CN101310223A - Photoactive compounds - Google Patents
Photoactive compounds Download PDFInfo
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- CN101310223A CN101310223A CNA2006800429133A CN200680042913A CN101310223A CN 101310223 A CN101310223 A CN 101310223A CN A2006800429133 A CNA2006800429133 A CN A2006800429133A CN 200680042913 A CN200680042913 A CN 200680042913A CN 101310223 A CN101310223 A CN 101310223A
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- sulfonium
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Abstract
The present invention relates to novel photoacid generators.
Description
Technical field
The present invention relates to new Photoactive compounds, it is used for the photoetching composition in the microlithography field, is particularly useful for negative imaging and positive map picture in the semiconductor element production, and the photoetching compositions and the technology that are used for the photoresist imaging.
Background technology
Photoetching compositions is used to make the microlithography typography of miniaturized electric sub-element, for example is used to make computer chip and integrated circuit.Usually, in these technologies, at first the film coating with photoetching compositions puts on the base material, for example is used for making the silicon chip of integrated circuit.With the substrate baking that applies, evaporate any solvent in the photoetching compositions, and coating is fixed in the substrate then.And then, make and be coated in the imaging mode of exposure suprabasil photoresist carries out to(for) radiation.
Radiant exposure causes the chemical transformation in the exposed surface of coating surface.Visible light, ultraviolet (UV) light, electron beam and X-radiation can be normally used emission types in microlithography technology now.After the exposure of this imaging mode, coated substrate is handled with developer solution, to dissolve and to remove the radiant exposure or the unexposed zone of photoresist.The miniaturization of semiconductor element tendency has caused the use of new photoresist that can sensitization in more and more lower radiated wave strong point, and has also caused the use of complicated multilevel system, to overcome the difficulty relevant with this miniaturization.
Two types photoetching compositions is arranged: negative effects and positivity effect.The photoresist type that specified point in photoetching technique uses is by the designing institute decision of semiconductor devices.When the imaging of negative effects photoetching compositions radiant exposure, the zone that is exposed to the photoetching compositions in the radiation becomes to be difficult for being dissolved in the developer solution and (cross-linking reaction for example takes place), and the unexposed area of photoresist coating is dissolvable in water in this solution relatively.Thereby, handle the negative resist of exposure with developer, can cause the removing of non-exposed area of photoresist coating, and in coating, produce negative-appearing image, expose the required part of bottom substrate surface thus, photoetching compositions is deposited on this surface.
On the other hand, when positivity effect photoresists composition with imaging mode during for radiant exposure, rearrangement reaction (for example takes place) in the zone that is exposed to the photoetching compositions in the radiation easier being dissolved in the developer solution that become, and unexposed area becomes and can not be dissolved in the developer solution relatively.Thereby, handle the positive-working photoresist that exposes with developer, can remove the exposure area of coating, and in photoresist coating, produce erect image.In addition, the required part of exposing lower surface.
Photoresist resolution is defined as: the resist composition can be transferred to minimal characteristic the substrate with height imaging edge sharpness from photomask after exposure and video picture.Make in the application in current many forward positions, approximately the photoresist resolution less than 1/2nd μ m (micron) is necessary.In addition, the photoresist wall profile of video picture is near normally desirable perpendicular to substrate.In the video picture of resist coating and this boundary line between the video picture zone not, can in substrate, change into the accurate pattern transmission of mask images.Because carry out the critical dimension that miniaturization can reduce device, this becomes even is more crucial.Be lower than 150 nanometers if the photoresist size has been reduced to, the roughness of photoresist image becomes critical problem.Edge roughness is commonly called line edge roughness, for lines and space diagram typically to be observed and typically to be observed with sidewall roughness for contact hole along the roughness of photoresist line.Edge roughness has minus effect on the lithography characteristic of photoresist, particularly can reduce aspect the critical dimension amplitude, and be transferred to aspect the substrate at the line edge roughness with photoresist.Therefore, the photoresist with minimum edge edge roughness is very desirable.
The photoresist responsive to short wavelength's (between about 100 nanometers and about 300 nanometers) usually is used for the geometric place of requirement sub-half-micron.Particularly preferably be the photoresist that comprises non-aromatic polymer, photoacid generator, optional dissolved inhibitor and solvent.
The pattern that the positive and negative tone photoresist of high resolving power, chemical amplification, deep ultraviolet (100-300 nanometer) can be used for having less than 1/4th microns geometric image forms.Up to now, three kinds of main deep ultraviolets (UV) exposure technique is arranged, it provides effective improvement aspect miniaturization, and these technology are used the laser instrument in 248 nanometers, 193 nanometers and 157 nanometer emitted radiations.The photoresist that is used for dark UV typically comprises polymkeric substance, and this polymkeric substance has acid groups and its acidic photolytic activity composition and solvent can go protection, light absorption under the situation that acid exists the time.
The photoresist that is used for 248 nanometers is typically based on polycarboxylated styrene that replaces and its multipolymer, for example at US4, and those that describe in 491,628 and US5,350,660.On the other hand, the photoresist that is used for the exposure of 193 nanometers requires non-aromatic polymer, because aromatic compounds is opaque at this wavelength place.US5,843,624 and GB2,320,718 disclose the photoresist that can be used for the exposure of 193 nanometers.Usually, the polymkeric substance that comprises clicyclic hydrocarbon can be used for the photoresist of the following exposure of 200 nanometers.Because all reasons are incorporated into clicyclic hydrocarbon in the polymkeric substance, main because they have than higher carbon: the hydrogen ratio, this can improve corrosion stability, and they also provide the transparency at low wavelength place, and they have the high glass transition of ratio.At the photoresist of 157 nanometers sensitivities based on fluorinated polymer, known its be transparent at this wavelength place.The photoresist that comes from polymkeric substance (it comprises fluorinated groups) is described among WO00/67072 and the WO00/17712.
It is transparent that the polymkeric substance that uses in photoresist is designed to imaging wavelength, but then, typically the photolytic activity composition has been designed to absorb to reach best photonasty at the imaging wavelength place.The photonasty of photoresist depends on the absorption characteristic of photolytic activity composition, and it is more little to absorb energy high more, that generation acid is required, and photoresist has photonasty more.
Summary of the invention
The present invention relates to have the compound of following formula
R wherein
A, R
BBe OR independently of one another
1, R
CBe hydrogen or OR independently
1, each R wherein
1Be hydrogen independently, alkyl, alkoxyalkyl, alkoxycarbonyl alkyl, alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl wherein, SO
2R
4And SiR
4 3, R wherein
4Be alkyl, aryl, or wherein cycloalkyl ring is chosen monocycle alkyl or the multi-ring alkyl that comprises one or more O atoms wantonly; described alkyl, alkoxyalkyl, alkoxycarbonyl alkyl; alkyl-carbonyl; aryl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, wherein cycloalkyl ring comprises the monocycle alkyl of one or more O atoms-or multi-ring alkyl oxygen base alkyl; wherein to comprise the monocycle alkyl of one or more O atoms or multi-ring alkyl be unsubstituted to cycloalkyl ring or replaced by one or more following group: halogen; alkyl, monocycle alkyl or multi-ring alkyl replace, alkoxy; cycloalkyloxy; dialkyl amido, dicyclo dialkyl amido, hydroxyl; cyano group; nitro, three fluoro ethane sulfonyls (tresy1), oxo; aryl; aralkyl, oxygen atom, CF
3SO
3, aryloxy group, the group of artyl sulfo and formula (II) to (VI):
R wherein
10And R
11Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl, or R
10And R
11Can represent alkylidene together forming five or hexatomic ring,
R
12The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, or aralkyl, or R
10And R
12Represent alkylidene together, with insert-the C-O-group forms five or hexatomic ring, the nuclear carbon atom is optional to be replaced by oxygen atom,
R
13The optional straight or branched alkyl chain that comprises one or more O atoms of expression, or monocycle alkyl or multi-ring alkyl,
R
14And R
15Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl,
R
16The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, aryl or aralkyl,
R
17The optional C that comprises one or more O atoms of expression
1-20The straight or branched alkyl chain, monocycle alkyl or multi-ring alkyl, aryl, aralkyl, group-SiR
16 2R
17, or group-O-SiR
16 2R
17, the optional C that comprises one or more O atoms
1-20Straight or branched alkyl chain, monocycle alkyl or multi-ring alkyl, aryl and aralkyl are unsubstituted or are substituted according to top mode; With
X
-It is negative ion.
The present invention also relates to be used for the photoetching compositions of dark UV imaging, it comprises polymkeric substance and compound of the present invention, and polymkeric substance comprises acid-unstable group.The invention still further relates to and make the photoresist imaging method, this method comprises the following steps: with composition coated substrate of the present invention, curing substrate desolvates to remove basically, photoresist coating is exposed with imaging mode, post exposure bake photoresist coating and photoresist coating is developed with alkaline aqueous solution.
Embodiment
The present invention relates to have the compound of following formula
R wherein
A, R
BBe OR independently of one another
1, R
CBe hydrogen or OR independently
1, each R wherein
1Be hydrogen independently, alkyl, alkoxyalkyl, alkoxycarbonyl alkyl, alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl wherein, SO
2R
4And SiR
4 3, R wherein
4Be alkyl, aryl, or optional one or more O atom single-ring alkyl or the multi-ring alkyl of comprising of cycloalkyl ring wherein; described alkyl, alkoxyalkyl, alkoxycarbonyl alkyl; alkyl-carbonyl; aryl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, wherein cycloalkyl ring comprises the monocycle alkyl of one or more O atoms-or multi-ring alkyl oxygen base alkyl; wherein to comprise the monocycle alkyl of one or more O atoms or multi-ring alkyl be unsubstituted to cycloalkyl ring or replaced by one or more following group: halogen; alkyl, monocycle alkyl or multi-ring alkyl replace, alkoxy; cycloalkyloxy; dialkyl amido, dicyclo dialkyl amido, hydroxyl; cyano group; nitro, three fluoro ethane sulfonyls (tresy1), oxo; aryl; aralkyl, oxygen atom, CF
3SO
3, aryloxy group, the group of artyl sulfo and formula (II) to (VI):
R wherein
10And R
11Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl, or R
10And R
11Can represent alkylidene together forming five or hexatomic ring,
R
12The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, or aralkyl, or R
10And R
12Represent alkylidene together, with insert-the C-O-group forms five or hexatomic ring, the nuclear carbon atom is optional to be replaced by oxygen atom,
R
13The optional straight or branched alkyl chain that comprises one or more O atoms of expression, or monocycle alkyl or multi-ring alkyl,
R
14And R
15Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl,
R
16The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, aryl or aralkyl and
R
17The optional C that comprises one or more O atoms of expression
1-20The straight or branched alkyl chain, monocycle alkyl or multi-ring alkyl, aryl, aralkyl, group-SiR
16 2R
17, or group-O-SiR
16 2R
17, the optional C that comprises one or more O atoms
1-20Straight or branched alkyl chain, monocycle alkyl or multi-ring alkyl, aryl and aralkyl are unsubstituted or are substituted according to top mode; With
X
-Be negative ion, preferred acceptable negative ion in photoresist is used.
The present invention also relates to be used for the photoetching compositions of UV imaging far away, it comprises polymkeric substance and compound of the present invention, and polymkeric substance comprises acid-unstable group.The invention still further relates to and make the photoresist imaging method, this method comprises the following steps: with composition coated substrate of the present invention, curing substrate desolvates to remove basically, photoresist coating is exposed with imaging mode, post exposure bake photoresist coating and photoresist coating is developed with alkaline aqueous solution.
Term alkyl used herein is meant the straight or branched hydrocarbon, and it preferably has 1 to 20 carbon atom.The exemplary of alkyl includes, but are not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methyl hexyl, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group, n-heptyl, n-octyl, n-nonyl and positive decyl.
Alkylidene refers to divalent alkyl, and it can be a straight or branched, methylene for example, ethylidene, propylidene, butylidene or the like.
Carbonyl is meant-C (O)-.
Term monocycle alkyl used herein is meant optional replace, the saturated or undersaturated mononaphthene basic ring of part shape system, preferably has 3 to 8 carbon atoms, if wherein ring is that part is undersaturated, then it is a monocyclic alkenyl.The example of this mononaphthene basic ring comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or suberyl.
Term multi-ring alkyl used herein is meant optional replace, the saturated or undersaturated multi-ring alkyl ring-type of part system, comprises two or more rings, preferably has 5 to 20 carbon atoms, if wherein member ring systems is that part is undersaturated, then it is many cycloalkenyl groups.The example of this polynaphthene basic ring includes, but are not limited to: 3-oxatricyclo [4.2.1.0
2,5] nonyl, Fourth Ring [5.2.2.0.0] undecyl, bornyl, isobornyl, norborny and adamantyl.
Term aryl used herein is meant by removing a hydrogen atom derived from the atomic group of aromatic hydrocarbons (preferably having 6 to 14 carbon atoms), and can be to replace or unsubstituted.Aromatic hydrocarbons can be monokaryon or multinuclear.The example of the aryl of monokaryon type comprises phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, cumenyl or the like.The example of the aryl of multinuclear type comprises naphthyl, anthryl, phenanthryl or the like.
Term thiazolinyl used herein is meant derived from the straight or branched hydrocarbon preferably have 2 to 20 carbon atoms, and comprises the group of at least one two key.
The term alkoxy is meant group alkyl-O-, and wherein alkyl as defined herein.The exemplary of alkoxy includes, but are not limited to: methoxyl, ethoxy, propoxyl group, 2-propoxyl group, butoxy, tert-butoxy, amoxy and own oxygen base.
Term aryloxy is meant aryl-O-group, and wherein aryl as defined herein.
The term alkoxycarbonyl alkyl is meant the alkyl of the alkoxy carbonyl group replacement that is defined by this paper.The example of alkoxycarbonyl alkyl comprises: methoxycarbonyl group methyl [CH
3O-C (=O)-CH
2-], ethoxycarbonylmethyl group [CH
3CH
2O-C (=O)-CH
2-], methoxycarbonyl group ethyl [CH
3O-C (=O)-CH
2CH
2-], and ethoxycarbonyl-ethyl [CH
3CH
2O-C (=O)-CH
2CH
2-].
The term cycloalkyloxy is meant group monocycle alkyl-O-or multi-ring alkyl-O-, and wherein monocycle alkyl or multi-ring alkyl are as defined herein.
Term alkyl-carbonyl used herein is meant by carbonyl defined herein and appends to alkyl defined herein on the parent molecule part, its generally can be expressed as alkyl-C (O)-.The exemplary of alkyl-carbonyl includes, but are not limited to: acetyl group (methyl carbonyl), and bytyry (propyl group carbonyl), caprylyl (heptyl carbonyl), dodecane acyl group (undecyl carbonyl), or the like.
Alkoxy carbonyl group be meant alkyl-O-C (O)-, wherein alkyl is as described previously.Non-limitative example comprises: methoxycarbonyl group [CH
3O-C (O)-] and carbethoxyl group [CH
3CH
2O-C (O)-], benzyloxycarbonyl group [C
6H
5CH
2O-C (O)-] or the like.
Alkoxyalkyl is meant that end alkyl is connected with moieties by ether oxygen atom, and it generally can be expressed as alkyl-O-alkyl, and wherein alkyl can be a straight or branched.The example of alkoxyalkyl includes, but are not limited to: methoxy-propyl, methoxyl butyl, ethoxycarbonyl propyl, methoxy.
The monocycle alkyl-or multi-ring alkyl oxygen base carbonylic alkyl be meant terminal monocycle alkyl or multi-ring alkyl by-O-C (=O)-be connected with moieties, generally be expressed as the monocycle alkyl-or multi-ring alkyl-O-C (=O)-alkyl.
The monocycle alkyl-or multi-ring alkyl oxygen base alkyl be meant that terminal monocycle alkyl or multi-ring alkyl are connected with moieties by ether oxygen atom, generally be expressed as monocycle alkyl-or multi-ring alkyl one O-alkyl.
Term aralkyl is meant the alkyl that hydrogen atom is wherein replaced by aryl, and wherein aryl and alkyl are as top definition.The example of aralkyl comprises (non-limiting): benzyl, 2-phenylethyl, 3-phenyl propyl, 4-phenyl butyl, 5-phenylpentyl, 4-benzyl ring hexyl, 4-benzyl rings hexyl, 4-benzyl ring hexyl methyl, 4-benzyl rings hexyl methyl, naphthyl methyl or the like.
Negative ion X
-Example comprise usually those that obtain with photoacid generator, for example can comprise CF
3SO
3 -, CHF
2SO
3 -, CH
3SO
3 -, CCl
3SO
3 -, C
2F
5SO
3 -, C
2HF
4SO
3 -, C
4F
9SO
3 -, phenyl-pentafluoride sulfonate radical, (Rf
1SO
2)
3C
-(Rf
1SO
2)
2N
-, each Rf wherein
1Be independently selected from highly fluorinated or complete fluorinated alkyl or fluoro aryl, and can be ring-type, as any two Rf
1Being connected when forming bridge of group, further, Rf
1Alkyl chain comprises 1-20 carbon atom, optional comprises stretched wire oxygen, and can be straight chain, side chain or ring-type, and divalence oxygen, trivalent nitrogen or sexavalence sulphur skeletal chain at interval is further like this, works as Rf
1When comprising ring texture, this structure has 5 or 6 ring persons, optional wherein 1 or 2 be heteroatoms, Rg-O-Rf
2-SO
3 -, Rf wherein
2Be selected from straight or branched (CF
2)
j, wherein j is from 4 to 10 integer, and C
1-C
12Perfluor naphthenic base bivalent radical, it is optional by perfluoro C
1-10Alkyl replaces.
Rg is selected from C
1-C
20The monocycle alkyl or the multi-ring alkyl of straight chain, side chain, C
1-C
21The monocyclic alkenyl of straight chain, side chain or many cycloalkenyl groups, aryl and aralkyl, alkyl, thiazolinyl, aralkyl and aryl be unsubstituted, replace, optional one or more stretched wire oxygen atom that comprises, partially fluorinated or fluoridize fully.Example comprises (C
2F
5SO
2)
2N
-, (C
4F
9SO
2)
2N
-, (C
8F
17SO
2)
3C
-, (CF
3SO
2)
3C
-, (CF
3SO
2)
2N
-, (SO
2C
8F
17)
2N
-, (SO
2CF
3) (SO
2C
8F
17) N
-, (CF
3SO
2) (C
4F
9SO
2) N
-, (SO
2C
3F
7)
2N
-, (C
2F
5SO
2)
3C
-, (C
4F
9SO
2)
3C
-, (CF
3SO
2)
2(C
2F
5SO
2) C
-, (C
4F
9SO
2) (C
2F
5SO
2)
2C
-, (CF
3SO
2) (C
4F
9SO
2) N
-, [(CF
3)
2NC
2F
4SO
2]
2N
-, (CF
3)
2NC
2F
4SO
2C
-(SO
2CF
3)
2, (3,5-two (CF
3) C
6H
3) SO
2N
-SO
2CF
3, C
6F
5SO
2C
-(SO
2CF
3)
2, C
6F
5SO
2N
-SO
2CF
3,
CF
3CHFO (CF
2)
4SO
3 -, CF
3CH
2O (CF
2)
4SO
3 -, CH
3CH
2O (CF
2)
4SO
3 -, CH
3CH
2CH
2O (CF
2)
4SO
3 -, CH
3O (CF
2)
4SO
3 -, C
2H
5O (CF
2)
4SO
3 -, C
4H
9O (CF
2)
4SO
3 -, C
6H
5CH
2O (CF
2)
4SO
3 -, C
2H
5OCF
2CF (CF
3) SO-, CH
2=CHCH
2O (CF
2)
4SO
3 -, CH
3OCF
2CF (CF
3) SO
3 -, C
4H
9OCF
2CF (CF
3) SO
3 -, C
8H
17O (CF
2)
2SO
3 -, and C
4H
9O (CF
2)
2SO
3 -Other example of suitable anion can be in U.S. Pat 6,841,333 and U.S. Pat 5,874,616 in obtain.
In one embodiment of the invention, R
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein independently, the wherein optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl, and SO
2R
4, R wherein
4Be aryl, alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl wherein, aryl is unsubstituted or replaces.
In further embodiment, R
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be alkyl-carbonyl unsubstituted or that replace independently.
In further embodiment, R
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1The monocycle alkyl that is unsubstituted independently or replaces-or multi-ring alkyl oxygen base carbonylic alkyl, wherein cycloalkyl ring is chosen wantonly and is comprised one or more O atoms.
In further embodiment, R
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be SO independently
2R
4, R wherein
4It is aryl unsubstituted or that replace.
Comprise according to compound of the present invention; for example; two [4-acetyl group oxygen base phenyl] phenyl sulfonium perfluoro fourth sulfonate; two [4-acetyl group oxygen base phenyl] phenyl sulfonium 4-(1,1,1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [2-methyl adamantane base-acetyl group Oxymethoxy phenyl] phenyl sulfonium perfluor fourth sulfonate, two [4,4-two (trifluoromethyl)-3-ethane diacid three ring [4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium perfluoro fourth sulfonate, two [4,4-two (trifluoromethyl)-3-ethane diacid three ring [4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium perfluoro mesylate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl anisyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] nonyl-anisyl] phenyl sulfonium two (trifluoromethyl sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5]-nonyl anisyl] phenyl sulfonium two (perfluoro ethylsulfonyl)-acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl anisyl] phenyl sulfonium (whole fluorinated methyl sulfonyl) (perfluoro butyl sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl anisyl] phenyl sulfonium two (perfluoro sulfonyl propyl base) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] the nonyl methoxyphenyl] phenyl sulfonium two (perfluoro butyl sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5]-nonyl anisyl] phenyl sulfonium three (trifluoromethyl-sulfonyl) methide; two [4-acetyl group oxygen base phenyl] phenyl sulfonium perfluoro mesylate; two [4-acetoxyl group phenyl] phenyl sulfonium two (trifyl) acid imide; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imides; two [4-acetoxyl group phenyl] phenyl sulfonium (perfluoro mesyl) (perfluoro fourth sulfonyl) acid imides; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluoro third sulfonyl) acid imide; two [4-acetoxyl group phenyl] phenyl sulfonium three (trifyl) methide; two [4-acetoxyl group phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluoro fourth sulfonyl) acid imide; two [2-methyl adamantane base acetyl group oxygen base anisyl] phenyl sulfonium-4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro butane-sulfonate; two [2-methyl adamantane base acetyl group oxygen base anisyl] phenyl sulfonium perfluoro mesylate; two [2-methyl adamantane base acetyl group oxygen base anisyl] phenyl sulfonium two (trifyl) acid imide; two [2-methyl adamantane base acetyl group oxygen base-methoxyphenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide; two [2-methyl adamantane base-acetyl group oxygen base anisyl] phenyl sulfonium (whole fluorinated methyl sulfonyl) (perfluoro fourth sulfonyl) acid imide; two [2-methyl adamantane base-acetyl group Oxymethoxy phenyl] phenyl sulfonium two (perfluoro third sulfonyl) acid imides; two [2-methyl adamantane base-acetyl group oxygen base anisyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [2-methyl adamantane base acetyl group oxygen base-anisyl] phenyl sulfonium three (trifluoromethyl-sulfonyl) methide; two [2-methyl adamantane base acetyl group Oxymethoxy phenyl] phenyl sulfonium two (perfluoro fourth sulfonyl) acid imide; two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5] the nonyl anisyl] phenyl sulfonium 4-propoxyl group perfluoro butane-sulfonate; two [4-hydroxy phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide; two [4-hydroxy phenyl] phenyl sulfonium two (trifyl) acid imides; two [4-hydroxy phenyl] phenyl sulfonium (perfluoro mesyl) (perfluoro butyl-sulfonyl) acid imide; two [4-hydroxy phenyl]-phenyl sulfoniums two (perfluoro sulfonyl propyl base) acid imide; two [4-hydroxy phenyl]-phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imides; two [4-hydroxy phenyl]-phenyl sulfonium three (trifyl) methides; two [4-hydroxy phenyl]-phenyl sulfonium 4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [4-hydroxy phenyl]-phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-hydroxy phenyl] phenyl sulfonium perfluoro fourth sulfonate; two [4-hydroxy phenyl]-phenyl sulfonium perfluoro methane-sulfonate; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium two (trifyl) acid imide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium (perfluoro mesyl) (perfluoro butyl-sulfonyl) acid imide; two [4-five fluoro-benzenesulfonyl oxygen base phenyl] phenyl sulfonium two (perfluoro third sulfonyl) acid imide; two [4-phenyl-pentafluoride sulfonyl oxygen base phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide; two [4-phenyl-pentafluoride sulfonyl-oxygen base phenyl] phenyl sulfonium three (trifyl) methide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium 4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [4-phenyl-pentafluoride sulfonyl-oxygen base phenyl] phenyl sulfonium 4-propoxyl group perfluor fourth sulfonate; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium perfluoro fourth sulfonate; two [4-phenyl-pentafluoride sulfonyl oxygen base phenyl] phenyl sulfonium perfluoro methane-sulfonate; two [4-(3; 5-two (trifluoromethyl)-benzenesulfonyl oxygen base) phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) benzenesulfonyl oxygen base)-and phenyl] phenyl sulfonium two (trifyl) acid imide; two [4-(3; 5-two (three fluoro-methyl) benzene-sulfonyl oxygen base) phenyl] phenyl sulfonium (perfluoro mesyl) (perfluoro fourth sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) benzenesulfonyl-oxygen base) phenyl] phenyl sulfonium two (perfluoro third sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) benzenesulfonyl oxygen base) phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) benzenesulfonyl oxygen base) phenyl] phenyl sulfonium three (trifyl) methide, two [4-(3,5-two (three fluoro-methyl) benzenesulfonyl oxygen base) phenyl] phenyl sulfonium 4-(1; 1; 1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [4-(3; 5-two (trifluoromethyl)-benzenesulfonyl oxygen base) phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-(3,5-two (trifluoromethyl)-benzenesulfonyl oxygen base) phenyl] phenyl sulfonium perfluoro fourth sulfonate, two [4-(3; 5-two (trifluoromethyl) benzenesulfonyl-oxygen base) phenyl] phenyl sulfonium perfluoro methane-sulfonate; two [4-trifyl oxygen base) phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imide, two [4-trifyl oxygen base) phenyl] phenyl sulfonium two (trifluoromethyl-sulfonyl) acid imide, two [4-trifyl oxygen base) phenyl] phenyl sulfonium (perfluoro mesyl) (perfluoro fourth sulfonyl) acid imide; two [4-trifyl oxygen base) phenyl] phenyl sulfonium two (perfluoro sulfonyl propyl base) acid imide; two [4-trifyl oxygen base) phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide, two [4-trifyl oxygen base) phenyl] phenyl sulfonium three (trifyl) methide, two [4-trifluoromethyl-sulfonyl oxygen base) phenyl] phenyl sulfonium 4-(1; 1; 1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [4-trifyl oxygen base) phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-trifluoromethyl-sulfonyl oxygen base) phenyl] phenyl sulfonium perfluoro fourth sulfonate and two [4-trifyl oxygen base) phenyl] phenyl sulfonium perfluoro mesylate.
The method that can generally acknowledge according to those skilled in the art and the method for for example describing are hereinafter synthesized compound of the present invention: Houben, Weyl, Methoden der OrganischenChemie (organic chemistry method), Thieme Verlag, Stuttgart, New York.
The method of describing among the further reference work embodiment, it can be used as the criterion of further preparation The compounds of this invention for those skilled in the art.
The polymkeric substance that is used for photoetching compositions comprises those polymkeric substance with acid-unstable group; acid-unstable group can make polymkeric substance can not be dissolved in the alkaline aqueous solution; but this polymkeric substance can go polymkeric substance catalysis protection under the situation that acid exists, and then polymkeric substance becomes and dissolves in the alkaline aqueous solution.Preferably, polymkeric substance is transparent below 200 nanometers, and is non-aromatics basically, preferred acrylate and/or cyclic olefin polymer.This polymkeric substance is such as but not limited to be described in US5, those in 843,624, US5,879,857, WO 97/33,198, EP789,278 and GB2,332,679.The preferred non-aromaticity polymkeric substance that is used for the following irradiation of 200 nanometers is tygon of the acrylate of replacement, cycloolefin, replacement or the like.Can also use aromatic polymer and its multipolymer, especially expose for 248 nanometers based on polycarboxylated styrene.
Usually based on poly-(methyl) acrylate, wherein at least one unit contains side extension alicyclic group and the acid-unstable group side hangs on polymer backbone and/or the alicyclic group based on the polymkeric substance of acrylate.The example that side is hung alicyclic group can be an adamantyl, three ring decyls, and isobornyl,
Base and their derivant.Other side group can also be incorporated in the polymkeric substance, for example mevalonolactone, gamma butyrolactone, alkyl oxy alkyl or the like.The example of structure of alicyclic group comprises:
Monomer type and its are incorporated into ratio optimization in the polymkeric substance, to obtain best lithographic performance.This polymkeric substance be described in following in: people such as R.R.Dammel, Advancesin Resist Technology and Processing, SPIE, Vol.3333, p144, (1998).The example of these polymkeric substance comprises poly-(2-methyl-2-adamantyl methacrylate-copolymerization-mevalonolactone methacrylate), poly-(carboxyl-Fourth Ring dodecyl methyl acrylate-copolymerization-THP trtrahydropyranyl-carboxyl Fourth Ring dodecyl methyl acrylate), poly-(three ring decyl acrylate-copolymerization-tetrahydrochysene-pyranose methacrylate-copolymerization-methacrylic acids) and poly-(3-oxo cyclohexyl methyl acrylate-copolymerization-adamantyl methacrylate).
By cyclenes and norborene and the synthetic polymkeric substance of tetracyclododecen derivant, can or use organo-metallic catalyst to carry out polymerization by ring-opening metathesis, free radical polymerization.Cycloalkene derivatives also can with cyclic anhydride or with the copolymerization of maleimide or derivatives thereof.The example of cyclic anhydride is maleic anhydride (MA) and itaconic anhydride.Cyclenes can be incorporated in the skeleton of polymkeric substance, and can be any replacement or the unsubstituted polycyclic hydrocarbon that contains unsaturated link.Monomer can connect acid-unstable group.Can come synthetic polymer by one or more cyclenes monomer with unsaturated link.The cyclenes monomer can be to replace or unsubstituted norborene or Fourth Ring dodecane.Substituting group on the cyclenes can be aliphatic series or cycloalphatic alkyl, ester, acid, hydroxyl, nitrile or alkyl derivative.The example of cyclenes monomer comprises without limitation:
Also operable other cyclenes monomer is in polymkeric substance is synthetic:
This polymkeric substance is described in below with reference in the document, and is introduced into this paper: people such as M-D.Rahman, Advances in Resist Technology and Processing, SPIE, Vol.3678, p1193, (1999).The example of these polymkeric substance comprises poly-((tert-butyl group 5-norborene-2-carboxylate-copolymerization-2-hydroxyethyl 5-norborene-2-carboxylate-copolymerization-5-norborene-2-carboxylic acid-copolymerization-maleic anhydride), poly-(tert-butyl group 5-norborene-2-carboxylate-copolymerization-isobornyl-5-norborene-2-carboxylate-copolymerization-2-hydroxyethyl 5-norborene-2-carboxylate-copolymerization-5-norborene-2-carboxylic acid-copolymerization-maleic anhydride), poly-(tetracyclododecen-5-carboxylate-copolymerization-maleic anhydride), poly-(tert-butyl group 5-norborene-2-carboxylate-copolymerization-maleic anhydride-copolymerization-2-methyl adamantane ylmethyl acrylate-copolymerization-2-mevalonolactone methacrylate), poly-(2-methyl adamantane ylmethyl acrylate-copolymerization-2-mevalonolactone methacrylate) or the like.
The polymkeric substance that contains (methyl) acrylate monomer, cycloolefin monomers and cyclic acid anhydride, wherein this monomer also can be incorporated in the hybridized polymer as mentioned above.The example of cyclenes monomer comprises and is selected from following those: norborene carboxylic acid tertiary butyl ester (BNC), norborene carboxylic acid hydroxyethyl ester (HNC), norborene carboxylic acid (NC), tert-butyl group Fourth Ring [4.4.0.1.
2,61.
7,10] 12-8-alkene-3-carboxylate and tert-butoxycarbonyl methyl Fourth Ring [4.4.0.1.
2,61.
7,10] 12-8-alkene-3-carboxylate.In some cases, the preferred example of cyclenes comprises norborene carboxylic acid tertiary butyl ester (BNC), norborene carboxylic acid hydroxyethyl ester (HNC) and norborene carboxylic acid (NC).The example of (methyl) acrylate monomer especially comprises and is selected from following those: mevalonolactone methacrylate (MLMA), 2-methyl-2-adamantyl methacrylate (MAdMA), 2-adamantyl methyl methacrylate (AdMA), 2-methyl-2-adamantyl acrylate (MAdA), 2-ethyl-2-adamantyl methacrylate (EAdMA), 3,5-dimethyl-7-hydroxyadamantane ylmethyl acrylate (DMHAdMA), different adamantyl methacrylate, hydroxyl-1-methacryl oxygen base diamantane (HAdMA; For example, hydroxyl is on the 3-position), hydroxyl-1-adamantyl acrylate (HADA; For example, hydroxyl is on the 3-position), ethyl cyclopentyl acrylate (ECPA), ethyl cyclopentyl-methyl acrylate (ECPMA), three rings [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate (TCDMA); 3; 5-dihydroxy-1-methacryl oxygen base diamantane (DHAdMA); Beta-methyl acryloxy-gamma-butyrolacton; α-or β-gamma-butyrolacton methacrylate (α-or β-GBLMA); 5-methacryloxy-2; 6-norbornane phenol lactone (carbolactone) (MNBL); 5-acryloxy-2; 6-norbornane phenol lactone (ANBL), isobutyl methacrylate (IBMA), α-gamma-butyrolacton acrylate (α-GBLA); 2-adamantyl acrylate (AdA); norborene lactone acrylate (NLA), spirolactone (methyl) acrylate, oxygen base tristane (methyl) acrylate; diamantane lactone (methyl) acrylate and Alpha-Methyl acryloxy-gamma-butyrolacton.Adopt the example of the polymkeric substance of these monomers formation to comprise: poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryloxy-diamantane-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(t-butyl norbornene carboxylate-copolymerization-maleic anhydride-copolymerization-2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-methacryl oxo norborene methyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3,5-dihydroxy-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3,5-dimethyl-7-hydroxyadamantane ylmethyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl acrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-ethyl cyclopentyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryloxy-diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(ethyl cyclopentyl-methyl acrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-isobutyl methacrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryloxy-diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate-copolymerization-3-hydroxyl-1-methacryloxy-diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryloxy-diamantane-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-ethyl-2-adamantyl-copolymerization-methyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-5-acryloyl group oxo-2,6-norbornane phenol lactone); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-norborene lactone acrylate-copolymerization-2-adamantyl methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-norborene lactone acrylate-copolymerization-2-adamantyl acrylate); With poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate).
Other example of suitable polymers comprises and is described in the following document those: U.S.Pat.Nos.6,610,465,6,120,977,6,136,504,6,013,416,5,985,522,5,843,624,5,693,453,4,491,628, WO 00/25178, WO 00/67072, JP 2000-275845, and JP 2000-137327 and JP 09-73173, the document is hereby incorporated by.Can use the potpourri of one or more photoresist resin.General use standard synthetic method prepares various types of suitable polymers.The technology or the list of references of appropriate criteria method (for example free radical polymerization) can obtain in above-mentioned document.
Think that cyclenes and cyclic acid anhydride monomer can form the alternating polymerization structure, the amount that is incorporated into (methyl) acrylate monomer in the polymkeric substance can change, to obtain optimum lithographic performance.With respect to cyclenes/anhydride monomer, the number percent of (methyl) acrylate monomer in polymkeric substance is in the scope of about 95 moles of % to about 5 moles of %, further from about 75 moles of % to about 25 moles of %, and further from about 55 moles of % to about 45 moles of %.
Can be used for the non-phenol polymer of fluoridizing of 157 nanometers exposure, also demonstrate line edge roughness, and can benefit from the use of the new blend of Photoactive compounds described in the invention.This polymkeric substance is described among WO 00/17712 and the WO 00/67072, and in being incorporated herein as a reference.An example of this polymkeric substance is poly-(the 2-norborene of tetrafluoroethene-copolymerization-norborene-copolymerization-5-hexafluoroisopropanol-replacement.
Be described in the US patent 6,686,429 by cyclenes and the synthetic polymkeric substance of the olefinic type monomers that contains cyano group, this paper introduces its content as a reference, also can use.Interested other polymkeric substance of people is included in obtain among the US patented claim publication No.2004/0166433 and describe those, its content is hereby incorporated by.Can also use other polymkeric substance, for example at the US patented claim sequence No.10/440 of on May 16th, 2003 application, those disclosed in 542, its title is: be used for photoetching compositions and the method thereof of dark UV, this paper introduces its content as a reference.
Based on chemicals type of using and the lithographic performance of wanting, with the molecular weight optimization of polymkeric substance.Usually, weight-average molecular weight within 3,000 to 30,000 scopes, polydispersity within 1.1 to 5 scopes, preferred 1.5 to 2.5.
When photoacid generator of the present invention uses in composition, its solid constituent is dissolved in the organic solvent.The amount of the solid in solvent or the solvent mixture is in the scope of about 1 weight % to about 50 weight %.Polymkeric substance can be in 5 weight % to 90 weight % scopes of solid, and photoacid generator can be at 1 weight % of solid to about 50 weight % scopes.The suitable solvent that is used for this photoresist for example can comprise: ketone, acetone for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, methyl isoamyl ketone, 2-heptanone 4-hydroxyl, and 4-methyl-2 pentanone; C
1To C
10Aliphatic alcohol, methyl alcohol for example, ethanol, and propyl alcohol; The alcohol that contains aromatic radical, for example phenmethylol; Cyclic carbonate, for example ethylene carbonate and propylene carbonate; Aliphatic series or aromatic hydrocarbon (for example, hexane, toluene, dimethylbenzene, or the like); Cyclic ethers, for example diox and tetrahydrofuran; Ethylene glycol; Propylene glycol; Hexanediol; Ethylene glycol monoalkyl ether, glycol monoethyl ether for example, ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetic acid esters, for example methylcellosolve acetate and ethyl cellosolve acetate; The ethylene glycol bisthioglycolate alkyl ether, glycol dimethyl ether for example, ethylene glycol diethyl ether, Ethylene Glycol Methyl ether, diglycol monotertiary alkyl ether, diethylene glycol monomethyl ether for example, diethylene glycol monoethyl ether, and diethylene glycol dimethyl ether; Propylene-glycol monoalky lether, propylene glycol monomethyl ether for example, propylene-glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetic acid ester, propylene glycol methyl ether acetate for example, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters and propylene glycol butyl ether acetic acid esters; Propylene glycol alkyl ether propionic ester, propylene glycol monomethyl ether acetate for example, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester and propylene glycol butyl ether propionic ester; 2-methoxy ethyl ether (diethylene glycol dimethyl ether); Solvent with ether and hydroxylic moiety, methoxybutanol for example, ethoxy butanols, methoxypropanol and ethoxy propyl alcohol; Ester, methyl acetate for example, ethyl acetate, propyl acetate and butyl acetate methyl pyruvate, ethyl pyruvate; The 2 hydroxy propanoic acid ethyl ester, 2-hydroxyl 2 Methylpropionic acid methyl esters, 2-hydroxyl 2 Methylpropionic acid ethyl ester, methyl glycolic acid esters, ethyl glycollic acid ester, the butylhydroxy acetic acid esters, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, methyl 2-hydroxyl 3 Methylbutanoic acid, methyl methoxy yl acetate, ethyl methoxyacetic acid ester, propyl group methoxyacetic acid ester, butyl methoxyacetic acid ester, methyl ethoxy acetic acid esters, ethyl ethoxyacetic acid ester, propyl group ethoxyacetic acid ester, butyl ethoxyacetic acid ester, methyl-prop ethoxyacetic acid ester, ethyl propoxyl group acetic acid esters, propyl group propoxyl group acetic acid esters, butyl propoxyl group acetic acid esters, methyl butoxy acetic acid ester, ethyl butoxy acetic acid ester, propyl group butoxy acetic acid ester, butyl butoxy acetic acid ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate and 3-butoxy butyl propionate; Oxygen base isobutyrate, for example, methyl-2-hydroxy-iso-butyric acid ester, α-methoxyl methyl isobutyrate, methoxyl ethyl isobutyrate, α-ethoxy methyl isobutyrate, α-ethoxy ethyl isobutyrate, the 'beta '-methoxy methyl isobutyrate, 'beta '-methoxy ethyl isobutyrate, β-ethoxy methyl isobutyrate, β-ethoxy ethyl isobutyrate, β-isopropoxy methyl isobutyrate, β-isopropoxy ethyl isobutyrate, β-isopropoxy isopropyl isobutyrate, β-isopropoxy butyl isobutyrate, the Beta-Butoxy methyl isobutyrate, Beta-Butoxy ethyl isobutyrate, Beta-Butoxy butyl isobutyrate, the alpha-hydroxybutyric dehydrogenase methyl esters, ethyl alpha-hydroxyisobutyrate, alpha-hydroxybutyric dehydrogenase isopropyl ester and alpha-hydroxybutyric dehydrogenase butyl ester; Solvent with ether and hydroxylic moiety, methoxybutanol for example, ethoxy butanols, methoxypropanol and ethoxy propyl alcohol; And other solvent, for example dibasic ester, and gamma-butyrolacton; Ether ketone derivant, for example diacetone alcohol methyl ether; Keto-alcohol derivant, for example acetol or diacetone alcohol; Lactone, for example butyrolactone; Amide derivatives, for example dimethyl acetamide or dimethyl formamide, methyl phenyl ethers anisole and its potpourri.
For example colorant, the dyestuff that does not play photochemical action, anti-striped reagent, plastifier, tackifier, dissolution inhibitor, coating auxiliary agent, light sensitivity reinforcing agent, other photoacid generator and dissolution enhancers be (for example for various other adjuvants, some low-level solvent need not be made main solvent part, its example comprises glycol ethers and glycol ethers acetic acid esters, valerolactone, ketone, lactone or the like) and surfactant can join in the photoetching compositions, then solution is coated in the substrate.Can improve the surfactant of film thickness uniformity, for example fluorinated surfactant can join in the photoresist solution.Energy can be passed to the sensitizer of various exposure wavelengths from the particular range wavelength, also can join in the photoetching compositions.Usually alkali is also joined in the photoresist, to prevent on the photoresist imaging surface, forming T type top (t-tops) or bridge type.The example of alkali is the alkali of amine, ammonium hydroxide and energy sensitization.Particularly preferred alkali is trioctylamine, diethanolamine and tetrabutylammonium hydroxide.
Can comprise dipping, spraying and spin coating by any conventional method of photoresist field use, ready photoetching compositions solution is applied in the substrate.When spin coating, for example, consider the permission time of employed whirligig type and rotating technics, can regulate the solids content number percent of photoresist solution, so that the coating thickness of wanting is provided.Suitable substrates comprises silicon, aluminium, fluoropolymer resin, silicon dioxide, doped silica, silicon nitride, tantalum, copper, polysilicon, pottery, aluminium/copper mixture; Gallium arsenide and other this III/V compounds of group.Photoresist also can be coated on the anti-reflection coating.
Photoresist coating by the preparation of description technology is particularly suitable for being applied to silicon/silicon dioxide wafer, for example is used to make microprocessor and other Small Scale Integration part.Can also use aluminium/aluminium oxide wafer.Substrate also can comprise various fluoropolymer resins, particularly transparent polymer, for example polyester.
Then photoetching compositions solution is coated in the substrate, on heating plate, handles (curing) substrate about 30 seconds to about 180 seconds to about 150 ℃ temperature from about 70 ℃, or processing about 15 to about 90 minutes in convective oven.Select this Temperature Treatment,, can not cause a large amount of thermal degradation of solid constituent simultaneously so that reduce the concentration of the residual solvent in the photoresist.Usually, wish solvent strength and this first temperature minimum.Handle (curing), till all solvent evaporations basically, and the shallow layer that is about half micron (micrometer) thick photoetching compositions is retained in the substrate.In preferred embodiments, temperature is from about 95 ℃ to about 120 ℃.Handle, up to remove solvent variation speed become relatively slight till.Film thickness, temperature and time select to depend on the desired photoresist performance of user, and the device and the commercial needed coating time of using.The substrate that applies can be exposed to photochemical radiation with any needed pattern imaging then, for example UV radiation (at wavelength from about 100nm (nanometer) to about 300nm), X ray, electron beam, ion beam or laser emission, described pattern uses appropriate mask, negative electrode, masterplate, model or the like generation.
Back secondary drying or thermal treatment, then development then expose photoresist.Heating-up temperature can about 90 ℃ to about 150 ℃ scope, more preferably from about 100 ℃ to about 130 ℃.Heating can be carried out about 30 seconds to about 2 minutes on heating plate, more preferably from about 60 seconds to about 90 seconds, or utilize convective oven to heat about 30 to about 45 minutes.
By in developer solution, soaking or developing, the substrate that the photoresist that exposes applies is developed, to remove the imaging exposure area by spray development technology.Preferred agitating solution for example utilizes the nitrogen strong agitation.Substrate is retained in the developer, till all or all basically photoresist coatings dissolve from the exposure area.Developer comprises the aqueous solution of ammonium or alkali metal hydroxide.A kind of preferred developer is the aqueous solution of tetramethyl ammonium hydroxide.Remove from developer solution after the coated wafers, the thermal treatment after the video picture that can choose wantonly or cure is with the adhesion that strengthens coating with for the chemical resistance of etch condition and other material.Thermal treatment after the video picture can comprise coating and substrate oven-baked or the UV sclerosis under the coating softening point.In commercial Application, special in the substrate of silicon/silicon dioxide type in the process of preparation miniaturized circuit element, the substrate that can handle development with the hydrofluorite sapping etching solution or the dry etching of buffering.Before dry etching, can handle photoresist with electronic beam curing, so that strengthen the anti-etching ability of photoresist.
The present invention further provides the method for preparing semiconductor devices, this method applies suitable substrates and produce light image in substrate by composition with photoresist.Target process comprises: composition applies suitable substrate with photoresist, with the substrate thermal treatment that applies, till all photoresist solvents are removed basically; Make the composition exposure image, remove the imaging exposure area of this composition with suitable developer.
The US sequence No.11/280 of application on November 16th, 2005, the content of the US sequence No.11/355/400 of application on February 16th, 842 and 2006, the application has required right of priority according to its content, is hereby incorporated by.
The following example is for example understood manufacturing and is used method of the present invention.Yet,, and should not be seen as in order to put into practice condition, parameter or numerical value that must unique use provided by the present invention in any case these embodiment want restriction or limit scope of the present invention.Unless otherwise mentioned, all umber and percentages are calculated.
Synthesizing of 1: two [4-acetoxyl group phenyl] phenyl sulfonium perfluoro of embodiment fourth sulfonate.
Two [4-hydroxy phenyl] phenyl sulfonium perfluoro fourth sulfonate (10 gram) and acetone are put into reaction vessel, and reaction vessel is equipped with stirrer, thermometer, reflux condenser and nitrogen is introduced the pipe of container.Under the blanket of nitrogen protection, 4.6 gram sal tartari are joined in the reaction vessel, stirred the mixture one hour.Add 3.43 gram acetic anhydrides, at room temperature stir and spend the night.Methylene chloride (150 milliliters) and water are joined in the reaction vessel, stirred the mixture 2 hours.Then potpourri is put into separating funnel, and keep organic (methylene chloride) layer.Water washs several times with dichloromethane layer, uses anhydrous sodium sulfate drying, filter, and with the volatile matter evaporation that keeps, remaining oil.Ether is joined in the oil, stir the mixture energetically.Obtain the very solid of thickness.
Synthesizing of 2: two [4-acetoxyl group phenyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) of embodiment perfluoro fourth sulfonate.
According to embodiment 1 this material of preparation, only be to use two [4-hydroxy phenyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate to replace dihydroxy phenyl phenyl sulfonium perfluoro fourth sulfonate.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 2:
Embodiment 2a: X=CF wherein
3SO
3
Embodiment 2b: X=N (SO wherein
2CF
3)
2
Embodiment 2c: X=N (SO wherein
2C
2F
5)
2
Embodiment 2d: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 2e: X=N (SO wherein
2C
3F
7)
2
Embodiment 2f: X=C (SO wherein
2CF
3)
3
Embodiment 2g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 2h: X=C wherein
4F
9SO
3
Synthesizing of 3: two [2-methyl adamantane base acetoxyl group methoxyphenyl] phenyl sulfonium perfluoro fourth sulfonate of embodiment.
Method according to embodiment 1 prepares this material, only is to use 2-methyl adamantane base bromacetate to replace acetic anhydride.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 3:
Embodiment 3a: X=CF wherein
3CHFO (CF
2)
4SO
3
Embodiment 3b: X=CF wherein
3SO
3
Embodiment 3c: X=N (SO wherein
2CF
3)
2
Embodiment 3d: X=N (SO wherein
2C
2F
5)
2
Embodiment 3e: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 3f: X=N (SO wherein
2C
3F
7)
2
Embodiment 3g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 3h: X=C (SO wherein
2CF
3)
3
Embodiment 3i: X=C wherein
4F
9SO
3
Embodiment 4: two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium perfluoro fourth sulfonate synthetic.
Dihydroxy phenyl phenyl sulfonium perfluoro fourth sulfonate (10 gram) and acetone are put into reaction vessel, and reaction vessel is equipped with stirrer, thermometer, reflux condenser and nitrogen is introduced the pipe of container.Under the blanket of nitrogen protection, 4.6 gram sal tartari are joined in the reaction vessel, stirred the mixture one hour.With 4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] nonyl chloromethyl ether (10.92 gram) joins in the reaction mixture, at room temperature stir the mixture and spend the night.Methylene chloride (150 milliliters) and water are joined in the reaction vessel, stirred the mixture 2 hours.Then potpourri is put into separating funnel, and keep organic (methylene chloride) layer.Water washs several times with dichloromethane layer, uses anhydrous sodium sulfate drying, filter, and with the volatile matter evaporation that keeps, remaining oil.Ether is joined in the oil, stir the mixture energetically.Obtain the very solid of thickness.
Embodiment 4a: two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium perfluoro mesylate synthetic.
Can be according to the method for embodiment 4, by dihydroxy phenyl phenyl sulfonium perfluor mesylate and 4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] the nonyl chloromethyl ether prepares this material.
Embodiment 4b: two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) perfluoro butyl sulfosalt synthetic.
Can be according to the method for embodiment 4, and by two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium perfluoro mesylate and 4-(1,1,1,2-tetrafluoro ethoxy) perfluoro fourth sulfonic acid lithium salts prepare this material.
Embodiment 4c: two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxy
The base phenyl] phenyl sulfonium two (trifluoromethyl sulfonyl) is imido synthetic.
Can be according to the method for embodiment 4, and by two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium perfluoro mesylate and two perfluoro methylsulfonyl imidic acids prepare this material.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 4:
Embodiment 4d: X=N (SO wherein
2C
2F
5)
2
Embodiment 4e: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 4f: X=N (SO wherein
2C
3F
7)
2
Embodiment 4g: X=N (SO wherein
2C
4F
9)
2
Embodiment 4h: X=C (SO wherein
2CF
3)
3
Embodiment 4i: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
5: two imido synthesizing of [4-hydroxy phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) of embodiment.
Two [4-hydroxy phenyl] phenyl sulfonium perfluoro mesylate (15.0 gram) and acetone-water mixture are put into reaction vessel, and reaction vessel is equipped with stirrer, thermometer, reflux condenser and nitrogen is introduced the pipe of container.Under the blanket of nitrogen protection, 9.6 grams, two perfluoro second sulfimide lithiums are joined in the reaction vessel, stirred the mixture 5 hours.Methylene chloride (150 milliliters) and water are joined in the reaction vessel, stirred the mixture 2 hours.Then potpourri is put into separating funnel, and keep organic (methylene chloride) layer.Water washs several times with dichloromethane layer, uses anhydrous sodium sulfate drying, filter, and with the volatile matter evaporation that keeps, remaining oil.Ether is joined in the oil, stir the mixture energetically.Obtain oil.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 5:
Embodiment 5a: X=N (SO wherein
2CF
3)
2
Embodiment 5b: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 5c: X=N (SO wherein
2C
3F
7)
2
Embodiment 5d: X=N (SO wherein
2C
4F
9)
2
Embodiment 5e: X=C (SO wherein
2CF
3)
3
Embodiment 5f: X=CF wherein
3CHFO (CF
2)
4SO
3
Embodiment 5g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 5h: X=C wherein
4F
9SO
3
Embodiment 5i: X=CF wherein
3SO
3
6: two [4-phenyl-pentafluoride sulfonyl oxygen base phenyl] phenyl sulfoniums two (perfluoro ethylsulfonyl) of embodiment are imido synthetic
Two [4-hydroxy phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide (6.33 gram) and the dry THF that are obtained from embodiment 5 are put into reaction vessel, and reaction vessel is equipped with stirrer, thermometer, reflux condenser and nitrogen is introduced the pipe of container.Place dry ice-propanone around reaction vessel and bathe, and under the blanket of nitrogen protection, 5.09 gram phenyl-pentafluoride sulfonic acid chlorides are joined in the reaction vessel, stirred the mixture 5 hours.Methylene chloride (150 milliliters) and water are joined in the reaction vessel, stirred the mixture 2 hours.Then potpourri is put into separating funnel, and keep organic (methylene chloride) layer.Water washs several times with dichloromethane layer, uses anhydrous sodium sulfate drying, filter, and with the volatile matter evaporation that keeps, remaining oil.Ether is joined in the oil, stir the mixture energetically.Reclaim white crystal, mp38 ℃.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 6:
Embodiment 6a: X=N (SO wherein
2CF
3)
2
Embodiment 6b: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 6c: X=N (SO wherein
2C
3F
7)
2
Embodiment 6d: X=N (SO wherein
2C
4F
9)
2
Embodiment 6e: X=C (SO wherein
2CF
3)
3
Embodiment 6f: X=CF wherein
3CHFO (CF
2)
4SO
3
Embodiment 6g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 6h: X=C wherein
4F
9SO
3
Embodiment 6i: X=CF wherein
3SO
3
7: two [4-(3,5-two (trifluoromethyl) benzenesulfonyl oxygen base) phenyl] phenyl sulfoniums two (perfluoro ethylsulfonyl) of embodiment are imido synthetic
Can use 3 according to the method for embodiment 6,5-two (trifluoromethyl) benzene sulfonyl chloride replaces the phenyl-pentafluoride sulfonic acid chloride, prepares this material.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 7:
Embodiment 7a: X=N (SO wherein
2CF
3)
2
Embodiment 7b: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 7c: X=N (SO wherein
2C
3F
7)
2
Embodiment 7d: X=N (SO wherein
2C
4F
9)
2
Embodiment 7e: X=C (SO wherein
2CF
3)
3
Embodiment 7f: X=CF wherein
3CHFO (CF
2)
4SO
3
Embodiment 7g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 7h: X=C wherein
4F
9SO
3
Embodiment 7i: X=CF wherein
3SO
3
8: two [4-trifluoromethyl sulfonyloxy phenyl] phenyl sulfoniums two (perfluoro ethylsulfonyl) of embodiment are imido synthetic
Can use trifluoromethanesulfchloride chloride to replace the phenyl-pentafluoride sulfonic acid chloride according to the method for embodiment 6, prepare this material.
In addition, can use corresponding negative ion, the preparation following compounds according to the method for embodiment 8:
Embodiment 8a: X=N (SO wherein
2CF
3)
2
Embodiment 8b: X=N (SO wherein
2CF
3) (SO
2C
4F
9)
Embodiment 8c: X=N (SO wherein
2C
3F
7)
2
Embodiment 8d: X=N (SO wherein
2C
4F
9)
2
Embodiment 8e: X=C (SO wherein
2CF
3)
3
Embodiment 8f: X=CF wherein
3CHFO (CF
2)
4SO
3
Embodiment 8g: X=CH wherein
3CH
3CH
3O (CF
2)
4SO
3
Embodiment 8h: X=C wherein
4F
9SO
3
Embodiment 8i: X=CF wherein
3SO
3
Embodiment 9
With poly-(the EAdMA/MAdMA/HAdM A/ α-GBLMA of 2.1625 grams; 20/20/25/35) polymkeric substance, 0.0504 gram (30 μ mol/g) are obtained from two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy perfluoro fourth sulfonate, 0.23 gram diisopropanolamine (the 10 weight % of embodiment 2, in PGMEA) and 0.0360 gram, 10 weight % surfactants (fluorine aliphatics polymerization ester, 3MCorporation, St.Paul Minnesota provides) PGMEA solution be dissolved among the 27.74 gram AZ Thinner, by 0.2 μ m pass filter, obtain 30 gram photoresist solutions.
Embodiment 10
By with bottom antireflective coating solution (AZ
EXP ArF-1, B.A.R.C. is obtained from AZ Electronic Materials USA Corp., and Somerville NJ) is spun on the silicon base and cures at 215 ℃ and prepared the silicon base that scribbles bottom antireflective coating (B.A.R.C.) in 60 seconds.The B.A.R.C film thickness is 29nm.The photoresist solution that will be obtained from embodiment 9 then is coated on the silicon chip of B.A.R.C coating.Regulate rotational speed, so that photoresist film thickness is 180nm is thick, Nikon 306D 0.85 NA ﹠amp; 4/5 ring light photograph, PAB100 ℃/60s, 110 ℃/60s of PEB, development time: 30s (ACT12), 6%PSM.Use the aqueous solution of 2.38 weight % tetramethyl ammonium hydroxides then, imaging and photo-etching glue was developed 30 seconds.Observation line and space diagram on scanning electron microscope then.Photoresist has 47.6mJ/cm
2Light sensitivity, have good exposure range (16.8%), good LER and contour shape.
Embodiment 11:
Two [2-methyl adamantane base acetyl group Oxymethoxy-phenyl] phenyl sulfonium perfluoro fourth sulfonate that use is obtained from embodiment 3 replaces two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy perfluoro fourth sulfonate, repeats embodiment 9.
Embodiment 12
Repeat embodiment 10 with the photoresist solution that is obtained from embodiment 11, obtain similar result.
Embodiment 13
Use be obtained from embodiment 4 two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5] the nonyl methoxyphenyl] phenyl sulfonium perfluoro fourth sulfonate replacement two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy perfluoro fourth sulfonate, repeat embodiment 9.
Embodiment 14
Repeat embodiment 10 with the photoresist solution that is obtained from embodiment 13, obtain similar result.
Embodiment 15
Use is obtained from embodiment's 5 [4-hydroxy phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide and replaces two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy perfluoro fourth sulfonate, repeats embodiment 9.
Embodiment 16
Repeat embodiment 10 with the photoresist solution that is obtained from embodiment 15, obtain similar result.
Embodiment 17
Use is obtained from embodiment's 6 [4-phenyl-pentafluoride sulfonyloxy phenyl] phenyl sulfonium two (perfluoro ethylsulfonyl) acid imide and replaces two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy perfluoro fourth sulfonate, repeats embodiment 9.
Embodiment 18
Repeat embodiment 10 with the photoresist solution that is obtained from embodiment 17, obtain similar result.
Embodiment 19
With the poly-(EAdMA/HAdA/NLA/AdMA of 2.1625 grams; 30/20/40/10) polymkeric substance, 0.0504 gram (30 μ mol/g) are obtained from two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy-perfluoro fourth sulfonate, 0.23 gram diisopropanolamine (the 10 weight % of embodiment 2, in PGMEA) and 0.0360 gram, 10 weight % surfactants (fluorine aliphatics polymerization ester, 3MCorporation, St.Paul Minnesota provides) PGMEA solution be dissolved among the 27.74 gram AZ Thinner, by 0.2 μ m pass filter, obtain 30 gram photoresist solutions.
Embodiment 20
By with bottom antireflective coating solution (AZ
EXP ArF-1, B.A.R.C. is obtained from AZ Electronic Materials USA Corp., and Somerville NJ) is spun on the silicon chip and cures 215 and prepared the silicon base that scribbles bottom antireflective coating (B.A.R.C.) in 60 seconds.The B.A.R.C film thickness is 29nm.The photoresist solution that will be obtained from embodiment 19 then is coated on the silicon chip of B.A.R.C coating.Regulate rotational speed, so that photoresist film thickness is 180nm is thick, Nikon 306D 0.85NA ﹠amp; 4/5 ring light photograph, PAB100 ℃/60s, 110 ℃/60s of PEB, development time: 30s (ACT12), 6%PSM.Use the aqueous solution of 2.38 weight % tetramethyl ammonium hydroxides then, imaging and photo-etching glue was developed 30 seconds.Observation line and space diagram on scanning electron microscope then.Photoresist has 55.5mJ/cm
2Light sensitivity, have good exposure range (16.8%), good LER and contour shape.
Embodiment 21
With the poly-(EAdMA/HAdA/NLA/AdA of 2.1625 grams; 30/20/40/10) polymkeric substance, 0.0504 gram (30 μ mol/g) are obtained from two [acetoxyl group phenyl] phenyl sulfonium trifluoro ethoxy-perfluoro fourth sulfonate, 0.23 gram diisopropanolamine (the 10 weight % of embodiment 2, in PGMEA) and 0.0360 gram, 10 weight % surfactants (fluorine aliphatics polymerization ester, 3MCorporation, St.Paul Minnesota provides) PGMEA solution be dissolved among the 27.74 gram AZ Thinner, by 0.2 μ m pass filter, obtain 30 gram photoresist solutions.
Embodiment 22
By with bottom antireflective coating solution (AZ
EXP ArF-1, B.A.R.C. is obtained from AZ Electronic Materials USA Corp., and Somerville NJ) is spun on the silicon base and cures at 215 ℃ and prepared the silicon base that scribbles bottom antireflective coating (B.A.R.C.) in 60 seconds.The B.A.R.C film thickness is 29nm.The photoresist solution that will be obtained from embodiment 21 then is coated on the silicon chip of B.A.R.C coating.Regulate rotational speed, so that photoresist film thickness is 180nm is thick, Nikon 306D 0.85NA ﹠amp; 4/5 ring light photograph, PAB100 ℃/60s, 110 ℃/60s of PEB, development time: 30s (ACT12), 6%PSM.Use the aqueous solution of 2.38 weight % tetramethyl ammonium hydroxides then, imaging and photo-etching glue was developed 30 seconds.Observation line and space diagram on scanning electron microscope then.Photoresist has 44.5mJ/cm
2Light sensitivity, have good exposure range (16.0%), good LER and contour shape.
Embodiment 23:
By using a kind of polymkeric substance that substitutes wherein in the following polymers, can repeat embodiment 9,11,13,15 and 17:
Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-isobutyl methacrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-β-gamma-butyrolacton acrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl acrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3,5-dihydroxy-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3,5-dimethyl-7-hydroxyadamantane ylmethyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-ethyl-2-adamantyl methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate-copolymerization-2-ethyl-2-adamantyl-copolymerization-methyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-methacryl oxo norborene methyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-α-gamma-butyrolacton methacrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β gamma-butyrolacton methacrylate-copolymerization-2-adamantyl methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-methacryl oxygen base diamantane-copolymerization-ethyl cyclopentyl acrylate); Poly-(2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-3-hydroxyl-1-adamantyl acrylate-copolymerization-three ring [5,2,1,0
2,6] last of the ten Heavenly stems-8-ylmethyl acrylate); Poly-(ethyl cyclopentyl-methyl acrylate-copolymerization-2-ethyl-2-adamantyl methacrylate-copolymerization-α-gamma-butyrolacton acrylate); With poly-(t-butyl norbornene carboxylate-copolymerization-maleic anhydride-copolymerization-2-methyl-2-adamantyl methacrylate-copolymerization-β-gamma-butyrolacton methacrylate-copolymerization-methacryl oxo norborene methyl acrylate), form photoresist solution.Can be according to embodiment 10 test photoresist solutions, this photoresist should have good performance.
The description explanation of the invention described above has also been described the present invention.In addition, the disclosure only shows and has described the preferred embodiments of the invention, but as mentioned above, should be appreciated that, the present invention can be used in various other combinations, remodeling and the environment, and conceive in the scope and can change or improve in the expressed the present invention of this paper, the technology or the knowledge of this variation or improvement and above-mentioned instruction and/or association area match.The above-described embodiment known practice best mode of the present invention that further is used for explaining, and make others skilled in the art in such embodiment or other embodiment, use the present invention, and carry out various improvement according to the needs of concrete application of the present invention or purposes.Therefore, this instructions is not to be used for the present invention is limited to form disclosed herein.In addition, wish additional claim is interpreted as comprising alternative embodiment.
Claims (13)
1. the compound that has following formula
R wherein
A, R
BBe OR independently of one another
1, R
CBe hydrogen or OR independently
1, each R wherein
1Be hydrogen independently, alkyl, alkoxyalkyl, alkoxycarbonyl alkyl, alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl wherein, SO
2R
4And SiR
4 3, R wherein
4Be alkyl, aryl, or wherein cycloalkyl ring is chosen monocycle alkyl or the multi-ring alkyl that comprises one or more O atoms wantonly; described alkyl, alkoxyalkyl, alkoxycarbonyl alkyl; alkyl-carbonyl; aryl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, wherein cycloalkyl ring comprises the monocycle alkyl of one or more O atoms-or multi-ring alkyl oxygen base alkyl; wherein to comprise the monocycle alkyl of one or more O atoms or multi-ring alkyl be unsubstituted to cycloalkyl ring or replaced by one or more following group: halogen; alkyl, monocycle alkyl or multi-ring alkyl, alkoxy; cycloalkyloxy; dialkyl amido, dicyclo dialkyl amido, hydroxyl; cyano group; nitro, three fluoro ethane sulfonyls, oxo; aryl; aralkyl, oxygen atom, CF
3SO
3, aryloxy group, the group of artyl sulfo and formula (II) to (VI):
R wherein
10And R
11Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl, or R
10And R
11Can represent alkylidene together forming five or hexatomic ring,
R
12The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, or aralkyl, or R
10And R
12Represent alkylidene together, with insert-the C-O-group forms five or hexatomic ring, the nuclear carbon atom is optional to be replaced by oxygen atom,
R
13The optional straight or branched alkyl chain that comprises one or more O atoms of expression, or monocycle alkyl or multi-ring alkyl,
R
14And R
15Each represents hydrogen atom independently, the optional straight or branched alkyl chain that comprises one or more O atoms, or monocycle alkyl or multi-ring alkyl,
R
16The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, aryl or aralkyl and
R
17The optional straight or branched alkyl chain that comprises one or more O atoms of expression, monocycle alkyl or multi-ring alkyl, aryl, aralkyl, group-SiR
16 2R
17, or group-O-SiR
16 2R
17, optional straight or branched alkyl chain, monocycle alkyl or the multi-ring alkyl that comprises one or more O atoms, wherein aryl and aralkyl are unsubstituted or are substituted according to top mode; With
X
-It is negative ion.
2. the compound of claim 1, wherein X
-Be selected from: CF
3SO
3 -, CHF
2SO
3 -, CH
3SO
3 -, CCl
3SO
3 -, C
2F
5SO
3 -, C
2HF
4SO
3 -, C
4F
9SO
3 -, phenyl-pentafluoride sulfonate radical, (Rf
1SO
2)
3C
-, (Rf
1SO
2)
2N
-, each Rf wherein
1Be independently selected from highly fluorinated or fluoridized alkyl or fluoro aryl, and can be ring-type, as any two Rf
1When moiety combinations is connected to form bridge joint, further, Rf
1Alkyl chain contains 1-20 carbon atom, optional contains stretched wire oxygen, and can be straight chain, side chain or ring-type, so that divalence oxygen, trivalent nitrogen or sexavalence sulphur skeletal chain at interval further, is worked as Rf
1When containing ring texture, this structure has 5 or 6 ring persons, and optional, wherein 1 or 2 is heteroatoms or Rg-O-Rf
2-SO
3 -,
Rf wherein
2Be selected from straight or branched (CF
2)
j, wherein j is from 4 to 10 integer, and C
1-C
12Perfluor naphthenic base bivalent radical, it is optional by perfluoro C
1-10Alkyl replaces,
Rg is selected from C
1-C
20Straight or branched alkyl, C
1-C
20Straight or branched thiazolinyl, monocycle alkyl or multi-ring alkyl, monocyclic alkenyl or many cycloalkenyl groups, aryl and aralkyl, alkyl, monocycle alkyl or multi-ring alkyl, thiazolinyl, monocyclic alkenyl or many cycloalkenyl groups, wherein aralkyl and aryl be unsubstituted, replace, the optional one or more stretched wire oxygen atoms, partially fluorinated or fluoridize fully that comprise.
3. according to the compound of claim 1 or 2, R wherein
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein independently, the wherein optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl, and SO
2R
4, R wherein
4Be aryl, alkyl-carbonyl, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base carbonylic alkyl wherein, the optional monocycle alkyl that comprises one or more O atoms of cycloalkyl ring-or multi-ring alkyl oxygen base alkyl wherein, wherein aryl is unsubstituted or replaces.
4. according to each compound of claim 1 to 3, R wherein
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be alkyl-carbonyl unsubstituted or that replace independently.
5. according to each compound of claim 1 to 3, R wherein
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1The monocycle alkyl that is unsubstituted independently or replaces-or multi-ring alkyl oxygen base carbonylic alkyl, wherein cycloalkyl ring is chosen wantonly and is comprised one or more O atoms.
6. according to each compound of claim 1 to 3, R wherein
CBe hydrogen, R
AAnd R
BEach is OR independently
1, each R
1Be SO independently
2R
4, R wherein
4It is aryl unsubstituted or that replace.
7. according to each compound of claim 1 to 6, be selected from two [4-acetoxyl group phenyl] phenyl sulfonium perfluoro fourth sulfonate, two [4-acetoxyl group phenyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [2-methyl adamantane base-acetoxyl group methoxyphenyl] phenyl sulfonium perfluor fourth sulfonate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium perfluoro fourth sulfonate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium perfluoro mesylate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium 4-(1,1,1,2-tetrafluoro ethoxy) perfluor fourth sulfonate, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] nonyl-methoxyphenyl] phenyl sulfonium two (trifluoromethyl-sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium two (perfluor ethylsulfonyl)-acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium (perfluoro-methyl-sulfonyl) (perfluor fourth sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium two (perfluoro propyl-sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo [4.2.1.0
2,5] nonyl methoxyl-phenyl] phenyl sulfonium two (perfluor fourth sulfonyl) acid imide, two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5]-nonyl methoxyphenyl] phenyl sulfonium three (trifluoromethyl-sulfonyl) methide; two [4-acetoxyl group phenyl] phenyl sulfonium perfluoro mesylate; two [4-acetoxyl group phenyl] phenyl sulfonium two (trifluoromethyl sulfonyl) acid imide; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imides; two [4-acetoxyl group phenyl] phenyl sulfonium (perfluor mesyl) (perfluor fourth sulfonyl) acid imides; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluor third sulfonyl) acid imide; two [4-acetoxyl group phenyl] phenyl sulfonium three (trifluoromethyl sulfonyl) methide; two [4-acetoxyl group phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-acetoxyl group phenyl] phenyl sulfonium two (perfluor fourth sulfonyl) acid imide; two [2-methyl adamantane base acetyl group-Oxymethoxy phenyl] phenyl sulfonium-4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [2-methyl adamantane base acetyl group-Oxymethoxy phenyl] phenyl sulfonium perfluoro mesylate; two [2-methyl adamantane base acetoxyl group methoxyphenyl] phenyl sulfonium two (trifluoromethyl sulfonyl) acid imide; two [2-methyl adamantane base acetoxyl group-methoxyl-phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imide; two [2-methyl adamantane base-acetoxyl group methoxyphenyl] phenyl sulfonium (perfluoro-methyl-sulfonyl) (perfluor fourth sulfonyl) acid imide; two [2-methyl adamantane base-acetoxyl group methoxyl-phenyl] phenyl sulfonium two (perfluor third sulfonyl) acid imide; two [2-methyl adamantane base-acetyl group-Oxymethoxy phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [2-methyl adamantane base acetoxyl group-methoxyphenyl] phenyl sulfonium three (trifluoromethyl-sulfonyl) methide; two [2-methyl adamantane base acetoxyl group methoxyphenyl] phenyl sulfonium two (perfluor fourth sulfonyl) acid imide; two [4,4-two (trifluoromethyl)-3-oxatricyclo-[4.2.1.0
2,5] the nonyl methoxyphenyl] phenyl sulfonium 4-propoxyl group perfluor fourth-sulfonate; two [4-hydroxy phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imide; two [4-hydroxy phenyl] phenyl sulfonium two (trifluoromethyl sulfonyl) acid imides; two [4-hydroxy phenyl] phenyl sulfonium (perfluor mesyl) (perfluoro butyl-sulfonyl) acid imide; two [4-hydroxy phenyl]-phenyl sulfonium two (perfluoro propyl-sulfonyl) acid imides; two [4-hydroxy phenyl]-phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imides; two [4-hydroxy phenyl]-phenyl sulfonium three (trifluoromethyl-sulfonyl) methides; two [4-hydroxy phenyl]-phenyl sulfonium 4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [4-hydroxy phenyl]-phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-hydroxy phenyl] phenyl sulfonium perfluoro fourth sulfonate; two [4-hydroxy phenyl]-phenyl sulfonium perfluor mesylates; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium two (trifluoromethyl-sulfonyl) acid imide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium (perfluor mesyl) (perfluoro butyl-sulfonyl) acid imide; two [4-five fluoro-benzenesulfonyl oxygen base phenyl] phenyl sulfonium two (perfluor third sulfonyl) acid imide; two [4-phenyl-pentafluoride sulfonyl oxygen base phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide; two [4-phenyl-pentafluoride sulphonyl-oxygen base phenyl] phenyl sulfonium three (trifluoromethyl sulfonyl) methide; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium 4-(1; 1; 1; 2-tetrafluoro ethoxy) perfluoro fourth sulfonate; two [4-phenyl-pentafluoride sulfonyl-oxygen base phenyl] phenyl sulfonium 4-propoxyl group perfluor fourth sulfonate; two [4-phenyl-pentafluoride-sulfonyl oxygen base phenyl] phenyl sulfonium perfluoro fourth sulfonate; two [4-phenyl-pentafluoride sulfonyl oxygen base phenyl] phenyl sulfonium perfluoromethane-sulfonate; two [4-(3; 5-two (trifluoromethyl)-phenylsulfonyloxy) phenyl] phenyl sulfonium two (perfluor ethylsulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) phenylsulfonyloxy)-and phenyl] phenyl sulfonium two (trifluoromethyl sulfonyl) acid imide; two [4-(3; 5-two (three fluoro-methyl) benzene-sulfonyloxy) phenyl] phenyl sulfonium (perfluor mesyl) (perfluor fourth sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) benzene sulfonyl-oxygen base) phenyl] phenyl sulfonium two (perfluor third sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) phenylsulfonyloxy) phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide; two [4-(3; 5-two (trifluoromethyl) phenylsulfonyloxy) phenyl] phenyl sulfonium three (trifluoromethyl sulfonyl) methide, two [4-(3,5-two (three fluoro-methyl) phenylsulfonyloxy) phenyl] phenyl sulfonium 4-(1; 1; 1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [4-(3; 5-two (trifluoromethyl)-phenylsulfonyloxy) phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-(3,5-two (trifluoromethyl)-phenylsulfonyloxy) phenyl] phenyl sulfonium perfluoro fourth sulfonate, two [4-(3; 5-two (trifluoromethyl) benzene sulfonyl-oxygen base) phenyl] phenyl sulfonium perfluoromethane-sulfonate; two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium two (perfluor ethyl-sulfonyl) acid imide, two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium two (trifluoromethyl-sulfonyl) acid imide, two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium (perfluor mesyl) (perfluor fourth sulfonyl) acid imide; two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium two (perfluoro propyl-sulfonyl) acid imide; two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium two (perfluoro butyl-sulfonyl) acid imide, two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium three (trifluoromethyl sulfonyl) methide, two [4-trifluoromethyl-sulfonyloxy) phenyl] phenyl sulfonium 4-(1; 1; 1,2-tetrafluoro ethoxy) perfluoro fourth sulfonate, two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium 4-propoxyl group perfluoro fourth sulfonate; two [4-trifluoromethyl-sulfonyloxy) phenyl] phenyl sulfonium perfluoro fourth sulfonate and two [4-trifluoromethyl sulfonyloxy) phenyl] phenyl sulfonium perfluoro mesylate.
8. be used for the photoetching compositions of dark UV imaging, comprise:
A) contain the polymkeric substance of acid-unstable group; With
B) compound of each of claim 1 to 7.
9. the composition of claim 8, it further comprises other photoacid generator.
10. make the photoresist imaging method, comprise the following steps:
A) with claim 8 or 9 composition coated substrate;
B) curing substrate desolvates to remove basically;
C) photoresist coating is exposed with imaging mode;
D) after the exposure, the baked photoresist coating; With
E) with alkaline aqueous solution photoresist coating is developed.
11. the method for claim 10, wherein the wavelength of imaging mode exposure is lower than 300nm.
12. according to the method for claim 10 or 11, wherein substrate is selected from microelectronic component and LCD substrate.
13. according to each compound of claim 1 to 7 purposes in photoetching compositions as photoacid generator.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28084205A | 2005-11-16 | 2005-11-16 | |
| US11/280,842 | 2005-11-16 | ||
| US11/355,400 | 2006-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100419702A Division CN102161635B (en) | 2005-11-16 | 2006-11-15 | Photoactive compound |
| CN2011100426104A Division CN102161637B (en) | 2005-11-16 | 2006-11-15 | Photoactive compound |
| CN201110042218XA Division CN102161636A (en) | 2005-11-16 | 2006-11-15 | Photoactive compound |
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| Publication Number | Publication Date |
|---|---|
| CN101310223A true CN101310223A (en) | 2008-11-19 |
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ID=40125807
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103676478A (en) * | 2012-09-15 | 2014-03-26 | 罗门哈斯电子材料有限公司 | Photoresists comprising multiple acid generator compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103676478A (en) * | 2012-09-15 | 2014-03-26 | 罗门哈斯电子材料有限公司 | Photoresists comprising multiple acid generator compounds |
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