CN1853141A - Compound for resist and radiation-sensitive composition - Google Patents

Compound for resist and radiation-sensitive composition Download PDF

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CN1853141A
CN1853141A CN 200480026859 CN200480026859A CN1853141A CN 1853141 A CN1853141 A CN 1853141A CN 200480026859 CN200480026859 CN 200480026859 CN 200480026859 A CN200480026859 A CN 200480026859A CN 1853141 A CN1853141 A CN 1853141A
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小黑大
越后雅敏
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Mitsubishi Gas Chemical Co Inc
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Abstract

A compound represented by the following formula (1): (1) wherein R<1>, R<2>, R<4>, R<5>, m0 to m2, and n0 to n2 are as defined in the description. Also provided is a radiation-sensitive composition which contains the compound of the formula (1) as a major component of the solid ingredients. The composition is excellent in sensitivity, resolution, heat resistance, etching resistance, and solvent solubility.

Description

Compound against corrosion and radiation-sensitive composition
Technical field
The present invention relates to be suitable for the compound against corrosion with special chemical structure of the non-polymeric erosion resistant of doing the acid amplification.The invention still further relates to the radiation-sensitive composition that comprises this compound and acid agent.The present invention's compound against corrosion is used to form the radiation-sensitive materials of mask etc. etc. in producing radiosensitive electronic component such as for example ultraviolet ray, far ultraviolet, Extreme Ultraviolet (EUV), electron beam and X-ray such as LSI and VLSI.
Background technology
Conventionally known erosion resistant normally can form the polymeric material of amorphous thin film.For example, form film against corrosion, form the linear pattern of the about 0.08 μ m of live width then with irradiation such as ultraviolet ray, far ultraviolet, electron beam, X-rays at the solution of coating polycarboxylated styrene derivant in solvent on the base material.
Known polymer-type erosion resistant has up to about 10 000 to 100 000 molecular weight and bread molecular weight distribution, and polymer chain tangles mutually.Thereby, to use in the meticulous imprint lithography of polymer-type erosion resistant, uneven causing of patterned surfaces is difficult to control pattern dimension, thereby product yield is descended and the transistor characteristic variation.Therefore, use traditional lithography technique of known polymer type erosion resistant can not be used to produce the fine pattern of 0.06 μ m or littler live width.For producing meticulousr pattern, various erosion resistant with low-molecular-weight and Narrow Molecular Weight Distribution has been proposed.
Known non-polymeric erosion resistant for example comprises: positivity or negative resist that (1) is derived by fullerene, (2) positivity and the negative resist of deriving by calixarenes, (3) by the positive corrosion-resisting agent of starlike compound deriving, (4) positive corrosion-resisting agent of deriving by dendritic, (5) positive corrosion-resisting agent of deriving by dendritic/calixarenes, (6) by the positive corrosion-resisting agent of highly branched starlike compound deriving and (7) positive corrosion-resisting agent by the starlike compound deriving that contains ester bond that mainly constitutes with the trimesic acid structure.
Erosion resistant (1) is though corrosion stability is good, and coating and susceptibility do not reach realistic scale (JP7-134413A, JP9-211862A, JP10-282649A, JP11-143074A and JP11-258796A).The corrosion stability of erosion resistant (2) is fabulous, but can not form satisfied pattern (JP11-72916A, JP11-322656A and JP9-236919A) because of poorly soluble in developer solution.The poor heat resistance of erosion resistant (3), thereby be tending towards causing image fault (JP2000-305270A, JP2002-99088A and JP2002-99089A) in the heat treatment process after exposure.Erosion resistant (4) needs complicated production technology and because of in the heat treatment process of poor heat resistance after exposure image fault taking place, thereby impracticable (" Proceedingsof SPIE ", vol.3999 (2000), pp.1202-1206).Erosion resistant (5) needs complicated production technology and cost of material height, thereby impracticable (JP2002-49152A and JP2003-183227A).Erosion resistant (6) needs complicated production technology, the cost of material height, and use the metallic catalyst that is unfavorable for semiconductor production, thereby impracticable.Image fault may take place in the heat treatment process after exposure in the poor heat resistance of erosion resistant (7), and with the poor adhesion of base material, thereby impracticable (JP2002-328466A).
Also disclose with the adjuvant of low molecular compound as photosensitive resin composition.The composition that has proposed comprises: photosensitive resin composition, the light-sensitive compound (JP2002-363123A) of the hydrophilic radical of the protecting group protection of include the hydrophobic grouping that is selected from alkyl and heterocyclic radical or binding groups, dissociating when also having by illumination; The resist composition comprises the low molecular melting inhibitor (JP2001-312055A) that two or more triphenyl methane structure is arranged except that the part the group that dissociates under the acid effect; The resin combination against corrosion (JP2004-137262A) that includes fluorene structured light-sensitive compound.But comprise the The compounds of this invention described later as the composition of key component from unexposed mistake.Because known resist composition contains resin, is not enough to be used for practical application by its corrosion-resisting pattern line limit unevenness ambassador said composition that forms.In addition, comprising known compound against corrosion exists following problem one of at least as the composition of key component: because of the crystallinity height causes film forming poor; Thermotolerance is low can not to stand semiconductor technology; Said composition is insoluble in the acceptable safety solvent of semiconductor factory such as propylene glycol monoethyl ether acetate and ethyl lactate; With with the adhesiveness deficiency of base material.Thereby known compound against corrosion is not suitable for independent use.
Summary of the invention
One of purpose of the present invention provides for example from radiosensitive compounds such as excimer laser, Extreme Ultraviolet (EUV), electron beam and the X-rays of KrF with the radiation-sensitive composition that comprises this compound is provided.Another object of the present invention provides the straightforward procedure that a kind of production has the non-polymeric radiation-sensitive composition of high sensitive, high resolving power, high-fire resistance, high corrosion stability and good solvent soluble.
Through extensive studies, the inventor finds to have the compound of special chemical structure and comprises this compound compositions and can realize above-mentioned purpose.
Therefore, the invention provides a kind of radiation-sensitive composition, comprise the solid constituent of 1-80 weight % and the solvent of 20-99 weight %, said composition contains the compd B that requires a and b below satisfying:
(a) have by by the aromatic ketone or the aromatic aldehyde that each have 5 to 45 carbon atoms and have introduce at least one phenolic hydroxyl of the polyphenolic substance A that the compound condensation reaction of 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl produces structure that acid dissociation functional group forms and
(b) has 300 to 3 000 molecular weight;
And the total amount of compd B and solubilizer (solubility improver) accounts for the 50-99.999 weight % of solid constituent gross weight.
The invention still further relates to compound shown in the following formula 1:
Figure A20048002685900121
Each R wherein 1Base is independently for being selected from the acid dissociation functional group of substituent methyl, 1-replacement ethyl, 1-replacement n-pro-pyl, 1-branched-alkyl, silicyl, acyl group, 1-substituted alcoxyl ylmethyl, cyclic ethers base and alkoxy carbonyl group;
Each R 2Base is independently for being selected from the group of halogen atom, alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkenyl (alkyenyl), acyl group, alkoxy carbonyl group, alkanoyloxy, aryl acyloxy, cyano group and nitro;
R 4Be hydrogen atom, C 1-6Alkyl or aryl, R 5For having the monovalence C of biphenyl structural or naphthalene structure 10-18Group, perhaps R 4With R 5Bonding time-CR each other 4R 5-can be have fluorene structured, acenaphthene structure, the divalence C of 1-ketone group acenaphthene structure or benzophenone structure 10-18Group;
Respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 3 integer of m0 and n0, m1 and n1,
Respectively do for oneself 0 to 4 integer of m2 and n2 all satisfies following formula: 1≤m0+m1+m2≤5,1≤n0+n1+n2≤5,1≤m1+n1≤6,1≤m0+m1≤3 and 1≤n0+n1≤3; With
Being positioned at-CR of two phenyl ring 4R 5-two carbon atoms at ortho position can form xanthene structure or thioxanthene structure shown in the following formula 2 by the mutual bonding of oxygen atom or sulphur atom:
R wherein 1, R 2, R 4And R 5Identical with the front; Respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 2 integer of respectively do for oneself 0 to 2 integer of p0 and q0, p1 and q1, p2 and q2 all satisfies: 1≤p0+p1+p2≤4,1≤q0+q1+q2≤4,1≤p1+q1≤4,1≤p0+p1≤2 and 1≤q0+q1≤2; With X be oxygen atom or sulphur atom.
Preferred forms
Describe the present invention below in detail.
Radiation-sensitive composition of the present invention comprises the solid constituent of 1-80 weight % and the solvent of 20-99 weight %.This radiation-sensitive composition contains the compd B that requires a and b below satisfying:
(a) have by by the aromatic ketone or the aromatic aldehyde that each have 5 to 45 carbon atoms and have introduce at least one phenolic hydroxyl of the polyphenolic substance A that the compound condensation reaction of 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl produces structure that acid dissociation functional group forms and
(b) has 300 to 3000 molecular weight.The total amount of compd B and solubilizer accounts for the 50-99.999 weight % of solid constituent gross weight.
Compd B (compound against corrosion) preferably has conjugated structure, comprises at least two phenyl ring and/or heteroatomic nonbonding electron pair.This conjugated structure is arranged, and compd B can improve film forming, improves corrosion stability, reduces the air output that is subjected between radiation era and pass through its sensibilization raising susceptibility.The energy part that sensibilization is attributable to radiation such as electron beam is for example absorbed by conjugated structure and absorbed energy is transferred to acid agent effectively.
The example of conjugated structure comprises biphenyl structural, naphthalene structure, fluorene structured, the anthracene structure, luxuriant and rich with fragrance structure, the pyrene structure, benzopyran structure, the acenaphthene structure, the acenaphthene structure, 1-ketone group acenaphthene structure, the benzophenone structure, the xanthene structure, the thioxanthene structure, the flavones structure, the isoflavones structure, the dihydroindene structure, the indenes structure, the indacene structure, the phenalene structure, the biphenylene structure, the coronene structure, the  structure, the trinaphthylene structure, the hexaphene structure, the hexacene structure, the rubicene structure, the fluoranthene structure, acephenanthrylene structure perylene structure Pi structure, the pentaphene structure, the heptaphene structure, the heptacene structure, the pyranthrene structure, the phenacene structure, the aphthacene structure, the pentacene structure, the aceanthrene structure, luxuriant and rich with fragrance structure, the acephenanthrene structure, the Azulene structure, the benzophenanthrene structure, p-terphenyl structure, m-terphenyl structure, 1,3,5-triphenylbenzene structure, 1,2,3-triphenylbenzene structure, 1,2,4-triphenylbenzene structure, the phenylnaphthalene structure, the phenylnaphthalene structure, the binaphthalene structure, with the ovalene structure, be selected from biphenyl structural, naphthalene structure, fluorene structured, the anthracene structure, the pyrene structure, the acenaphthene structure, 1-ketone group acenaphthene structure, the benzophenone structure, the xanthene structure, with at least a structure of thioxanthene structure be particularly preferred because their available lower-cost initial compounds are introduced in compd B.
Compd B (compound against corrosion) is preferably at least a compound that is selected from compound shown in the following formula 1:
In the formula 1, each R 1Base is independently for being selected from the acid dissociation functional group of substituent methyl, 1-replacement ethyl, 1-replacement n-pro-pyl, 1-branched-alkyl, silicyl, acyl group, 1-substituted alcoxyl ylmethyl, cyclic ethers base and alkoxy carbonyl group.
The example of substituent methyl comprises methoxy, methylthiomethyl, ethoxyl methyl, ethylmercapto group methyl, methoxy ethoxy methyl, benzyloxymethyl, benzylthio methyl, phenacyl, 4-bromobenzene formyl methyl, 4-methoxybenzoyl methyl, piperonyl, methoxycarbonyl group methyl, ethoxycarbonylmethyl group, the positive third oxygen carbonyl methyl, the different third oxygen carbonyl methyl, positive butoxy carbonyl methyl and tertiary butyloxycarbonyl ylmethyl.
The example that 1-replaces ethyl comprises 1-methoxy ethyl, 1-methylmercaptoethyl, 1,1-dimethoxy-ethyl, 1-ethoxyethyl group, 1-ethylmercapto group ethyl, 1,1-diethoxy ethyl, 1-phenoxy group ethyl, 1-thiophenyl ethyl, 1,1-two phenoxy group ethyls, 1-cyclopentyloxy ethyl, 1-cyclohexyloxy ethyl, 1-phenylethyl and 1, the 1-diphenyl-ethyl.
The example that 1-replaces n-pro-pyl comprises 1-methoxyl n-pro-pyl and 1-ethoxy n-pro-pyl.
The example of 1-branched-alkyl comprises isopropyl, sec-butyl, the tert-butyl group, 1,1-dimethyl propyl, 1-methyl butyl and 1,1-dimethylbutyl.
The example of silicyl comprises trimethyl silyl, ethyl dimetylsilyl, methyl diethylsilane base, triethylsilyl, t-butyldimethylsilyl, tert-butyl group diethylsilane base, t-butyldiphenylsilyl, tri-tert silicyl and triphenyl silicyl.
The example of acyl group comprises acetyl group, phenoxy group acetyl group, propiono, bytyry, heptanoyl group, caproyl, valeryl, valeryl, isovaleryl, lauroyl, adamantyl (adamantyl), benzoyl and naphthoyl.
The example of 1-substituted alcoxyl ylmethyl comprises 1-cyclopentyl methoxy, 1-cyclopentyl ethoxyl methyl, 1-cyclohexyl methoxy, 1-cyclohexyl ethoxyl methyl, 1-ring octyl group methoxy and 1-adamantyl methoxy.
The example of cyclic ethers base comprises THP trtrahydropyranyl, tetrahydrofuran base, tetrahydro thiapyran base, tetrahydro-thienyl, 4-methoxyl THP trtrahydropyranyl and 4-methoxyl tetrahydro thiapyran base.
The example of alkoxy carbonyl group comprises methoxycarbonyl group, carbethoxyl group, the positive third oxygen carbonyl, the different third oxygen carbonyl, positive butoxy carbonyl and tertbutyloxycarbonyl.
In these acid dissociation functional groups, preferably tertbutyloxycarbonyl, tertiary butyloxycarbonyl ylmethyl, 1-methoxy ethyl, 1-ethoxyethyl group, 1-cyclohexyloxy ethyl, 1-phenylethyl, the tert-butyl group, trimethyl silyl, THP trtrahydropyranyl and 1-cyclohexyl methoxy.
Each R 2Base is independently for being selected from the group of halogen atom, alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkenyl (alkyenyl), acyl group, alkoxy carbonyl group, alkanoyloxy, aryl acyloxy, cyano group and nitro.
The example of halogen atom comprises chlorine atom, bromine atoms and iodine atom; The example of alkyl comprises C 1-4Alkyl such as methyl, ethyl, propyl group, n-pro-pyl, normal-butyl, isobutyl, sec-butyl and the tert-butyl group; The example of naphthenic base comprises cyclohexyl, norborny and adamantyl; The example of aryl comprises phenyl, tolyl, xylyl and naphthyl; The example of aralkyl comprises benzyl; The example of alkoxy comprises C 1-4Alkoxy such as methoxyl, ethoxy, hydroxy ethoxy, propoxyl group, propoxyl, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; Examples of aryloxy comprises phenoxy group; The example of alkenyl comprises C 2-4Alkenyl such as vinyl, propenyl, allyl and butenyl group; The example of acyl group comprises C 1-5Aliphatic acyl such as formoxyl, acetyl group, propiono, bytyry, valeryl, isovaleryl and valeryl and aromatic acyl group such as benzoyl and toluyl groups; The example of alkyl oxy carbonyl oxygen comprises C 2-5Alkyl oxy carbonyl oxygen such as methoxy carbonyl oxygen base, ethoxy carbonyl oxygen base, the third oxygen carbonyl oxygen base, the different third oxygen carbonyl oxygen base, positive fourth oxygen carbonyl oxygen base, isobutyl oxygen carbonyl oxygen base, Zhong Ding oxygen carbonyl oxygen base and tertiary butyloxycarbonyl oxygen base; The example of alkanoyloxy comprises acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, penta acyloxy, isoamyl acyloxy and new pentane acyloxy; Comprise benzoyloxy with the example of aryl acyloxy.
Be positioned at the R at the ortho position of phenolic hydroxyl 2Be preferred, because the crystallinity of its control compd B is improved film forming.Be positioned at the R at the ortho position of phenolic hydroxyl 2Also control compd B in alkaline-based developer solubleness and reduce the introducing degree of acid dissociation functional group in the phenolic hydroxyl, thereby improve solubility in solvent, with the adhesiveness and the resist susceptibility of base material.For obtaining these effects, R 2Be preferably huge and/or electron donating group, for example alkyl such as methyl, ethyl, isopropyl, the tert-butyl group, phenyl, benzyl, cyclohexyl, norborny and adamantyl; With alkoxy such as methoxyl, ethoxy, isopropoxy and phenoxy group.Under some situation, electron withdraw group such as halogen improve the solubleness of compd B in alkaline-based developer.
R 4Be hydrogen atom, C 1-6Alkyl or aryl, R 5For the monovalence C of biphenyl structural or naphthalene structure is arranged 10-18Group.
Be used for R 4C 1-6The example of alkyl comprises straight chain, side chain or naphthenic base such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, hexyl and cyclohexyl.Be used for R 4Aryl can be phenyl.
R 5Be preferably the univalent perssad of biphenyl structural that following formula is shown with or naphthalene structure:
Figure A20048002685900161
Or
R wherein 3Be hydrogen atom or C 1-6Alkyl; P3 is 0 to 4 integer; Q3 is 0 to 3 integer; And p3 and the satisfied 0≤p3+q3 of q3≤7.C 1-6Alkyl is selected from R 4Described alkyl.
-CR 4R 5-R 4And R 5Bonding is formed with the divalence C of fluorene structured, acenaphthene structure, 1-ketone group acenaphthene structure or benzophenone structure each other 10-18Group, divalent group shown in the preferred following formula:
Figure A20048002685900171
Or
R wherein 3, p3 is defined identical with the front with q3, Y is singly-bound or carbonyl, Z is methylene or carbonyl.
Respectively do for oneself 0 to 4 integer of respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 3 integer of m0 and n0, m1 and n1, m2 and n2 satisfies 1≤m0+m1+m2≤5,1≤n0+n1+n2≤5,1≤m1+n1≤6,1≤m0+m1≤3 and 1≤n0+n1≤3.
In the formula 1, just-CR 4R 5-two carbon atoms being positioned at the ortho position of two phenyl ring can form xanthene structure or thioxanthene structure shown in the following formula 2 by the mutual bonding of oxygen atom or sulphur atom:
Figure A20048002685900173
R wherein 1, R 2, R 4And R 5Defined identical with the front; Respectively do for oneself 0 to 2 integer of p0 and q0; Respectively do for oneself 0 to 2 integer of p1 and q1; Respectively do for oneself 0 to 3 integer of p2 and q2; Satisfy 1≤p0+p1+p2≤4,1≤q0+q1+q2≤4,1≤p1+q1≤4,1≤p0+p1≤2 and 1≤q0+q1≤2; With X be oxygen atom or sulphur atom.
Film forming, thermotolerance and anti-dry corrosion are fabulous though formula 1 compound molecular weight is low, and air output is little.Thereby the resist compositions display that comprises this compound goes out high resolving power, high sensitive and very little line edge unevenness.
Compd B is preferably at least a compound that is selected from compound shown in following formula 3 and the 5-12.
Formula 3
Figure A20048002685900181
R wherein 1, R 2, R 4, R 5, m2 is defined identical with the front with n2, just-CR 4R 5-two carbon atoms being positioned at the ortho position of two phenyl ring can form xanthene structure or thioxanthene structure shown in the following formula 4 by the mutual bonding of oxygen atom or sulphur atom:
Figure A20048002685900182
R wherein 1, R 2, R 4, R 5, X, p2 be defined identical with the front with q2.
Formula 3 compounds are fit to actual the use because of lower with the adhesiveness of base material, dissolubility in solvent and good heat resistance and raw materials cost very much.
Formula 5:
Figure A20048002685900183
R wherein 1To R 4, m0 to m2, n0 to n2, p3 be defined identical with the front with q3.
Formula 6:
Figure A20048002685900184
R wherein 1To R 4, m0 to m2, n0 to n2, p3 be defined identical with the front with q3.
Formula 7:
R wherein 1To R 3, Y, m0 to m2, n0 to n2, p3 be defined identical with the front with q3.
Formula 8:
Figure A20048002685900192
R wherein 1To R 3, Z, m0 to m2, n0 to n2, p3 be defined identical with the front with q3.
Formula 9:
Figure A20048002685900193
R wherein 1To R 4, p0 to p3 is defined identical with the front with q0 to q3.
Formula 10:
Figure A20048002685900201
R wherein 1To R 4, p0 to p3 is defined identical with the front with q0 to q3.
Formula 11:
R wherein 1To R 3, Y, p0 to p3 be defined identical with the front with q0 to q3.
Formula 12:
Figure A20048002685900203
R wherein 1To R 3, Z, p0 to p3 be defined identical with the front with q0 to q3.
Produce in the compd B, produce polyphenolic substance A by aromatic ketone or aromatic aldehyde that each has 5 to 45 carbon atoms and the compound condensation that 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl are arranged earlier.In at least one phenolic hydroxyl of polyphenolic substance A, introduce acid dissociation functional group then and produce compd B.
There are the aromatic ketone of 5 to 45 carbon atoms or the example of aromatic aldehyde to comprise acetophenone, benzophenone, α-acetonaphthone, β-Nai Yitong, the 9-Fluorenone, acenaphthenone, benzoquinones, naphthoquinones, anthraquinone, acenaphthene quinone, benzoyl biphenyl, the benzoyl naphthalene, acyl group biphenyl, the acyl group anthracene, the acyl group phenanthrene, the acyl group phenothiazine, the acyl group pyrene, the acyl group benzopyrene, acylindacene, acylphenacene, the acyl group acenaphthene, the acyl group aphthacene, the acyl group pentacene, the acyl group benzophenanthrene, acyl pyridine, acylimidazole, the acyl group furans, acyl pyrroline, the acyl group ovalene, indenone, tetralone, the acyl group thiazole, acridone, flavones, and isoflavones; And aromatic aldehyde such as benzaldehyde, tolyl aldehyde, anisaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, anthracene aldehyde, biphenyl aldehyde, formyl fluorenes, formyl biphenyl, formyl anthracene, formyl phenanthrene, formyl phenothiazine, formyl pyrene, formyl benzopyrene, formylindacene, formylphenacene, formyl acenaphthene, formyl aphthacene, formyl pentacene, formyl benzophenanthrene, formylpyridine and formyl ovalene.
In the above-claimed cpd; particularly preferably be α-acetonaphthone, β-Nai Yitong, 9-Fluorenone, acetyl group anthracene, acetyl group pyrene, acenaphthenone, acenaphthene quinone, anthraquinone, 1-naphthaldehyde and 4-biphenyl aldehyde because they easily with low cost obtain, reactive higher and easily produce polyphenolic substance A.
There is the example of the compound of 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl to comprise phenol, (C 1-6-alkyl) phenol (for example cresols such as orthoresol, metacresol and paracresol, o-phenyl phenol, with the 2-cyclohexylphenol), dialkyl group phenol (for example 2, the 3-xylenol, 2, the 5-xylenol, 2, the 6-xylenol, with 2, the 6-DI-tert-butylphenol compounds), trialkyl phenol, alkoxy phenol (for example anisole such as o-methoxyphenol), aryl phenol (for example phenylphenol such as o-phenyl phenol and a phenylphenol), naphthenic base phenol (for example 2-cyclohexylphenol), halophenol (chlorophenol for example, two chlorophenols, chloreresol, bromine phenol, dibromophenol), and polyhydric phenol (catechol for example, the alkyl catechol, the chloro catechol, resorcinol, alkyl-resorcin, quinhydrones, the alkyl quinhydrones, the chloro resorcinol, chlorohydroquinone, 1,2,3,-thrihydroxy-benzene, the alkyl 1,2,3,-thrihydroxy-benzene, phloroglucin, with 1,2,4-three oxybenzene phenol).These compounds can use separately, also can two or multiple being used in combination.Its purity is generally, but is not limited to 95 weight % or higher, preferred 99 weight % or higher.
In the above-mentioned compound that 1 to 3 phenolic hydroxyl arranged, preferably phenol, (C 1-6-alkyl) phenol 2-(C for example 1-6-alkyl) phenol (orthoresol, o-phenyl phenol, 2-cyclohexylphenol etc.), catechol, resorcinol and 1,2,3,-thrihydroxy-benzene are because their easy acquisitions.Use the ortho position that the phenolic compound of huge group and/or electron donating group is arranged, the crystallinity of may command compd B is to improve film forming.In addition, the introducing degree of acid dissociation functional group is reduced in the controlled and phenolic hydroxyl of the solubleness of compd B in alkaline-based developer, thus improve solubility in solvent, with the adhesiveness and the resist susceptibility of base material.There is the example of the phenolic compound of this effect to comprise 2-(C 1-6-alkyl) phenol such as orthoresol, o-phenyl phenol, 2-cyclohexylphenol, 2-tert-butyl phenol and 2,6 di t butyl phenol and 2-alkoxy phenol such as 2-metoxyphenol, 2-isopropoxy phenol and 2-phenoxy phenyl.
The production method of polyphenolic substance A does not have particular restriction, by one mole of aromatic ketone or aromatic aldehyde and one mole or the excessive compound that 1 to 3 phenolic hydroxyl is arranged such as phenol and orthoresol under 60 to 150 ℃ at acid catalyst example hydrochloric acid and sulfuric acid be used to prevent to generate reaction production in about 0.5 to 20 hour in the presence of the promotor of accessory substance such as thioacetic acid and the β-Qiu Jibingsuan.After the reaction, in reaction solution, add methyl alcohol or isopropyl alcohol, stirred 0.5 to 2 hour down, add an amount of pure water then and make the reaction product deposition at 60 to 80 ℃.After being cooled to room temperature, the reaction product of isolated by filtration deposition, drying obtains polyphenolic substance A.Perhaps, make isolated dihalide and the compound reaction that 1 to 3 phenolic hydroxyl is arranged produce polyphenolic substance A then by making aromatic ketone or aromatic aldehyde change into dihalide with hydrogen halides or halogen gas.
Compd B by but be not limited to following method production: polyphenolic substance A and the compound that is used to introduce acid dissociation functional group such as tertbutyloxycarbonyl and THP trtrahydropyranyl were reacted 6 to 24 hours in the presence of amine catalyst such as triethylamine and dimethylamino naphthyridine or acid catalyst such as toluenesulfonic acid pyridine  under 20 to 60 ℃ and normal pressure.Reaction product liquid poured into be settled out white solid in the distilled water, with the distilled water washing, purify by silica gel column chromatography alternatively then, dry then, obtain compd B.
The example that is used to introduce the compound of acid dissociation functional group includes but not limited to acid chloride, acid anhydrides, supercarbonate, alkyl halide, vinyl alkyl ethers, dihydropyrane, and acid dissociation functional group is all arranged.
This paper indication acid dissociation functional group is the functional group that fracture produces phenolic hydroxyl in the presence of acid.In order to form the resist pattern that has than high sensitive and resolution, preferably this acid dissociation group adjoining land fracture in the presence of acid.
Acid dissociation functional group preferably adds with 10 to 95%, more preferably 20 to 80% ratio of the phenolic hydroxyl sum of polyphenolic substance A.In above-mentioned scope, the dissolubility of compd B in solvent, become better with the adhesiveness and the susceptibility of base material.
The molecular weight of compd B is 300 to 3000, preferred 300 to 1500, more preferably 400 to 1000.In above-mentioned scope, improve resolution and keep the required film forming of resist simultaneously.
Compd B preferably is dissolved in propylene glycol methyl ether acetate or ethyl lactate with 5 weight % or more amount under 23 ℃.This solubleness is arranged, can use the safety solvent that allows use in the semiconductor factory.
Radiation-sensitive composition of the present invention comprises the solid chemical compound of 1 to 80 weight % and the solvent of 20 to 99 weight %, the solvent of the solid constituent of preferred 1 to 50 weight % and 50 to 99 weight %, the more preferably solvent of the solid constituent of 5 to 40 weight % and 60 to 95 weight %.The total amount of compd B and solubilizer is 50-99.999 weight %, preferred 60 to 99 weight %, more preferably 80 to 99 weight %, all based on the gross weight of solid constituent.In above-mentioned scope, obtain high resolving power and line edge unevenness and diminish.The content of solubilizer is preferably 0 to 80 weight %, more preferably 20 to 80 weight %, more preferably 30 to 70 weight % also, all based on the gross weight of solid constituent.In above-mentioned scope, obtain high sensitive and resolution and line edge unevenness and diminish.
Because radiation-sensitive composition of the present invention contains the compd B of meet the demands a and b, can realize the desired character of resist composition simultaneously, if can stand that air output is little in thermotolerance, the solubleness in safety solvent such as propylene glycol methyl ether acetate and ethyl lactate, film forming, the adhesiveness with silicon substrate, alkali developable, corrosion stability, the exposure process of semiconductor technology, resolution is high and the edge unevenness is little.
The example of solvent includes but not limited to ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Ethylene glycol monoalkyl ether such as glycol monoethyl ether and ethylene glycol monoethyl ether; Propylene-glycol monoalky lether acetic acid esters such as propylene glycol methyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; Propylene-glycol monoalky lether such as propylene glycol monomethyl ether (PGME) and dihydroxypropane single-ether; Lactate such as methyl lactate and ethyl lactate (EL); Alphatic carboxylic acid ester such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; Other ester such as 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters and 3-ethoxyl ethyl propionate; Aromatic hydrocarbons such as toluene and dimethylbenzene; Ketone such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; And cyclic ethers such as tetrahydrofuran and two  alkane.These solvents can use separately, also can two or multiple being used in combination.
Among the present invention, acidic method does not have particular restriction, as long as intrasystem true generation acid.For example replacing with excimer laser, ultraviolet ray such as g-ray and i-ray can make processing meticulousr.If use high-energy ray such as electron beam, Extreme Ultraviolet, X-ray and ion beam, then the resist composition can carry out meticulousr processing.
Solid constituent preferably contains at least a acidic acid agent when for example being subjected to x ray irradiation x such as Extreme Ultraviolet (EUV), electron beam and X-ray.The content of acid agent is preferably 0.001 to 50 weight % of solid constituent gross weight, more preferably 1 to 40 weight %, more preferably 3 to 20 weight % also.In above-mentioned scope, can obtain high sensitive and the little pattern of edge unevenness.
Acid agent is preferably at least a compound that is selected from compound shown in the following formula 13 to 20, but is not limited thereto.
Formula 13:
Figure A20048002685900241
R wherein 13Base can be identical or different, is hydrogen independently of one another, straight chain, side chain or cyclic alkyl, straight chain, side chain or cyclic alkoxy, hydroxyl or halogen; With X-be the azochlorosulfonate acid ion that alkyl, aryl, haloalkyl or halogenated aryl are arranged, or halogen ion.
Compound shown in the formula 13 is preferably and is selected from least a of following compound: the trifluoromethanesulfonic acid triphenylsulfonium, the positive fourth sulfonic acid of nine fluorine triphenylsulfonium, the positive fourth sulfonic acid of nine fluorine diphenylmethyl phenyl sulfonium, the positive hot sulfonic acid triphenylsulfonium of perfluor, trifluoromethanesulfonic acid diphenyl-4-aminomethyl phenyl sulfonium, trifluoromethanesulfonic acid two-2,4,6-trimethylphenyl sulfonium, trifluoromethanesulfonic acid diphenyl-4-tert-butoxy phenyl sulfonium, the positive fourth sulfonic acid diphenyl of nine fluorine-4-tert-butoxy phenyl sulfonium, trifluoromethanesulfonic acid diphenyl-4-hydroxyphenyl sulfonium, trifluoromethanesulfonic acid two (4-fluorophenyl)-4-hydroxyphenyl sulfonium, the positive fourth sulfonic acid diphenyl of nine fluorine-4-hydroxyphenyl sulfonium, trifluoromethanesulfonic acid two (4-hydroxyphenyl) phenyl sulfonium, trifluoromethanesulfonic acid three (4-methoxyphenyl) sulfonium, trifluoromethanesulfonic acid three (4-fluorophenyl) sulfonium, the p-toluenesulfonic acid triphenylsulfonium, the benzene sulfonic acid triphenylsulfonium, p-toluenesulfonic acid diphenyl-2,4,6-trimethylphenyl sulfonium, 2-trifluoromethyl benzene sulfonic acid diphenyl-2,4,6-trimethylphenyl sulfonium, 4-trifluoromethyl benzene sulfonic acid diphenyl-2,4,6-trimethylphenyl sulfonium, 2,4-difluoro benzene sulfonic acid diphenyl-2,4,6-trimethylphenyl sulfonium, phenyl-hexafluoride sulfonic acid diphenyl-2,4,6-trimethylphenyl sulfonium, trifluoromethanesulfonic acid diphenyl naphthyl sulfonium, p-toluenesulfonic acid diphenyl-4-hydroxyphenyl sulfonium, 10-camphorsulfonic acid triphenylsulfonium and 10-camphorsulfonic acid diphenyl-4-hydroxyphenyl sulfonium.
Formula 14:
Figure A20048002685900251
R wherein 14Base can be identical or different, is hydrogen independently of one another, straight chain, side chain or cyclic alkyl, straight chain, side chain or cyclic alkoxy, hydroxyl or halogen.X-is defined identical with the front.
Compound shown in the formula 14 is preferably and is selected from least a of following formula: compound: trifluoromethanesulfonic acid two (4-tert-butyl-phenyl) iodine , the positive fourth sulfonic acid two of nine fluorine (4-tert-butyl-phenyl) iodine , the positive hot sulfonic acid two of perfluor (4-tert-butyl-phenyl) iodine , p-toluenesulfonic acid two (4-tert-butyl-phenyl) iodine , benzene sulfonic acid two (4-tert-butyl-phenyl) iodine , 2-trifluoromethyl benzene sulfonic acid two (4-tert-butyl-phenyl) iodine , 4-trifluoromethyl benzene sulfonic acid two (4-tert-butyl-phenyl) iodine , 2,4-difluoro benzene sulfonic acid two (4-tert-butyl-phenyl) iodine , phenyl-hexafluoride sulfonic acid two (4-tert-butyl-phenyl) iodine , 10-camphorsulfonic acid two (4-tert-butyl-phenyl) iodine , trifluoromethanesulfonic acid diphenyl iodine , the positive fourth sulfonic acid of nine fluorine diphenyl iodine , the positive hot sulfonic acid diphenyl iodine  of perfluor, p-toluenesulfonic acid diphenyl iodine , benzene sulfonic acid diphenyl iodine , 10-camphorsulfonic acid diphenyl iodine , 2-trifluoromethyl benzene sulfonic acid diphenyl iodine , 4-trifluoromethyl benzene sulfonic acid diphenyl iodine , 2,4-difluoro benzene sulfonic acid diphenyl iodine , phenyl-hexafluoride sulfonic acid diphenyl iodine , trifluoromethanesulfonic acid two (4-trifluoromethyl) iodine , the positive fourth sulfonic acid two of nine fluorine (4-trifluoromethyl) iodine , the positive hot sulfonic acid two of perfluor (4-trifluoromethyl) iodine , p-toluenesulfonic acid two (4-trifluoromethyl) iodine , benzene sulfonic acid two (4-trifluoromethyl) iodine  and 10-camphorsulfonic acid two (4-trifluoromethyl) iodine .
Formula 15:
Wherein Q is alkylidene or arlydene, and R 15Be alkyl, aryl, haloalkyl or halogenated aryl.
Compound shown in the formula 15 is preferably and is selected from least a of following compound: N-(trifluoro-methanesulfonyl oxy) succinimide, N-(trifluoro-methanesulfonyl oxy) phthalimide, N-(trifluoro-methanesulfonyl oxy) diphenyl maleimide, N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(trifluoro-methanesulfonyl oxy) naphthyl acid imide, N-(10-camphor sulfonyloxy) succinimide, N-(10-camphor sulfonyloxy) phthalimide, N-(10-camphor sulfonyloxy) diphenyl maleimide, N-(10-camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(10-camphor sulfonyloxy) naphthyl acid imide, N-(positive hot sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(positive hot sulfonyloxy) naphthyl acid imide, N-(tolysulfonyl oxygen base) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(tolysulfonyl oxygen base) naphthyl acid imide, N-(2-trifluoromethyl phenylsulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(2-trifluoromethyl phenylsulfonyloxy) naphthyl acid imide, N-(4-trifluoromethyl phenylsulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(4-trifluoromethyl phenylsulfonyloxy) naphthyl acid imide, N-(perfluor phenylsulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(perfluor phenylsulfonyloxy) naphthyl acid imide, N-(1-naphthalene sulfonyl oxygen base) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(1-naphthalene sulfonyl oxygen base) naphthyl acid imide, N-(the positive fourth sulfonyloxy of nine fluorine) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide, N-(the positive fourth sulfonyloxy of nine fluorine) naphthyl acid imide, N-(the positive hot sulfonyloxy of perfluor) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide and N-(the positive hot sulfonyloxy of perfluor) naphthyl acid imide.
Formula 16:
R wherein 16Base can be identical or different, is straight chain, side chain or the cyclic alkyl that replaces alternatively independently of one another, the aryl of Qu Daiing alternatively, the heteroaryl of Qu Daiing alternatively, or the aralkyl of replacement alternatively.
Compound shown in the formula 16 is preferably and is selected from least a of following compound: diphenyl two sulfones, two (4-aminomethyl phenyl) two sulfones, dinaphthyl two sulfones, two (4-tert-butyl-phenyl) two sulfones, two (4-hydroxyphenyl) two sulfones, two (3-hydroxyl naphthyl) two sulfones, two (4-fluorophenyl) two sulfones, two (2-fluorophenyl) two sulfones and two (4-trifluoromethyl) two sulfones.
Formula 17:
R wherein 17Base can be identical or different, is straight chain, side chain or the cyclic alkyl that replaces alternatively independently of one another, the aryl of Qu Daiing alternatively, the heteroaryl of Qu Daiing alternatively, or the aralkyl of replacement alternatively.
Compound shown in the formula 17 is preferably and is selected from least a of following compound: α-(sulfonyloxy methyl oxyimino group) phenylacetonitrile, α-(sulfonyloxy methyl oxyimino group)-4-methoxyphenyl acetonitrile, α-(trifluoromethyl sulphonyl oxyimino group) phenylacetonitrile, α-(trifluoromethyl sulphonyl oxyimino group)-4-methoxyphenyl acetonitrile, α-(ethyl sulphonyl oxyimino group)-4-methoxyphenyl acetonitrile, α-(sulfonyl propyl oxyimino group)-4-methoxyphenyl acetonitrile and α-(sulfonyloxy methyl oxyimino group)-4-bromophenyl acetonitrile.
Formula 18:
R wherein 18Can be identical or different, independently of one another for the haloalkyl of one or more chlorine atom and one or more bromine atoms is arranged.This haloalkyl preferably has 1 to 5 carbon atom.
Formula 19 and 20:
Figure A20048002685900281
Figure A20048002685900282
R wherein 19And R 20Base is C independently of one another 1-C 3Alkyl such as methyl, ethyl, n-pro-pyl and isopropyl, C 3-C 6Naphthenic base such as cyclopentyl and cyclohexyl, C 1-C 3Alkoxy such as methoxyl, ethoxy and propoxyl group, or aryl, preferred C 6-C 10Aryl such as phenyl, tolyl and naphthyl; L 19And L 20Base is independently of one another for having 1, the organic group of 2-naphthoquinones diazido.Have 1; the preferred embodiment of the organic group of 2-naphthoquinones diazido comprises 1; 2-naphthoquinones two nitrine sulfonyls are as 1; 2-naphthoquinones diazido-4-sulfonyl, 1; 2-naphthoquinones diazido-5-sulfonyl and 1,2-naphthoquinones diazido-6-sulfonyl, wherein 1; 2-naphthoquinones diazido-4-sulfonyl and 1,2-naphthoquinones diazido-the 5-sulfonyl more preferably.Subscript p is 1 to 3 integer, and subscript q is 0 to 4 integer, satisfies 1≤p+q≤5; J 19Be singly-bound, C 1-C 4Group shown in polymethylene, cycloalkylidene, phenylene, the following formula 21:
Carbonyl, ester group, amide group or ether; Y 19Be hydrogen, alkyl or aryl; X 19And X 20Be group shown in the following formula 22 independently of one another.
Formula 22:
Z wherein 22Base is alkyl, naphthenic base or aryl independently of one another; R 22Be alkyl, naphthenic base or alkoxy; With r be 0 to 3 integer.
The example of other acid agent comprises that the disulfonyl diazomethane is as two (tolysulfonyl) diazomethane, two (2,4-dimethyl benzene sulphonyl) diazomethane, two (tert-butyl group sulphonyl) diazomethane, two (normal-butyl sulphonyl) diazomethane, two (isobutyl sulphonyl) diazomethane, two (isopropyl sulphonyl) diazomethane, two (n-pro-pyl sulphonyl) diazomethane and two (cyclohexyl sulphonyl) diazomethane; With halogen-containing pyrrolotriazine derivatives such as 2-(4-methoxyphenyl)-4,6-(two trichloromethyl)-1,3,5-triazines, 2-(4-methoxyl naphthyl)-4,6-(two trichloromethyl)-1,3,5-triazines, three (2, the 3-dibromopropyl)-1,3,5-triazine and three (2, the 3-dibromopropyl) isocyanuric acid ester.
Solubilizer is by improving the compound that the solubleness (if this solubleness lower) of compd B in developer solution such as alkali suitably improves the dissolution velocity of compd B in the development operation.Preferred this solubilizer does not cause chemical change in etchant resist baking, electron beam irradiation and development step.For example, use such as low-molecular-weight phenolic compounds such as bisphenols, three (hydroxyphenyl) methane and four phenols and make solubilizer.The example of bisphenols comprises bis-phenol, two (4-hydroxyphenyl) propane, two (4-hydroxyphenyl) ketone, methylene bis-phenol, ethidine bis-phenol, cyclohexylidene base bis-phenol and phenyl ethidine bis-phenol.The example of three phenols comprises three (4-hydroxyphenyl) methane, three (4-hydroxyphenyl) ethane and three (4-hydroxyphenyl) benzene.The example of four phenols comprises 4,4 ', 4 " and, 4 -(1,2-ethane y-bend base) four phenol, 4,4 ', 4 " and, 4 -(1,2-benzene two methene bases) four phenol, calix[4] allene and four (two cyclohexylidene base) phenol.These solubilizer can use separately, also can two or multiple being used in combination.The content of solubilizer is regulated according to the kind of compound used therefor B, is preferably 0 to 80 weight % of solid constituent gross weight, more preferably 20 to 80 weight %, more preferably 30 to 70 weight % also.
The low-molecular-weight phenolic compound is preferably represented with following formula 25:
R wherein 2, R 4And R 5Define as the front; Respectively do for oneself 1 to 3 integer of m3 and n3; Respectively do for oneself 0 to 4 integer of m4 and n4; All satisfy 1≤m3+m4≤5 and 1≤n3+n4≤5; Being positioned at-CR of two phenyl ring 4R 5-two carbon atoms at ortho position can form xanthene structure or thioxanthene structure shown in the following formula 26 by the mutual bonding of oxygen atom or sulphur atom:
R wherein 2, R 4, R 5Define with X such as front; Respectively do for oneself 1 to 2 integer of p3 and q3; Respectively do for oneself 0 to 3 integer of p4 and q4.
Radiation-sensitive composition of the present invention can also contain various adjuvants such as sour diffusion control agent, solubleness controlling agent, sensitizer and surfactant.
The agent of acid diffusion control has the acid effect of undesirable chemical reaction in the diffusion control unexposed area in etchant resist that produces when acid agent is subjected to x ray irradiation x by suppressing.Use this sour diffusion control agent can improve the storage stability and the resolution of radiation-sensitive composition.In addition, resist pattern line width variation due to the variation that can prevent to postpone because of the electron beam irradiation surrounding time, thus make the excellent stability of this technology.Degradable alkali compounds such as alkaline sulfonium compound and alkaline iodine  compound when its example comprises nitrogenous alkali compounds and is subjected to electron beam irradiation.These sour diffusion control agent can be used separately, also can two or multiple being used in combination.
The content of acid diffusion control agent is preferably 0 to 10 weight % of solid constituent gross weight, more preferably 0.001 to 5 weight %, more preferably 0.001 to 3 weight % also.If be lower than 0.001 weight %, under some process conditions, may reduce resolution, pattern contour and dimensional accuracy.In addition, if the time delay that heats after prolonging from electron beam irradiation to irradiation then may lose suitable pattern contour.If surpass 10 weight %, then can be detrimental to the development of the susceptibility and the unexposed area of resist composition.
The solubleness controlling agent is by reducing the compound that the solubleness appropriateness reduces the dissolution velocity of compd B in developer solution such as alkali when solubleness is higher.Preferred dissolution degree controlling agent does not cause chemical change in etchant resist baking, x ray irradiation x and development step.
The example of solubleness controlling agent comprises aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene and acenaphthene; Ketone such as acetophenone, benzophenone and phenyl napthyl ketone; With sulfone such as methyl phenyl sulfone, diphenyl sulfone and dinaphthyl sulfone.These solubleness controlling agents can use separately, also can two or multiple being used in combination.The content of solubleness controlling agent changes with the kind of compound used therefor B, is preferably 0 to 50 weight % of solid constituent gross weight, more preferably 0 to 50 weight %, more preferably 0.1 to 20 weight %, more preferably 1 to 10 weight % also.
Thereby sensitizer is to be transferred to the compound that acid agent increase product acid amount improves the apparent susceptibility of resist by the energy that absorbs the irradiation ray and with it.The example of sensitizer includes but not limited to Benzophenones, biacetyl class, pyrene class, phenothiazines and fluorenes class.These sensitizers can use separately, also can two or multiple being used in combination.The content of sensitizer is preferably 0.1 to 20 weight % of solid constituent gross weight, more preferably 1 to 10 weight % also.
Surfactant is the compound that improves the coating of radiation-sensitive composition and the development of striped and resist etc.As surfactant, can use any negative ion, kation, nonionic and amphoteric surfactant, wherein non-ionic surfactant is preferred, because the affinity of they and radiation-sensitive composition solvent for use is good.The example of non-ionic surfactant includes but not limited to the higher fatty acid diester of polyoxyethylene senior alkyl ether, polyoxyethylene senior alkyl phenyl ether and polyglycol, can be purchased with following trade name: " EFTOP " of Jemco Inc.; Dai-Nippon Ink ﹠amp; Chemicals, " MEGAFACE " of Incorporated; " FLUORAD " of Sumitomo 3M Ltd.; Asahi Glass Co., " ASAHIGUARD " of Ltd. and " SURFLON "; Toho Chemical IndustryCo., " PEPOL " of Ltd.; Shin-Etsu Chemical Co., " KP " of Ltd.; With Kyoeisha Chemical Co., " POLYFLOW " of Ltd..
The content of surfactant is preferably 0 to 2 weight % of solid constituent gross weight, more preferably 0.0001 to 1 weight %, more preferably 0.001 to 0.1 weight % also.In addition, but blending dyestuff or pigment make the latent image of exposed portion visual in the radiation-sensitive composition, thereby reduce the adverse effect of halation in the exposing operation process.But in the radiation-sensitive composition also the blending adhesion promotor to improve the adhesiveness with base material.
Except that above-mentioned adjuvant, radiation-sensitive composition can also contain water insoluble but dissolve in the resin of alkaline aqueous solution or water insoluble but dissolve in the resin that alkaline aqueous solution obtains alkaline aqueous solution development property under the acid effect.The example of this resinoid comprises the phenol resin that can add acid dissociation functional group therein; The lacquer resin that can add acid dissociation functional group therein; The hydrogenation lacquer resin that can add acid dissociation functional group therein; O-polycarboxylated styrene, m-polycarboxylated styrene, p-polycarboxylated styrene and the multipolymer thereof that can add acid dissociation functional group therein; The polycarboxylated styrene that can add the alkyl replacement of acid dissociation functional group therein; The polycarboxylated styrene that can add acid dissociation functional group therein; The alkylating polycarboxylated styrene of part o-that can add acid dissociation functional group therein; Styrene-hydroxy styrenes the multipolymer that can add acid dissociation functional group therein; α-Jia Jibenyixi-hydroxy styrenes the multipolymer that can add acid dissociation functional group therein; The polyalkyl methacrylate that can add acid dissociation functional group therein; Polyolefin; Polyester; Polyamide; Polyureas; And polyurethane.Because line edge unevenness improves with the increase of this resin content, it would be better to its use to be tending towards obtaining good pattern contour when avoiding using this resin.
Radiation-sensitive composition of the present invention under agitation mixes production by compd B, solvent, solubilizer and optional adjuvant such as acid agent.The amount of every kind of optional adjuvant (if you are using) in above-mentioned scope, select so that in the solid constituent total content of each component amount to 100 weight %.Stirring means, mixed method and order by merging are unimportant, and those skilled in the art are easy to select.
In process in the radiation-sensitive composition formation corrosion-resisting pattern of the present invention, on such as base materials such as silicon wafer, gallium-arsenic wafer and aluminising wafers, be coated with radiation-sensitive composition formation etchant resist by coating processes such as for example spin coating, curtain coating coating and roller coat earlier.
Base material can be handled with surface conditioning agent as required.The example of surface conditioning agent comprises silane coupling agent such as hexa-methylene disilazane when hydrolysis (for example polymerisable silane coupling agent), tackify (anchor) finishing agent or priming paint (for example polyvinyl acetal, acrylic resin, vinyl acetate resin, epoxy resin and urethane resin) and comprises the finishing agent of the potpourri of priming paint and fine inorganic particle.
The thickness of etchant resist is preferably 0.01 to 10 μ m, more preferably 0.05 to 1 μ m, more preferably 0.08 to 0.5 μ m also, but is not limited thereto.
When needing, after forming etchant resist, can form resist-protecting membrane and enter etchant resist with the amine that prevents to suspend in the air etc.Allow with to the compound of responding property of acid when being suspended in airborne amine reaction as impurity, will make to be subjected to the acid that radiation produces and to lose activity.Can prevent that with this resist-protecting membrane deactivation causes resist pattern to descend as variation and susceptibility thus.Resist-protecting membrane is preferably formed by water-soluble acidic polymer such as polyacrylic acid and poly-sulfonic acid vinyl acetate.
Make etchant resist be exposed to for example radiation such as ultraviolet ray, Extreme Ultraviolet (EUV) and electron beam then with institute's desirable pattern.Compd B after the exposure becomes the compound that dissolves in alkaline developer solution, because its acid dissociation functional group breaks to form phenolic hydroxyl.Conditions of exposure can be selected according to prescription of radiation-sensitive composition etc.Among the present invention, preferably behind x ray irradiation x, heat-treat stably to form high-precision meticulous exposing patterns.This thermal treatment is preferably 20 to 250 ℃, more preferably 40 to 150 ℃, although it depends on the prescription of radiation-sensitive composition etc.
With alkaline-based developer etchant resist after the exposure is developed then and form the corrosion-resisting pattern of wanting.As alkaline-based developer, can use at least a alkali compounds with preferred 1 to 10 quality %, the more preferably lysigenous alkaline aqueous solution of the concentration of 1 to 5 quality %, that described alkali compounds for example is selected from is single-, two-or trialkylamine, single-, two-or trialkanolamine, heterocyclic amine, tetramethylammonium hydroxide (TMAH) and choline.
In addition, alkaline-based developer can contain an amount of alcohol such as methyl alcohol, ethanol and isopropyl alcohol or above-mentioned surfactant, especially preferably adds the isopropyl alcohol of 10 to 30 quality %.After this alkaline aqueous solution development, water cleans developing pattern usually.
Form after the corrosion-resisting pattern, make the substrate passed etching obtain the wiring plate of patterning.Etching can be finished by dry corrosion that adopts plasma gas and the known methods such as wet corrosion that use alkaline solution, cupric chloride (II) solution, iron chloride (III) solution etc.
After forming corrosion-resisting pattern, base material can carry out plating, for example copper facing, zinc-plated, nickel plating or gold-plated.
Available organic solvent or the stronger alkaline aqueous solution of the ratio used alkaline aqueous solution of development are peeled off remaining corrosion-resisting pattern.Representative examples of organic comprises PGMEA, PGME and EL.The example of strong alkaline aqueous solution comprises 1 to 20 quality % sodium hydrate aqueous solution and 1 to 20 quality % potassium hydroxide aqueous solution.Peeling off of corrosion-resisting pattern can be finished by infusion process, spray-on process etc.The wiring plate that corrosion-resisting pattern is arranged above can be multiwiring board and can be formed with small through hole.
Wiring plate can be by peeling off (lift off) method production, and wherein vacuum deposited metal is removed the residue resist pattern by being dissolved in solution then after forming corrosion-resisting pattern.
The present invention is described with the following Examples in more detail.But should notice that following examples only are to illustrate and do not limit the scope of the invention.
Assessing compound, radiation-sensitive composition and resist pattern by the following method.
The evaluation of I compound and radiation-sensitive composition
(1) dissolubility of compound in safety solvent
Test the dissolubility of each compound in 23 ℃ of safety solvents (PGMEA or EL).Meltage be 5 weight % or when higher dissolubility be assessed as " A ", meltage is 0.1 weight % or higher but be assessed as " B " when being lower than 5 weight %, is assessed as during not with 0.1 weight % or higher amount dissolving " C ".
(2) film forming of radiation-sensitive composition
The 10 weight % solution of each compound in PGMEA are spin-coated on the thick etchant resist of the about 0.2 μ m of formation on the silicon wafer with spinner.After 3 minutes, observing the state of etchant resist in about 110 ℃ of heating on the electric furnace.Be assessed as during injustice that etchant resist bleaches or its surface becomes " C ", part bleaches or part is assessed as " B " when becoming injustice, is assessed as " A " when appearance is good.
(3) the dissolving inhibiting effect in alkaline-based developer
Soaked 3 minutes in developer solution (2.38%TMAH aqueous solution) estimating the etchant resist that forms in 2.Be assessed as during the state no change of visualization film " A ", the surface becomes and is assessed as " C " when injustice or part film are dissolved to be fallen.
(4) with the adhesiveness of silicon substrate
Adhesiveness is assessed as " A " when estimating the unstripped silicon wafer of the etchant resist that forms in 2, uses under the situation of surface conditioning agent (silane coupling agent) and is assessed as " B " when unstripped, even be assessed as " C " when also peeling off under the situation of using surface conditioning agent.
(5) alkali developable
Test the developing property of the polyphenolic substance A corresponding with alkaline-based developer with introducing acid dissociation functional group each compound before.
The 10 weight % solution of each polyphenolic substance A in PGMEA are formed the thick etchant resist of about 0.2 μ m with the spinner spin coating., after 3 minutes etchant resist was being soaked 10 seconds in the 2.38%TMAH aqueous solution in about 110 ℃ of heating on the electric furnace.Etchant resist dissolves fully and is assessed as " A " when disappearing, etchant resist even be assessed as " C " during not with oligodynamical.
The evaluation of II corrosion-resisting pattern
(1) formation of etchant resist
Each preparaton shown in the table 5 is filtered the preparation radiation-sensitive composition with 0.2 μ m teflon (registered trademark) filtrator.Each radiation-sensitive composition is spin-coated on the silicon wafer with spinner, then on electric furnace in about 110 ℃ the heating 60 seconds, form the thick etchant resist of about 0.2 μ m.
(2) the one-tenth figure of etchant resist
With electron beam lithography system (accelerating potential: 50keV) make etchant resist be exposed to radiation.After the exposure, etchant resist was heated 60 seconds down in the temperature of postexposure bake shown in the table 6 (PEB).Then etchant resist was soaked 30 seconds in the 2.38%TMAH aqueous solution, with distilled water rinsing 30 seconds, dry then.Observation post gets single lines or lines and interval (line-and-space) pattern under scanning electron microscope.
(3) evaluation of susceptibility and resolution
With the limiting resolution on single lines or lines and the intermittent pattern as resolution.The susceptibility minimum exposure time representation that limiting resolution is provided.
Embodiment 1: compound 5-1's is synthetic
Figure A20048002685900351
(1) 1-(2-naphthyl)-1,1-two (3-methyl-4-hydroxyphenyl) ethane synthetic
To 4 3.2 g (0.4mol) orthoresol (from Kanto Chemical Co., Inc. reagent) and 17.1g (0.1mol) β-Nai Yitong (from Kanto Chemical Co., Inc. mixture heated reagent) adds 0.1ml sulfuric acid, 0.8ml3-mercaptopropionic acid and 10ml toluene to the solution of about 30 ℃ of preparations.Under agitation react.Confirm that by vapor-phase chromatography conversion ratio reaches after 100%, add 100ml toluene.After the cooling, isolated by vacuum filtration goes out precipitated solid, under agitation cleans with 60 ℃ of warm water, purifies by silica gel column chromatography, obtains the 24g title compound.
(2) compound 5-1's is synthetic
The 1-(2-naphthyl)-1 that above 1.84g (5mmol), synthesizes, 1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are (from KantoChemical Co., Inc. reagent) in the solution that is mixed with, dripped 2.62g (12mmol) di-tert-butyl dicarbonate (from Kanto Chemical Co., the reagent of Inc.) through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.The gained white powder cleans three times with distilled water, suction filtration, and drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 2: compound 5-2's is synthetic
Figure A20048002685900361
The 1-(2-naphthyl)-1 that in 1.84g (5mmol) embodiment 1, synthesizes, in the solution that 1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 1.32g (6mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri stirred 24 hours down at 40 ℃.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 3: compound 5-3's is synthetic
Figure A20048002685900362
(1) two catechol compounds is synthetic
Remove with 44.0g (0.4mol) catechol (from Kanto Chemical Co., Inc. reagent) replace outside 43.2g (0.4mol) orthoresol with embodiment 1 (1) in the identical synthetic 1-(2-naphthyl)-1 of mode, 1-two (3, the 4-dihydroxyphenyl) ethane.
(2) compound 5-3's is synthetic
The 1-(2-naphthyl)-1 that synthesizes above 1.84g (5mmol) is in the solution that 1-two (3, the 4-dihydroxyphenyl) ethane and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, through 10 minutes Dropwise 5 .28g (24mmol) di-tert-butyl dicarbonates.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.The gained white powder cleans three times with distilled water, suction filtration, and drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 4: compound 5-4's is synthetic
Figure A20048002685900371
With 1-(2-naphthyl)-1 synthetic among 1.84g (5mmol) embodiment 1,1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  are (from Kanto Chemical Co., Inc. reagent) and the solution that is mixed with of 0.43g (6mmol) ethyl vinyl ether (from Kanto Chemical Co., the reagent of Inc.) at room temperature stirred 24 hours.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 5: compound 5-5's is synthetic
Figure A20048002685900372
With 1-(2-naphthyl)-1 synthetic among 1.84g (5mmol) embodiment 1, the solution that 1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.76g (6mmol) cyclohexyl vinyl ether are mixed with at room temperature stirred 24 hours.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 6: compound 5-6's is synthetic
With 1-(2-naphthyl)-1 synthetic among 1.84g (5mmol) embodiment 1, the solution that 1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.50g (6mmol) dihydropyrane (from Kanto Chemical Co., the reagent of Inc.) are mixed with at room temperature stirred 24 hours.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 7: compound 5-7's is synthetic
Figure A20048002685900382
(1) 1-(2-naphthyl)-1,1-two (3-cyclohexyl-4-hydroxyphenyl) ethane synthetic
Remove with 53.0g (0.3mol) 2-cyclohexylphenol (from Honshu ChemicalIndustry Co., the reagent of Inc.) replace outside 43.2g (0.4mol) orthoresol with embodiment 1 (1) in identical mode synthesising title compound.
(2) compound 5-7's is synthetic
The 1-(2-naphthyl)-1 that synthesizes above 2.52g (5mmol), the solution that 1-two (3-cyclohexyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.43g (6mmol) ethyl vinyl ether are mixed with at room temperature stirred 24 hours.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/4) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 8: compound 5-8's is synthetic
Figure A20048002685900391
(1) 1-(2-naphthyl)-1,1-two (4-hydroxyphenyl) ethane synthetic
Except that replace with 37.4g (0.4mol) phenol 43.2g (0.4mol) orthoresol with embodiment 1 (1) in identical mode bisphenol synthesis acetonaphthone.
(2) compound 5-8's is synthetic
Remove with 1.70g (5mmol) 1-(2-naphthyl)-1,1-two (4-hydroxyphenyl) ethane replaces 1.84g (5mmol) 1-(2-naphthyl)-1, outside 1-two (3-methyl-4-hydroxyphenyl) ethane with embodiment 1 (2) in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 9: compound 5-9's is synthetic
(1) 1-(1-naphthyl)-1,1-two (4-hydroxyphenyl) methane synthetic
Remove with 15.6g (0.1mol) α-naphthaldehyde (from Kanto Chemical Co., Inc. reagent) replace outside 17.1g (0.1mol) β-Nai Yitong with embodiment 1 (1) in the identical synthetic 1-(1-naphthyl)-1 of mode, 1-two (4-hydroxyphenyl) methane.
(2) compound 5-9's is synthetic
Remove with 1.63g (5mmol) 1-(1-naphthyl)-1,1-two (4-hydroxyphenyl) methane replaces 1.84g (5mmol) 1-(2-naphthyl)-1, outside 1-two (3-methyl-4-hydroxyphenyl) ethane with embodiment 1 (2) in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 10: compound 6-1's is synthetic
Figure A20048002685900401
(1) 1-(4 '-biphenyl)-1,1-two (4-hydroxyphenyl) methane synthetic
Remove with 18.2g (0.1mol) 4 '-biphenylcarboxaldehyde (from Mitsubishi GasChemical Company, Inc.) replace outside 17.1g (0.1mol) β-Nai Yitong with embodiment 1 (1) in the identical synthetic biphenylcarboxaldehyde of mode.
(2) compound 6-1's is synthetic
Remove with 1-(4 '-biphenyl)-1 synthetic above the 1.76g (5mmol), 1-two (4-hydroxyphenyl) methane replaces 1.84g (5mmol) 1-(2-naphthyl)-1, outside 1-two (3-methyl-4-hydroxyphenyl) ethane with embodiment 6 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 11: compound 7-1's is synthetic
Figure A20048002685900402
(, Ltd.) in the solution that is mixed with 5ml dimethyl acetamide (DMAc), slowly add 4.80g (22mmol) di-tert-butyl dicarbonate and 2.4g triethylamine to the two catechol fluorenes of 1.91g (5mmol) from Osaka Gas Chemicals Co..The gained potpourri stirred 7 hours down at 60 ℃.Pour into reaction liquid in the excessive water and repeat to precipitate again.Gained white powder drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 12: compound 7-2's is synthetic
Figure A20048002685900411
(, Ltd.) in the solution that is mixed with 5ml dimethyl acetamide (DMAc), slowly add 3.27g (15mmol) di-tert-butyl dicarbonate and 2.4g triethylamine to the two catechol fluorenes of 1.91g (5mmol) from Osaka Gas Chemicals Co..The gained potpourri stirred 7 hours down at 60 ℃.Reaction liquid separated by silica gel column chromatography and purify that (eluant, eluent: ethyl acetate/hexane=1/4), drying under reduced pressure obtains title compound then.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 13: compound 7-3's is synthetic
Synthesizing of (1) 9,9-two (3,4,5-three hydroxyphenyl) fluorenes
To 50.4g (0.4mol) 1,2,3,-thrihydroxy-benzene (Kanto Chemical Co., reagent) and 18.0g (0.1mol) 9-Fluorenone (Kanto Chemical Co. Inc., Inc. mixture heated reagent) adds 0.1ml sulfuric acid, 0.8ml3-mercaptopropionic acid and 10ml toluene to the solution of about 60 ℃ of preparations.Under agitation react.The conversion ratio of 9-Fluorenone reaches after 100%, adds 100ml toluene.Vacuum filtration is collected by cooling precipitated solid material, under agitation cleans with 60 ℃ of warm water, and recrystallization, obtain the 4.30g title compound.
(2) compound 7-3's is synthetic
Synthetic 9 above 0.103g (0.25mmol), in the solution that 9-two (3,4,5-three hydroxyphenyl) fluorenes and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, through 30 minutes dropping 0.39g (1.8mmol) di-tert-butyl dicarbonates.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.Gained white powder drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 14: compound 7-4's is synthetic
Figure A20048002685900421
(from Osaka Gas Chemicals Co., Ltd.) solution that is mixed with 5ml anhydrous propanone, 0.07 3g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.50g (6mmol) dihydropyrane at room temperature stirred 24 hours with 1.75g (5mmol) bisphenol fluorene.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 15: compound 7-5's is synthetic
With 1.89g (5mmol) 10, (from HonshuChemicals Industry Co., Ltd.) solution that is mixed with 20ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.50g (6mmol) dihydropyrane at room temperature stirred 24 hours 10-two (4-hydroxyphenyl)-9-anthrone.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 16: compound 8-1's is synthetic
Synthesizing of (1) 1,1-two (4-hydroxyphenyl) acenaphthene
To the solution of about 30 ℃ of preparations, add 0.1ml sulfuric acid, 0.8ml3-mercaptopropionic acid and 10ml toluene to the mixture heated of 43.2g (0.4mol) phenol and 16.8g (0.1mol) acenaphthenone.Under agitation react.Conversion ratio reaches after 100%, adds 100ml toluene.Vacuum filtration is collected by cooling precipitated solid material, under agitation cleans with 60 ℃ of warm water, and recrystallization, obtain title compound.
(2) compound 8-1's is synthetic
Synthetic 1 above 1.69g (5mmol), the solution that 1-two (4-hydroxyphenyl) acenaphthene and 10ml anhydrous propanone, 0.073g (0.29mmol) p-toluenesulfonic acid pyridine  and 0.50g (6mmol) dihydropyrane are mixed with at room temperature stirred 24 hours.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 17: compound 8-2's is synthetic
Figure A20048002685900432
Synthesizing of (1) 1,1-two (4-hydroxyphenyl) acenaphthene-2-ketone
Remove with 16.2g (0.1mol) acenaphthene quinone (from Kanto Chemical Co., Inc.) replace outside 16.8g (0.1mol) acenaphthenone with embodiment 16 (1) in identical mode synthetic 1,1-two (4-hydroxyphenyl) acenaphthene-2-ketone.
(2) compound 8-2's is synthetic
Remove with 1.83g (5mmol) 1,1-two (4-hydroxyphenyl) acenaphthene-2-ketone replaces 1.69g (5mmol) 1, outside 1-two (4-hydroxyphenyl) acenaphthene with embodiment 16 (2) in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 18: compound 8-3's is synthetic
Figure A20048002685900441
Synthesizing of (1) 1,1-two (3-cyclohexyl-4-hydroxyphenyl) acenaphthene
Except that replace with 53.0g (0.3mol) 2-cyclohexylphenol 43.2g (0.4mol) phenol with embodiment 16 (1) in identical mode synthetic 1,1-two (3-cyclohexyl-4-hydroxyphenyl) acenaphthene.
(2) compound 8-3's is synthetic
Remove with 2.51g (5mmol) 1,1-two (3-cyclohexyl-4-hydroxyphenyl) acenaphthene replaces 1.84g (5mmol) 1-(2-naphthyl)-1, outside 1-two (3-methyl-4-hydroxyphenyl) ethane with embodiment 4 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 19: compound 8-4's is synthetic
Figure A20048002685900451
Synthetic 1 in 1.76g (5mmol) embodiment 17 (1), in the solution that 1-two (4-hydroxyphenyl) acenaphthene-2-ketone and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, through 10 minutes dropping 2.64g (12mmol) di-tert-butyl dicarbonates.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.The gained white powder cleans three times with distilled water, suction filtration, and drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 20: compound 8-5's is synthetic
Except that replace with 51.0g (0.3mol) 2-phenylphenol 53.0g (0.3mol) the 2-cyclohexylphenol with embodiment 18 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 21: compound 9-1's is synthetic
Figure A20048002685900453
Except that replace with 44.0g (0.4mol) resorcinol 43.2g (0.4mol) orthoresol with embodiment 6 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 22: compound 10-1's is synthetic
Synthesizing of (1) 2,8-dihydroxy-5-(4-xenyl) xanthene
Except that replace with 44.0g (0.4mol) resorcinol 37.4g (0.4mol) phenol with embodiment 10 (1) in identical mode Synthetic 2,8-dihydroxy-5-(4-xenyl) xanthene.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
(2) compound 10-1's is synthetic
Remove with 1.83g (5mmol) 2,8-dihydroxy-5-(4-xenyl) xanthene replaces 1.76g (5mmol) 1, outside 1-two (4-hydroxyphenyl) acenaphthene-2-ketone with embodiment 19 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 23: compound 10-2's is synthetic
Except that replace with 44.0g (0.4mol) resorcinol 37.4g (0.4mol) phenol with embodiment 10 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 24: compound 11-1's is synthetic
Figure A20048002685900471
Except that replace with 44.0g (0.4mol) resorcinol 43.2g (0.4mol) orthoresol and with 18.0g (0.1mol) 9-fluorenes replace 17.1g (0.1mol) β-Nai Yitong with embodiment 1 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 25: compound 11-2's is synthetic
Remove with 18.0g (0.1mol) 9-Fluorenone (from Kanto Chemical Co., the reagent of Inc.) replace outside 18.2g (0.1mol) biphenylcarboxaldehyde with embodiment 22 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 26: compound 11-3's is synthetic
Figure A20048002685900473
Remove with among 1.82g (5mmol) embodiment 24 synthetic 2,8-dihydroxy-5-(9, the 9-fluorenyl) xanthene replaces 1.84g (5mmol) 1-(2-naphthyl)-1, outside 1-two (3-methyl-4-hydroxyphenyl) ethane with embodiment 4 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 27: compound 12-1's is synthetic
Except that replace with 16.8g (0.1mol) acenaphthenone 18.0g (0.1mol) the 9-Fluorenone with embodiment 26 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Embodiment 28: potpourri 13-1's is synthetic
Figure A20048002685900482
R=H or tertbutyloxycarbonyl
Introducing degree=55% of tertbutyloxycarbonyl
In the solution that 1.75g (5mmol) bisphenol fluorene and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 1.20g (5.5mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain the title potpourri.By 1When H-NMR measured, the introducing degree of acid dissociation functional group was 55% in the phenolic hydroxyl.Analysis result is shown in table 1 and 2.
Embodiment 29: potpourri 13-2's is synthetic
R=H or tertbutyloxycarbonyl
Introducing degree=75% of tertbutyloxycarbonyl
In the solution that the two catechol fluorenes of 1.91g (5mmol) and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 3.27g (15mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain the title potpourri.When measuring by 1H-NMR, the introducing degree of acid dissociation functional group is 75% in the phenolic hydroxyl.Analysis result is shown in table 1 and 2.
Embodiment 30: potpourri 13-3's is synthetic
R=H or tertbutyloxycarbonyl
Introducing degree=80% of tertbutyloxycarbonyl
Synthetic 9 in 0.103g (0.25mmol) embodiment 13 (1), in the solution that 9-two (3,4,5-three hydroxyphenyl) fluorenes and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, through 30 minutes dropping 0.26g (1.2mmol) di-tert-butyl dicarbonates.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.Gained white powder drying under reduced pressure obtains the title potpourri.When measuring by ultimate analysis and 1H-NMR, the introducing degree of acid dissociation functional group is 80% in the phenolic hydroxyl.Analysis result is shown in table 1 and 2.
Embodiment 31: potpourri 13-4's is synthetic
Figure A20048002685900501
R=H or tertbutyloxycarbonyl
Introducing degree=95% of tertbutyloxycarbonyl
To 1.84g (5mmol) 1-(2-naphthyl)-1, in the solution that 1-two (3-methyl-4-hydroxyphenyl) ethane and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 1.20g (9.5mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain the title potpourri.When measuring by 1H-NMR, the introducing degree of acid dissociation functional group is 95% in the phenolic hydroxyl.Analysis result is shown in table 1 and 2.
Embodiment 32: potpourri 13-5's is synthetic
R=H or tertbutyloxycarbonyl
Introducing degree=95% of tertbutyloxycarbonyl
In the solution that the two catechol fluorenes of 1.91g (5mmol) and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 3.27g (19mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid is by silica gel column chromatography purification (eluant, eluent: ethyl acetate/hexane=1/3) obtain the title potpourri.By 1When H-NMR measured, the introducing degree of acid dissociation functional group was 95% in the phenolic hydroxyl.Analysis result is shown in table 1 and 2.
Comparative Examples 1: compound 14-1's is synthetic
Figure A20048002685900511
In the solution that 1.14g (5mmol) bisphenol-A (from Kanto Chemical Co., the reagent of Inc.) and 5ml anhydrous propanone and 1.2mg dimethylamino naphthyridine are mixed with, dripped 2.62g (12mmol) di-tert-butyl dicarbonate through 10 minutes.The gained potpourri was stirred 24 hours down at 40 ℃.Reaction liquid poured in the excessive water be settled out solid matter.The gained white powder cleans three times with distilled water, suction filtration, and drying under reduced pressure obtains title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Comparative Examples 2: compound 14-2's is synthetic
Remove with 1.34g (5mmol) bisphenol Z (from Kanto Chemical Co., the reagent of Inc.) replace outside 1.14g (5mmol) bisphenol-A with Comparative Examples 1 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Comparative Examples 3: compound 14-3's is synthetic
Figure A20048002685900521
Remove with 1.46g (5mmol) three (4-hydroxyphenyl) methane (from Honshu ChemicalIndustry Co., Inc.) amount that replaces 1.14g (5mmol) bisphenol-A and di-tert-butyl dicarbonate by 2.62g (12mmol) change into outside the 3.93g (16mmol) with Comparative Examples 1 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Comparative Examples 4: compound 14-4's is synthetic
Figure A20048002685900522
Remove the amount that replaces 1.14g (5mmol) bisphenol-A and di-tert-butyl dicarbonate with 1.77g (5mmol) three (4-hydroxyphenyl) benzene (from Aldrich Chemical Co., the reagent of Inc.) by 2.62g (12mmol) change into outside the 3.93g (16mmol) with Comparative Examples 1 in identical mode synthesising title compound.By ultimate analysis and 1H-NMR measures the structure of determining this compound.Analysis result is shown in table 1 and 2.
Comparative Examples 5
Remove polycarboxylated styrene (PHS-1) with 0.74g (5mmol) weight-average molecular weight 8000 (from Aldrich Chemical Co., Inc.) amount that replaces 1.14g (5mmol) bisphenol-A and di-tert-butyl dicarbonate by 2.62g (12mmol) change into outside the 0.37g (1.5mmol) with Comparative Examples 1 in identical mode synthetic mixture (PHS-2).By 1When H-NMR measured, the introducing degree of acid dissociation functional group was 30% in the phenolic hydroxyl.
Table 1
Compound number Molecular formula Molecular weight Calculate Measure
Embodiment
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 6-1 7-1 7-2 7-3 7-4 7-5 8-1 8-2 8-3 8-4 8-5 9-1 10-1 10-2 11-1 11-2 11-3 12-1 13-1 13-2 13-3 13-4 13-5 C 36H 40O 6 C 31H 32O 4 C 44H 52O 12 C 30H 32O 3 C 34H 38O 3 C 31H 32O 3 C 40H 48O 3 C 29H 28O 4 C 28H 26O 4 C 30H 28O 3 C 45H 50O 12 C 40H 42O 10 C 55H 66O 18 C 30H 26O 3 C 31H 26O 4 C 29H 26O 3 C 29H 24O 4 C 40H 46O 3 C 34H 32O 7 C 40H 34O 3 C 29H 26O 4 C 35H 34O 7 C 30H 26O 4 C 30H 24O 5 C 35H 32O 7 C 29H 24O 4 C 28H 24O 4 - - - - - 568 468 772 440 494 452 576 440 426 436 782 682 1014 434 462 422 436 574 552 528 438 566 450 464 564 436 424 - - - - - C：76.03，H：7.09，O：16.88 C：79.46，H：6.88，O：13.66 C：68.38，H：6.78，O：24.84 C：81.78，H：7.32，O：10.89 C：82.55，H：7.74，O：9.70 C：82.27，H：7.13，O：10.61 C：83.29，H：8.39，O：8.32 C：79.07，H：6.41，O：14.53 C：78.83，H：6.14，O：15.01 C：82.54，H：6.46，O：11.00 C：69.04，H：6.44，O：24.54 C：70.37，H：6.20，O：23.43 C：65.08，H：6.55，O：28.37 C：82.92，H：6.03，O：11.05 C：80.50，H：5.67，O：13.84 C：82.44，H：6.20，O：11.36 C：79.80，H：5.54，O：14.66 C：83.58，H：8.07，O：8.35 C：73.90，H：5.84，O：20.27 C：83.38，H：6.09，O：8.53 C：79.43，H：5.98，O：14.59 C：74.19，H：6.05，O：19.76 C：79.98，H：5.82，O：14.21 C：77.57，H：5.21，O：17.22 C：74.45，H：5.71，O：19.84 C：79.80，H：5.54，O：14.66 C：79.22，H：5.70，O：15.08 - - - - - C：76.14，H：7.00 C：79.50，H：6.83 C：68.51，H：6.71 C：81.80，H：7.35 C：82.70，H：7.60 C：82.38，H：7.02 C：83.41，H：8.30 C：79.16，H：6.31 C：78.95，H：6.04 C：82.50，H：6.53 C：69.13，H：6.38 C：70.45，H：6.04 C：65.18，H：6.65 C：83.01，H：6.00 C：80.40，H：5.77 C：82.42，H：6.22 C：79.91，H：5.50 C：83.40，H：8.27 C：73.81，H：5.80 C：83.42，H：6.02 C：79.53，H：5.91 C：74.11，H：6.15 C：80.05，H：5.72 C：77.64，H：5.16 C：74.55，H：5.61 C：79.63，H：5.67 C：79.16，H：5.80 - - - - -
Comparative Examples
1 2 3 4 14-1 14-2 14-3 14-4 C 25H 32O 6 C 28H 36O 6 C 34H 40O 9 C 39H 42O 9 428 469 592 654 C：70.07，H：7.53，O：22.40 C：71.77，H：7.74，O：20.49 C：68.97，H：6.80，O：24.3 C：71.54，H：6.47，O：21.99 C：70.0，H：7.61 C：71.73，H：7.62 C：69.2，H：6.71 C：71.73，H：6.25
Table 2
Compound number 1H-NMRδ(ppm)
Embodiment
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 6-1 7-1 7-2 7-3 7-4 7-5 8-1 8-2 8-3 8-4 8-5 9-1 10-1 10-2 11-1 11-2 11-3 12-1 13-1 7.6-6.8(13H，m)，2.1(9H，d)，1.4(18H，s) 7.8-6.6(13H，m)，4.7(1H，br)，2.2(9H，t)，1.5(9H，s) 7.8-7.3(13H，m)，2.3(3H，s)，1.5(36H) 7.8-6.6(13H，m)，5.4(1H，m)，4.7(1H，br)， 3.7-3.4(2H，m)，2.2(9H，t)，1.4(3H，s)，1.1(3H，t) 7.8-6.6(13H，m)，5.5(1H，s)，3.5(1H，br)， 2.3-1.5(22H，m) 7.8-6.6(13H，m)，5.5(1H，s)，4.7(1H，br)， 3.7-3.5(2H，m)，2.2(9H，t)，2.1-1.8(6H，m) 7.8-6.5(13H，m)，5.2(1H，s)，4.9(1H，br)，3.5(2H，q)， 2.7(2H，m)，2.3(3H，s)，1.7-1.2(26H，m) 7.8-6.6(15H，m)，4.7(1H，br)，2.2(3H，s)，1.5(9H，s) 7.9-6.5(15H，m)，4.9(1H，br)，1.5(9H，s) 7.6-7.0(17H，m)，5.6(1H，s)，5.5(1H，s)，5.4(1H，s)， 3.8-3.6(2H，m)，2.1-1.8(6H，m) 7.9-7.1(14H，m)，2.1(3H，s)，1.5(36H，s) 7.9-7.1(14H，m)，5.5(1H，br)，2.1(3H，s)， 1.5(27H，s) 7.7-7.3(8H，s)，6.9(4H，s)，1.5(54H，s) 8.1-7.0(16H，m)，5.5(1H，s)，5.4(1H，br)， 3.8-3.6(2H，m)，2.1-1.8(6H，m) 8.1-6.6(16H，m)，5.5(1H，s)，5.4(1H，br)， 3.8-3.6(2H，m)，2.1-1.8(6H，m) 7.7-6.8(14H，m)，5.5(1H，s)，5.4(1H.s)， 4,1-3.9(2H，q)，3.8-3.6(2H，m)，2.1-1.8(6H，m) 8.2-6.9(14H，m)，5.5(1H.s)，5.4(1H，br)， 3.8-3.6(2H，m)，2.1-1.8(6H，m) 7.7-6.5(12H，m)，5.2(1H，s)，4.9(1H，br)，4.1-3.8(2H，q)， 3.5(2H，q)，2.8-2.5(2H，m)，1.7-1.2(16H，m) 8.2-6.9(14H，m)，1.4(18H，s) 7.7-6.9(22H，m)，5.5(1H，q)，5.3(1H，br)， 4.1-3.8(2H，q)，3.5(2H，q)，1.6(3H，d)，1.2(3H，t) 7.9-7.2(7H，m)，6.8-6.6(4H，q)，6.4(2H，d)，5.4(1H，s)，3.7 (2H，t)，2.4(3H，s)，2.1-1.8(6H，m) 7.7-7.0(13H，m)，6.8(2H，s)，5.4(1H，s)，1.5(18H，s) 7.7-7.2(9H，m)，6.9-6.4(6H，m)，6.2(1H，s)，5.5(1H，s)，5.4 (1H，s)，3.9-3.7(2H，t)，2.1-1.8(6H，m) 8.2-6.5(14H，m)，6.2(1H，br)，1.5(9H，s) 8.2-7.0(14H，m)，1.5(18H，s)，1.2(3H，t) 8.2-6.5(14H，m)，6.2(1H，br)，3.5(2H，q)，1.6(3H，d)， 7.7-6.4(12H，m)，6.2(1H，br)，5.3(1H，s)，3.8-3.6(2H，q)， 3.5-3.4(2H，q)，1.6(3H，d)，1.2(3H，t) 8.0-7.0(17H，m)，1.5(10H，s)
29 30 31 32 13-2 13-3 13-4 13-5 7.9-7.1(14H，m)，5.5(1H，br)，2.1(3H，s)，1.5(27H，s) 7.7-7.3(8H，s)，6.9(4H，s)，5.5(1H，br)，1.5(43H，s) 7.6-6.8(13H，m)，2.1(9H，d)，1.4(17H，s) 7.9-7.1(14H，m)，5.5(1H，br)，2.1(3H，s)，1.5(34H，s)
Comparative Examples
1 2 3 4 14-1 14-2 14-3 14-4 7.3(2H，d)，7.1(2H，d)，2.2(4H，s)，1.5(18H，s) 7.3(2H，d)，7.1(2H，d)，2.2-1.5(28H，m) 7.3(12H，s)，1.5(27H，s) 7.7(9H，m)，7.3(6H，d)，1.5(27H，m)
Embodiment 33-64 and Comparative Examples 5-9: the character of compound and radiation-sensitive composition
The character of gained compound and composition among test implementation example 1-32 and the Comparative Examples 1-4.The results are shown in table 3 and 4.
Embodiment 65
Test is by 50mol% compound 5-6 and its middle product 1-(2-naphthyl)-1 of 50mol%, the character of the potpourri that 1-two (3-methyl-4-hydroxyphenyl) ethane (compound 14-5) is formed.Substituting group OR 1Quantity account for substituting group OR 1With 25% of OH sum.The results are shown in table 3 and 4.
Figure A20048002685900561
Embodiment 66
Test is by 40mol% compound 5-7 and its middle product 1-(2-naphthyl)-1 of 60mol%, the character of the potpourri that 1-two (3-cyclohexyl-4-hydroxyphenyl) ethane (compound 14-6) is formed.Substituting group OR 1Quantity account for substituting group OR 1With 20% of OH sum.The results are shown in table 3 and 4.
Figure A20048002685900562
Comparative Examples 9
The character of test compounds 14-5.The results are shown in table 3 and 4.
Table 3
Compound number (1) dissolubility in safety solvent (2) film forming (3) the dissolving inhibiting effect in developer solution
Embodiment
33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 6-1 7-1 7-2 7-3 7-4 7-5 8-1 8-2 8-3 8-4 8-5 A A A A A A A A A A B A A A A A A A A A A A A A A A A A A A B A A A A A A A A A A A A A A A A A A A A A A A A A A A A A
53 54 55 56 57 58 59 60 61 62 63 64 65 66 9-1 10-1 10-2 11-1 11-2 11-3 12-1 13-1 13-2 13-3 13-4 13-5 (5-6)/(14-5) ＝50/50 (5-7)/(14-6) ＝40/60 A A A A B A A A A A A B A A A A A A B A A A A A A B A A A A A A A A A A A A A A A A
Comparative Examples
5 6 7 8 9 14-1 14-2 14-3 14-4 14-5 C C A A A - - A B A - - A A C
Table 4
Compound number (4) with the adhesiveness of Si base material (5) alkali developable
Embodiment
33 34 35 36 37 38 39 40 41 42 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 6-1 A A B A A A A A A A A A A A A A A A A A
43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 7-1 7-2 7-3 7-4 7-5 8-1 8-2 8-3 8-4 8-5 9-1 10-1 10-2 11-1 11-2 11-3 12-1 13-1 13-2 13-3 13-4 13-5 (5-6)/(14-5)＝50/50 (5-7)/(14-6)＝40/60 B A A A A A A A A A A B A A B A A A A A A B A A B A A A A A A A A A A A A A A A A A A A A A A A
Comparative Examples
5 6 7 8 9 14-1 14-2 14-3 14-4 14-5 - - C C - A A A A A
Embodiment 67-68 and Comparative Examples 10-16: the evaluation of corrosion-resisting pattern and anti-dry corrosion
Gained compound among the preparation embodiment 1-32 as shown in table 5, the gained preparation filters the preparation radiation-sensitive composition with 0.2 μ m teflon (registered trademark) filtrator.The resolution and the susceptibility of the resist pattern that evaluation is formed by described radiation-sensitive composition.The results are shown in the table 6.All obtain unevenness minimum good pattern in edge among the embodiment 67-88.And air output is little in the exposure process.
Each radiation-sensitive composition with embodiment 72 and 86 forms the thick etchant resist of 100nm on gallium-arsenic wafer.With this etchant resist with RIE Etaching device etching period with tetrafluoromethane etching gas dry corrosion 30 seconds, 60 seconds, 90 seconds and 120 seconds under the etching condition of 70sccm, 50W and 20Pa.Measure the thickness of each etching period with measurer for thickness.Determine the etching speed of each etchant resist by the slope of the proximal line of match measured value.Etching speed is 8.8nm/min among the embodiment 72, is 20nm/min among the embodiment 86, shows the corrosion stability height.
Table 5
Resist compound or composition (g) Resin (g) Acid agent (g) Acid diffusion control agent (g) Solvent (g)
Embodiment Comparative Examples
67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 5-1(0.5) 5-2(0.5) 5-2(0.5) 5-2(0.5) 5-2(0.5) 5-5(0.5) 5-6(0.5) 5-6(0.5) 6-1(0.5) 7-2(0.5) 7-2(0.5) 7-3(0.5) 7-3(0.5) 8-2(0.5) 8-3(0.5) 9-1(0.5) 10-2(0.5) 11-3(0.5) 13-2(0.5) 13-2(0.5) (5-6)/(14-5) 50/50 (0.5) (5-7)/(14-6) 40/60 (0.5) - - - PHS-1(0.1) PHS-2(0.1) - - - - - - - PHS-1(0.1) - - - - - - - - - PAG-1(0.05) PAG-1(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) PAG-1(0.05) PAG-2(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1(0.05) PAG-1/PAG-2 (0.02/0.03) PAG-1(0.05) PAG-1(0.05) Q-1(0.005) Q-1(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) Q-1(0.005) Q-2(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.005) Q-1(0.0005) Q-1(0.005) Q-1(0.005) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2)
Comparative Examples
10 11 12 13 14 15 16 14-3(0.5) 14-3(0.5) 5-1(0.2) 5-2(0.2) 5-1(0.2) 7-3(0.2) 7-3(0.2) - - PHS-1(0.3) PHS-1(0.3) PHS-2(0.3) PHS-1(0.3) PHS-2(0.3) PAG-1(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) PAG-2(0.05) Q-1(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) Q-2(0.005) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2) S-1/S-2(1.3/3.2)
PAG-1: nine fluorine fourth sulfonic acid diphenylmethyl phenyl sulfoniums
PAG-2: trifluoromethanesulfonic acid triphenylsulfonium
Q-1: trioctylamine
Q-2: diazabicyclo octane
S-1：PGMEA
S-2：EL
Table 6
PEB (℃) Susceptibility (μ C/cm 2) Resolution (nm)
Embodiment
67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 100 80 80 80 80 80 80 80 80 100 100 100 80 80 80 80 80 80 80 80 80 80 40 20 20 10 10 10 10 10 10 20 20 30 10 10 10 10 10 10 20 20 10 5 50 50 50 60 60 50 50 50 50 50 50 50 60 50 50 50 50 50 50 50 50 50
Comparative Examples
10 11 12 13 14 15 16 80 80 80 80 80 80 80 60 60 20 20 20 20 20 100 100 80 80 80 80 80
Embodiment 89: anti-dry corrosion
Each radiation-sensitive composition with embodiment 72 and 86 forms the thick etchant resist of 100nm on gallium-arsenic wafer.With this etchant resist with RIE Etaching device etching period with tetrafluoromethane etching gas dry corrosion 30 seconds, 60 seconds, 90 seconds and 120 seconds under the etching condition of 70sccm, 50W and 20Pa.Measure the thickness of each etching period with measurer for thickness.Determine the etching speed of each etchant resist by the slope of the proximal line of match measured value.Etching speed is 8.8nm/min among the embodiment 72, is 20nm/min among the embodiment 86, shows the corrosion stability height.
Industrial applicibility
The radiosensitive compound of the present invention is as the main component of non-polymeric radiation-sensitive composition, and said composition not containing metal catalyst and susceptibility, resolution ratio, heat resistance, corrosion stability and the dissolubility in solvent is fabulous. Described radiation-sensitive composition and solubilizer are used in combination to provide has high-resolution and high sensitive pattern, thereby can high yield produce highly integrated semiconductor device.

Claims (18)

1. a radiation-sensitive composition comprises the solid constituent of 1-80 weight % and the solvent of 20-99 weight %, and said composition contains the compd B that requires a and b below satisfying:
(a) have by by the aromatic ketone or the aromatic aldehyde that each have 5 to 45 carbon atoms and have introduce at least one phenolic hydroxyl of the polyphenolic substance A that the compound condensation reaction of 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl produces structure that acid dissociation functional group forms and
(b) has 300 to 3000 molecular weight;
And the total amount of compd B and solubilizer accounts for the 50-99.999 weight % of solid constituent gross weight.
2. the described radiation-sensitive composition of claim 1, wherein said compd B has conjugated structure, comprises at least two phenyl ring and/or heteroatomic nonbonding electron pair.
3. the described radiation-sensitive composition of claim 2, wherein said conjugated structure are at least a structures that is selected from biphenyl structural, naphthalene structure, anthracene structure, luxuriant and rich with fragrance structure, pyrene structure, fluorene structured, acenaphthene structure, 1-ketone group acenaphthene structure, benzophenone structure, xanthene structure and thioxanthene structure.
4. acidic acid agent when the arbitrary described radiation-sensitive composition of claim 1 to 3, wherein said solid constituent contain at least a x ray irradiation x that is subjected to for example Extreme Ultraviolet, electron beam and X-ray.
5. the arbitrary described radiation-sensitive composition of claim 1 to 3, wherein said compd B is at least a compound that is selected from compound shown in the following formula 1:
Figure A2004800268590002C1
Each R wherein 1Base is independently for being selected from the acid dissociation functional group of substituent methyl, 1-replacement ethyl, 1-replacement n-pro-pyl, 1-branched-alkyl, silicyl, acyl group, 1-substituted alcoxyl ylmethyl, cyclic ethers base and alkoxy carbonyl group;
Each R 2Base is independently for being selected from the group of halogen atom, alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkenyl, acyl group, alkoxy carbonyl group, alkanoyloxy, aryl acyloxy, cyano group and nitro;
R 4Be hydrogen atom, C 1-6Alkyl or aryl, R 5For having the monovalence C of biphenyl structural or naphthalene structure 10-18Group, perhaps R 4With R 5Bonding time-CR each other 4R 5-can be have fluorene structured, acenaphthene structure, the divalence C of 1-ketone group acenaphthene structure or benzophenone structure 10-18Group;
Respectively do for oneself 0 to 4 integer of respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 3 integer of m0 and n0, m1 and n1, m2 and n2 all satisfies following formula: 1≤m0+m1+m2≤5,1≤n0+n1+n2≤5,1≤m1+n1≤6,1≤m0+m1≤3 and 1≤n0+n1≤3; With
Being positioned at-CR of two phenyl ring 4R 5-two carbon atoms at ortho position can form xanthene structure or thioxanthene structure shown in the following formula 2 by the mutual bonding of oxygen atom or sulphur atom:
R wherein 1, R 2, R 4And R 5Identical with the front; Respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 2 integer of respectively do for oneself 0 to 2 integer of p0 and q0, p1 and q1, p2 and q2 all satisfies: 1≤p0+p1+p2≤4,1≤q0+q1+q2≤4,1≤p1+q1≤4,1≤p0+p1≤2 and 1≤q0+q1≤2; With X be oxygen atom or sulphur atom.
6. the described radiation-sensitive composition of claim 5, wherein R 5Represent with following formula:
Or
Figure A2004800268590003C3
R wherein 3Be hydrogen atom or C 1-6Alkyl; P3 is 0 to 4 integer; Q3 is 0 to 3 integer; And p3 and the satisfied 0≤p3+q3 of q3≤7.
7. the described radiation-sensitive composition of claim 5, wherein-CR 4R 5-R 4And R 5Bonding makes-CR each other 4R 5Divalent group shown in the-formation following formula:
Or
R wherein 3Be hydrogen atom or C 1-6Alkyl; Y is singly-bound or carbonyl; Z is methylene or carbonyl; P3 is 0 to 4 integer; Q3 is 0 to 3 integer; And p3 and the satisfied 0≤p3+q3 of q3≤7.
8. the arbitrary described radiation-sensitive composition of claim 5 to 7, wherein said compd B is represented with following formula 3:
R wherein 1, R 2, R 4, R 5, m2 is defined identical with the front with n2, just-CR 4R 5-two carbon atoms being positioned at the ortho position of two phenyl ring can form xanthene structure or thioxanthene structure shown in the following formula 4 by the mutual bonding of oxygen atom or sulphur atom:
R wherein 1, R 2, R 4, R 5, X, p2 be defined identical with the front with q2.
9. the arbitrary described radiation-sensitive composition of claim 1 to 8, wherein said compd B are to produce by introduce acid dissociation functional group in the 10-95% of the phenolic hydroxyl sum of polyphenolic substance A.
10. the arbitrary described radiation-sensitive composition of claim 1 to 9, wherein said compd B are dissolved in propylene glycol methyl ether acetate or ethyl lactate with 5 weight % or more amount under 23 ℃.
11. the arbitrary described radiation-sensitive composition of claim 1 to 10 comprises the solid constituent of 5-40 weight % and the solvent of 60-95 weight %, contains the compd B of the 80-99 weight % that accounts for the solid constituent gross weight.
12. compound shown in the following formula 1:
Figure A2004800268590005C1
Each R wherein 1Base is independently for being selected from the acid dissociation functional group of substituent methyl, 1-replacement ethyl, 1-replacement n-pro-pyl, 1-branched-alkyl, silicyl, acyl group, 1-substituted alcoxyl ylmethyl, cyclic ethers base and alkoxy carbonyl group;
Each R 2Base is independently for being selected from the group of halogen atom, alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkenyl, acyl group, alkoxy carbonyl group, alkanoyloxy, aryl acyloxy, cyano group and nitro;
R 4Be hydrogen atom, C 1-6Alkyl or aryl, R 5For having the monovalence C of biphenyl structural or naphthalene structure 10-18Group, perhaps R 4With R 5Bonding time-CR each other 4R 5-can be have fluorene structured, acenaphthene structure, the divalence C of 1-ketone group acenaphthene structure or benzophenone structure 10-18Group;
Respectively do for oneself 0 to 4 integer of respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 3 integer of m0 and n0, m1 and n1, m2 and n2 all satisfies following formula: 1≤m0+m1+m2≤5,1≤n0+n1+n2≤5,1≤m1+n1≤6,1≤m0+m1≤3 and 1≤n0+n1≤3; With
Being positioned at-CR of two phenyl ring 4R 5-two carbon atoms at ortho position can form xanthene structure or thioxanthene structure shown in the following formula 2 by the mutual bonding of oxygen atom or sulphur atom:
Figure A2004800268590005C2
R wherein 1, R 2, R 4And R 5Identical with the front; Respectively do for oneself 0 to 3 integer of respectively do for oneself 0 to 2 integer of respectively do for oneself 0 to 2 integer of p0 and q0, p1 and q1, p2 and q2 all satisfies: 1≤p0+p1+p2≤4,1≤q0+q1+q2≤4,1≤p1+q1≤4,1≤p0+p1≤2 and 1≤q0+q1≤2; With X be oxygen atom or sulphur atom.
13. the described compound of claim 12, wherein R 5Represent with following formula:
Figure A2004800268590006C1
Or
R wherein 3Be hydrogen atom or C 1-6Alkyl; P3 is 0 to 4 integer; Q3 is 0 to 3 integer; And p3 and the satisfied 0≤p3+q3 of q3≤7.
14. the described compound of claim 12, wherein-CR 4R 5-R 4And R 5Bonding makes-CR each other 4R 5Divalent group shown in the-formation following formula:
Or
R wherein 3Be hydrogen atom or C 1-6Alkyl; Y is singly-bound or carbonyl; Z is methylene or carbonyl; P3 is 0 to 4 integer; Q3 is 0 to 3 integer; And p3 and the satisfied 0≤p3+q3 of q3≤7.
15. the arbitrary described compound of claim 12 to 14 is represented with following formula 3:
R wherein 1, R 2, R 4, R 5, m2 is defined identical with the front with n2, just-CR 4R 5-two carbon atoms being positioned at the ortho position of two phenyl ring can form xanthene structure or thioxanthene structure shown in the following formula 4 by the mutual bonding of oxygen atom or sulphur atom:
Figure A2004800268590007C1
R wherein 1, R 2, R 4, R 5, X, p2 be defined identical with the front with q2.
16. the arbitrary described compound of claim 12 to 14 is to be selected from following at least a compound:
Figure A2004800268590008C1
With
Figure A2004800268590009C1
R wherein 1To R 4, Y, Z, m0 to m2, n0 to n2, p0 to p3 and q0 to q3 define as the front.
17. the arbitrary described compound of claim 12 to 16, wherein OR 1The quantity of base accounts for OR 1The 10-95% of base and OH base sum.
18. the arbitrary described compound of claim 12 to 17, it is dissolved in propylene glycol methyl ether acetate or ethyl lactate with 5 weight % or more amount under 23 ℃.
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