The polymer (1) can be dissolved in toluene, acetone, THF, PGMEA, respectively. The polymer (1) has a Μη of 4,600, a Mw of 9000, and a Mw/Μη of 1.96. 1) As a result of analysis by 19F-NMR and 1H-NMR, it was confirmed that the polymer (1) contained 40 mol% of the following repeating order with respect to all repeating units. (FV11), 30 mol% of the following repeating unit (Gv 11), 30 mol% of the following repeating unit (qV31) fluoropolymer.

C(CF3)2OH 0CH(CH3)0CH2CH3 (F 11) (Gv11) (QV31) -28- 200832057 [Example 1-2] Production example of polymer (2) in a pressure-resistant reaction container (internal volume 30 ml, combined (fvll) (3.0g), compound (qv31) (7.8g), then placed in AIBN (0.3g) as a polyreactor to freeze degassing, the reactor sealing tube temperature was 60 ° C, and 18 The polymerization was carried out for a few hours. Then the solution was added dropwise to hexane, and the obtained solid component was taken out, and vacuum dried in vacuo to give white powdery compound (p2) (2.7 g) at 25 ° C. The polymer (P2) was divided into acetone. THF, PGMEA. In a round bottom flask (internal volume 50 ml, glass (p2) (2.0 g), methanol (l〇g), and then placed in a methanol solution of sodium hydroxide (2.2 g), The mixture was stirred for 8 hours in a nitrogen ° C flask, and then distilled off, and dehydrated THF (20 ml) 〇.26 g) was placed in a flask, and then reacted at 25 ° C for 12 hours. The solution inside was taken up, and the obtained solid component was taken out. The solid was dried under vacuum for 12 hours to obtain a white powder polymer (2) (1·8 g) at 25 °C. The compound (2) can be divided into acetone, THF, and PGMEA. The polymer (2) has a 1^11 of 5 8 00, and the 1^~ is 1·90 〇 glass) is added (〇.4g) and toluene. Initiator. The solution in the reactor was prepared by dissolving the amorphous polymorphism of 24 in the reactor at 80 ° C in toluene, and then placing it in a polymerization solution containing 6 mass % of the gas in a 25-in-bottle solution. Solvent ^ CH30CH2C1 (in order to remove the filtered droplets into the methane in the reaction), the final amorphous gender at 80 °c was dissolved in toluene, 1 1 0 0 0, M w/Mn -29-

200832057 The polymer (2) was subjected to 19F-NMR and 1 H-NMR, and it was confirmed that the polymer (2) was 28 mol% of the following repeating unit (Fv21) and 42 mol unit with respect to all the repetitions. (Fvll), 30 mol% of the repeating unit (Qv31). [C12] CH2 - CH^- (FV21) C(CF3)2〇CH2〇CH3 [Example 1-3] Production example of polymer (3) in a pressure-resistant reaction container (internal volume: 100 ml, glass) The compound (fv31) (1.5 g), the compound (gv31) (3.0 g) (qvll) (1.7 g) and toluene (5.0 g) were placed in 〇.8 g) as a polymerization initiator. After the reactor was freed and degassed, the reactor was sealed, and the retanning temperature was 60 ° C, and polymerization was carried out for 18 hours. Then, the anti-J® solution was dropped into hexane, and the obtained solid component was taken out, and dried under vacuum at 80 ° C for one hour to obtain a white powdery non-combined compound (3) (2.1 g) at 25 °C. The polymer (3) can be dissolved in the annual ketone, THF, PGMEA, respectively. The polymer (3) had a Μη of 5,200 and a Mw of 11,000, which was 2·12. The polymer (3) was subjected to 19F-NMR and 1 H-NMR, and it was confirmed that the polymer (3) was contained in the repeated fluorine-containing polyfluorene with respect to all of the repeating mono--30-analyzed elements. Compound AIBN (the following QV11 for the analysis of 24 crystallized polyphenylene and propylene M w/Mn ί1 in the i-device of I) has 19 mol% of the following repeating unit (fv31) ), 45 mol% repeats the following repeating unit (Gv31), 36 mol% of the following repeating unit (fluoropolymer).

[Example 1-4] A production example of the polymer (4) was used in a pressure-resistant reaction vessel (internal volume: 1 ml, glass) (fv31) (0.33 g), and compound (gv21) (pqvl 1 ) ( 1.6 g) and toluene (2.2 g), followed by O.Olg) and compound (x1) (0.004 g) as a polymerization initiator in the reactor. After the degassing in the reactor, the reactor was sealed to a reaction temperature of 60. At room temperature, the living radical polymerization was carried out for 18 hours. The solution in the reactor was dropped into methanol, and the obtained solid was taken out and dried under vacuum at 8 ° C for 24 hours to obtain a peach-colored non-crystalline polymer (P4) (2.8 g) at 25 °C. The reaction of the glass was carried out into a polymer () (2.8 g) and THF (10 ml), followed by a 1.0 mol/L solution of tetrabutylammonium fluoride in THF (25 m to make the temperature in the reactor 25 The polymerization was carried out for 4 hours at ° C. Then, the solution and the solution were dropped into water, and the obtained solid was taken back to 80. (: Vacuum drying was performed for 24 hours, and a tea-like amorphous polymer was obtained at 25 ° C. (4) (1.8g). Polymer (4) Put in, compound AIBN (〇: after the device: will be divided into the end of the k-shaped device: put in the liter), body color The powder can be dissolved in toluene, acetone, THF, pgmEA, respectively, from -31 to 200832057. Polymer (Ο 为 is 8800, Mw is 1 2000, Mw/Mn is 1 · 3 6 〇 Polymer (4 ) is 19F_NMR and 1 As a result of analysis by H-NMR, it was confirmed that the polymer (4) contained 9 mol% of the repeating unit (Fv31) and 46 mol% of the following repeating unit (Gv21), 45 mol with respect to all the repeating units. Ear % of repeating unit (Qvn) i fluoropolymer.

[Example 1-5 (Comparative Production Example)] A production example of a polymer (〇) was placed in a pressure-resistant reaction container (inner volume 10 (ml), glass), and a compound (gV31) (3.0 g) and a compound (qv31) were placed. (〇8g), compound (qVll) (1.7g) and toluene (10g), followed by AIBN (〇.6g) as a polymerization initiator. After deaeration in the reactor, the reactor was sealed, and the temperature in the reactor was maintained at 60 ° C for 18 hours. Then, the solution in the reactor was dropped into hexane, and the obtained solid component was taken out, and vacuum-dried at 8 〇〇c for 24 hours to obtain a white powdery amorphous polymer at 25 ° C (c). (3.5g). The polymer (c) can be dissolved in toluene, acetone, THF, PGMEA 〇-32- 200832057, the water inlet (c) is 7300' Mw is 12000, M w / η η is 1 · 64 °, and the polymer (c) As a result of analysis by 1H-NMR, it was confirmed that the polymer (c) contained 33 mol% of repeating units (Qvn) and 42 mol% of repeating units (Gv31), 25 mol with respect to all repeating units. Polymer of the repeat unit (Qv3i) of % by ear. [Example 2] Example of exposure evaluation of EUV light A polymer (1) (1 g) and an acid generator (〇.ig) were dissolved in PGMEA (20 g), and the resulting solution was passed through a filter having a pore size of 0.2 // m ( Filtration was carried out to obtain a photoresist forming composition (1). The photoresist forming composition (1) was spin-coated on a ruthenium substrate surface-treated with hexamethyldioxane, and the ruthenium substrate was heated at 100 ° C for 90 seconds to obtain a composition having a photoresist formation ( 1) The formed resist film (film thickness 0.15 / / m) of the cut substrate. The EUV light having an exposure intensity of 0.1, 0.5, 1, 2, 3, 5, 8, 10 mJ/cm 2 was exposed to each specific portion of the photoresist film of the ruthenium substrate. For the exposure of EUV light, EUVES-7000 manufactured by Litho Tech Japan Co., Ltd. was used. Then, the sand substrate was heated at 1 〇 〇 ° C for 90 seconds, and an alkaline solution was used to develop the photoresist film to remove the photoresist film which was exposed to EUV light. Next, the residual film thickness of the photoresist film was measured in accordance with the difference in exposure intensity of the exposed EUV light. Further, in addition to the use of the polymer (c) in place of the polymer (1), the EUV exposure test was carried out in the same manner as in -33-200832057. Each EUV exposure test was measured, and the exposure intensity of different exposed EUV light's photoresist residual thickness (unit: nm) was shown in 袠1. [Table 1] Exposure intensity of exposed EUV light (mJ/cm2) Residual film thickness of photoresist Resin polymer film forming photoresist film (1) Polymer (C) 0 (unexposed) 150 150 0.1 84.2 149.5 0.5 0 146.5 1 0 144 2 0 140 3 0 130 5 0 129 8 0 0 10 0 0

Further, in the case where the EUV exposure test is carried out in the same manner except that the polymer (2), (3) or (4) is used instead of the polymer (1), the photoresist film is completely sensitized and removed by development. The exposure intensity of the EUV light is 1.0 mJ/cm2 or less. From the above results, a photoresist film comprising a fluoropolymer (polymers (1) to (4)) having a repeating unit having a fluorine-containing aromatic ring structure, and a polymer not containing the above repeating unit are known. Compared with the photoresist film formed by (polymer (c)), it can be completely sensitized by low-intensity EUV light, and has high sensitivity to EUV light. -34-200832057 [Example 3] Evaluation example of etching resistance The polymer (1) (lg) was dissolved in PGMEA (15 g), and the obtained solution was filtered through a filter (PTFE type) having a pore size of 0.2://m. Polymer solution. The polymer solution was spin-coated on the ruthenium substrate ', and the ruthenium substrate was heated at 100 Torr for 90 seconds to obtain a ruthenium substrate having a film (film thickness 〇 2 # m) of the polymer (1) _. Next, the feed rate test of the tantalum substrate was performed to measure the etching rate of the film of the polymer (1 φ ). The etching test was carried out using a RIE-10NR manufactured by SAMCO Co., Ltd. (etching conditions: pressure · 2 Pa, etching gas: CF4 (80% by volume), and 〇 2 (20% by volume). 7 0 W, time · · 60 seconds). Using the film of polymer (c) or poly-p-hydroxystyrene (Mw8000), replacing the polymer (1), the same etching test was carried out to determine the etch rate of the polymer (c) and the poly-p-hydroxystyrene (unit : nm / min) 〇 φ The etching rate ratio of the polymer (1) or the polymer (c) with respect to the etching rate of polyparaphenylene styrene is shown in Table 2. [Table 2] Etching speed ratio of polymer to polystyrene styrene at a hungry speed: .. _ polymer (1) 1.13 a polymer (c) 1.15 Moreover, except for using polymers (2), (3 Or (4) in place of the polymerization -35 " 200832057 (1), in the same manner as the etching test, the polymer (2), (3) or (relative to the etching rate of polypara-hydroxystyrene) 4) The etching speed ratio is about 1.1. From the above results, it was found that a fluorine-containing polymer (polymers (1) to (4)) having a repeating unit having a fluorine-containing "aromatic ring structure" has sufficient tentacle resistance. INDUSTRIAL APPLICABILITY According to the present invention, there is provided a photoresist composition excellent in resolution and etching resistance for electron beams, X-rays, and EUV light used in lithography using electron beams, X-rays, and EUV light. . The photoresist composition of the present invention satisfies a good pattern shape and line edge roughness due to high sensitivity and high resolution (the edge between the pattern formed by the photosensitive photoresist material and the substrate interface, perpendicular to the line direction) A positive resist composition in which the direction is changed, and the edge has a concavity and convexity from the upper side of the figure. By using the photoresist composition of the present invention, a very fine pattern can be formed by the aforementioned lithography. In addition, 'the Japanese Patent Application No. 2006-278841 filed on Oct. 12, 2006, and the Japanese Patent Application No. 2007- 151 687, filed on Jun. The entire contents of the disclosure are taken as the disclosure of the specification of the present invention. -36-

Claims (1)

200832057 X. Patent Application No. 1 · A photoresist composition used in lithography using electron beam, X-ray or EUV light, characterized by containing: a repeating unit having a fluorine-containing aromatic ring structure containing a side chain (F The role of the acid, the fluoropolymer (F) which increases the solubility of the base; and the compound which produces the acid. 2. The photoresist composition according to claim 1, wherein the repeating unit (F) is a repeating unit represented by the following formula (Fv), [Chemical Formula 1] The symbol in the formula indicates the following meaning, RF • indicates a hydrogen atom, a halogen atom, a methyl group or a halomethyl group, and three RFs may be the same or different, and YF: an acid atom or an acid decomposition of 1 to 20 carbon atoms. The base, p, q and r are each independent, representing an integer of 〇5, and the sum of p, q and r is an integer of 1 to 5. 3. The photoresist composition according to claim 1 or 2, wherein the repeating unit (F) is at least one selected from the group consisting of the following formula (Fvl), the following formula (Fv2), and the following formula (FV3) Group of repeating units (Fvn), -37- 200832057 The symbols in the formula indicate the following meanings rl, r2, and ql: each is an integer of 1 to 3 independently, and YF 2 is an acid-decomposable group having 1 to 2 carbon atoms. 4. The photoresist composition according to any one of claims 1 to 3, wherein the fluoropolymer (F) has a weight average molecular weight of 1,000 to 10,000,000 ° 5 · as claimed in claim 1 The photoresist composition according to any one of the items 4 to 4, wherein the ratio of the weight average molecular weight to the number average molecular weight of the fluoropolymer (F) is 2.2 or less. The photo-resist composition of any one of the first to fifth aspects of the present invention, wherein the ratio of the molecular weight of the number average molecular weight of the fluoropolymer (F) is 1.5 or less. 7. The photoresist composition according to any one of claims 1 to 6, wherein the fluoropolymer (F) further contains at least one selected from the group consisting of the following formula (Gvl • ), butyl (GV2), and Repeat unit (G%) in a group of repeating units represented by formula (Gv3), -38- 200832057 The symbol in the formula indicates the following meaning, RG: represents a hydrogen atom, a halogen atom, a methyl group or a halomethyl group, and three R0" may be the same or different, 1^: a hydrogen atom, a halogen atom, a methyl group or a halomethyl group. ZQ and: each independently is an acid-decomposable group having 1 to 20 carbon atoms, and g is an integer of 1 to 4. 8. The photoresist composition according to any one of claims 1 to 7, wherein the fluoropolymer (F) further contains at least one selected from the group consisting of the following formula (Qvl), the following formula (QV2), and the following formula ( Qv3) and the repeating unit (Q%) of the repeating unit represented by the following formula (Qv4), -39- 200832057 TQ : hydrogen atom, halogen atom, methyl group or halomethyl group, q: an integer of 1 to 4. The photo-resist composition of any one of claims 1 to 8 wherein the compound which produces the acid is diazonium, phosphonium, sulfonium, iodine. Key salt (iodonium), imidosulfonate, oximesulfonate, diazodisulfone, disulfone or o-nitrobenzyl sulfonate, relative to fluorine The total mass of the polymer (F), the acid-producing compound containing 0.1 to 20% by mass 〇1 〇. A photoresist forming composition used in lithography using electron beam, X-ray or EUV light, characterized by A photoresist composition and an organic solvent according to any one of claims 1 to 9 of the patent application. 11. The photoresist forming composition according to claim 10, wherein the organic solvent is an alcohol compound, a ketone compound, an ester compound, an aromatic hydrocarbon compound, an ether compound or a guanamine compound. -40 - 200832057 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3-