CN101421673A - The resist-protecting membrane for immersion lithography material - Google Patents
The resist-protecting membrane for immersion lithography material Download PDFInfo
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- CN101421673A CN101421673A CNA2007800132668A CN200780013266A CN101421673A CN 101421673 A CN101421673 A CN 101421673A CN A2007800132668 A CNA2007800132668 A CN A2007800132668A CN 200780013266 A CN200780013266 A CN 200780013266A CN 101421673 A CN101421673 A CN 101421673A
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- polymkeric substance
- compound
- resist
- repetitive
- immersion lithography
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Abstract
The invention provides the resist-protecting membrane for immersion lithography material.The alkali-soluble resist-protecting membrane for immersion lithography material that comprises polymkeric substance (F), described polymkeric substance (F) comprise by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U).For example, repetitive (F
U) repetitive that forms for the polymerization of the compound (f) by being selected from following compound (f1)～(f4); R
FExpression H, F, the alkyl of carbon number 1～3 or the fluoro-alkyl of carbon number 1～3, X
FExpression F, OH or CH
2OH.
Description
Technical field
The present invention relates to liquid immersion lithography (immersion lithography) forms composition and corrosion-resisting pattern with resist-protecting membrane material, resist-protecting membrane for immersion lithography polymkeric substance, resist-protecting membrane for immersion lithography composition, resist-protecting membrane for immersion lithography formation method.
Background technology
In the manufacturing of the integrated circuit of semiconductor etc., employing will to mask shine exposure light source light and the pattern image of mask be projected in photonasty resist on the substrate, this pattern image is needed on the photoetching process of photonasty resist.Usually, described pattern image Jie is projected in the desired position of photonasty resist with the projecting lens that relatively moves on the photonasty resist.
The light of exposure light source is the closer to short-wavelength light, and the exploring degree of pattern image that is needed on the photonasty resist is high more, therefore as exposure light source, is studying 220nm following short-wavelength light (ArF excimer laser, F
2Laser etc.).And, the used erosion resistant of photoetching process that also big quantity research uses this short-wavelength light.For example, as with F
2Laser is the used photonasty erosion resistant of the photoetching process of exposure light source, records the polymkeric substance (multipolymer of following 3 kinds of compounds etc.) of polyfluoro adamantyl (methyl) acrylate in the patent documentation 1.
In recent years, studying the immersion lithography process that comprises following operation: utilize light wavelength in the liquid medium to be the exposure process of inverse phenomenon doubly of the refractive index of liquid medium, be about between projecting lens bottom and photonasty resist top with the high liquid medium of refractive index liquid mediums such as () ultrapure waters when (the following immersion liquid that also claims) is full, the pattern image of mask is situated between with the projecting lens projection in the operation of photonasty resist (with reference to patent documentation 2 etc.).
In the immersion lithography process, full between projecting lens and photonasty resist with immersion liquid, so the composition of photonasty resist (photoacid generator etc.) may stripping in immersion liquid, or the photonasty resist is because of the immersion liquid swelling.
Therefore, the someone attempts in immersion lithography process, and the resist-protecting membrane layer is set on the photonasty resist, suppresses the stripping and the swelling of photonasty resist.
As the resist-protecting membrane for immersion lithography material, record the alkali-soluble polymkeric substance that comprises the repetitive that contains polymerizable compound (following compound etc.) and the resist-protecting membrane composition of fluorine class surfactant in the patent documentation 3 with polar group.
In addition, record by passing through CF in the patent documentation 4
2=CFCF
2C (CF
3) (OR
g) CH
2CH=CH
2(b
gThe alkoxy or the alkoxyalkyl of expression hydrogen atom or carbon number 1～15) cyclopolymerization and resist-protecting membrane polymkeric substance that the polymkeric substance that contains following repetitive that forms forms.
Record by following compound and CH in the patent documentation 5
2=CHC (O) O CH
2CF
2CF
2CF
2CHF
2The resist-protecting membrane polymkeric substance that forms etc. the multipolymer of non-ring type Polyfluoroalkyl (methyl) acrylate.
Patent documentation 1: the Jap.P. spy opens the 2004-182796 communique
Patent documentation 2: the international text that discloses No. 99/049504
Patent documentation 3: the Jap.P. spy opens the 2005-352384 communique
Patent documentation 4: the Jap.P. spy opens the 2005-264131 communique
Patent documentation 5: the Jap.P. spy opens the 2006-070244 communique
The announcement of invention
Be provided with in the immersion lithography process of resist-protecting membrane layer, it is desirable to the resist-protecting membrane material that uses dynamic liquid-repellant good, make immersion liquid well with the projecting lens servo-actuated of on resist-protecting membrane, moving.For example, immersion liquid is in the immersion lithography process of water, it is desirable to the resist-protecting membrane material that uses dynamic water repellency good.
But, do not find the resist-protecting membrane material that described dynamic water repellency is good yet.For example, the fluorine class surfactant of record is nothing but the polymkeric substance of non-polymer shape fluorochemicals and non-ring type fluoro-alkyl (methyl) acrylate in the patent documentation 3, and the dynamic water repellency of the resist-protecting membrane composition of patent documentation 3 is low.In addition, the dynamic water repellency of patent documentation 4 or 5 resist-protecting membrane polymkeric substance is also not enough.
Therefore, need dynamic water repellency height, can easily make the resist-protecting membrane for immersion lithography material of immersion liquid and the projecting lens servo-actuated of moving.
The inventor for obtain the resist-protecting membrane for immersion lithography characteristic (suppress the photonasty resist that the intrusion of water causes swelling, suppress the stripping of photonasty resist composition in liquid medium etc.) good and to the liquid-repellant of immersion liquid (water etc.), the particularly dynamic good resist-protecting membrane for immersion lithography material of liquid-repellant, carried out conscientiously research.Consequently, found the resist-protecting membrane for immersion lithography material that described rerum natura is good.
That is, the present invention has following main idea.
[1] alkali-soluble resist-protecting membrane for immersion lithography material wherein, comprises polymkeric substance (F), and described polymkeric substance (F) comprises by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U).
[2] as [1] described resist-protecting membrane for immersion lithography material, wherein, polymerizable compound (f
m) be the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
In addition, the fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
[3] alkali-soluble resist-protecting membrane for immersion lithography polymkeric substance, it is to comprise repetitive (F
U) and repetitive (B
U) polymkeric substance (FB), described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form described repetitive (B
U) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and form.
[4] as [3] described resist-protecting membrane for immersion lithography polymkeric substance, wherein, polymerizable compound (f
m) be the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
In addition, the fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
[5] as [3] or [4] described resist-protecting membrane for immersion lithography polymkeric substance, wherein, polymerizable compound (b
m) be to have (CF with formula-C
3) (OH)-, formula-C (CF
3)
2(OH) or the polymerizable compound of the group represented of formula-C (O) OH.
[6] as each the described resist-protecting membrane for immersion lithography polymkeric substance in [3]～[5], wherein, polymerizable compound (b
m) be the compound (b) that is selected from the compound of following formula (b1), following formula (b2), following formula (b3) and following formula (b4) expression;
CF
2＝CF—Q
B1—CH＝CH
2 (b1)
CH
2＝CR
B2—C(O)O—Q
B2(—C(CF
3)
2OH)
b (b2)
CH
2＝CH—Q
B3(—C(CF
3)
2OH)
b (b3)
Mark in the formula is represented following implication,
Q
B1: with formula-CF
2C (CF
3) (OH) (CH
2)
m-expression group, with formula-CH
2CH ((CH
2)
nC (CF
3)
2(OH)) (CH
2)
m-expression group or with formula-CH
2CH (C (O) OH) (CH
2)
mThe group of-expression,
M and n: independently be respectively 0,1 or 2,
R
B2: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
Q
B2And Q
B3: independent respectively is (b+1) valency alkyl of carbon number 1～20,
B:1 or 2,
Q
B4: the divalent alkyl of singly-bound or carbon number 1～10;
In addition, Q
B2, Q
B3Or Q
B4In carbon atom can be combined with fluorine atom.
[7] as each the described resist-protecting membrane for immersion lithography polymkeric substance in [3]～[6], wherein, polymkeric substance (FB) is the repetitive (F that comprises 1～70 mole of % with respect to all repetitives
U), the above repetitive (B of 10 moles of %
U) polymkeric substance.
[8] as each the described resist-protecting membrane for immersion lithography polymkeric substance in [3]～[7], wherein, polymkeric substance (FB) is the repetitive (F that comprises 3～15 moles of % with respect to all repetitives
U), the repetitive (B of 85～97 moles of %
U) polymkeric substance.
[9] resist-protecting membrane for immersion lithography forms composition, wherein, comprises [3]～each described resist-protecting membrane for immersion lithography polymkeric substance and organic solvent in [8].
[10] the formation method of corrosion-resisting pattern, it is the formation method that adopts the corrosion-resisting pattern of immersion lithography process, wherein, carries out following operation successively, forming corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate, the operation of formation photonasty resist film on substrate; [9] described resist-protecting membrane for immersion lithography is formed composition coat the photonasty resist film, on the photonasty resist film, form the operation of resist-protecting membrane layer; The liquid immersion lithography operation; And developing procedure.
[11] alkali-soluble resist-protecting membrane for immersion lithography composition wherein, comprises polymkeric substance (F) and polymkeric substance (B), and described polymkeric substance (F) comprises by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U), described polymkeric substance (B) comprises by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and the repetitive (B that forms
U).
[12] as [11] described resist-protecting membrane for immersion lithography composition, wherein, polymerizable compound (f
m) be the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
In addition, the fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
[13] as [11] or [12] described resist-protecting membrane for immersion lithography composition, wherein, polymerizable compound (b
m) be to have (CF with formula-C
3) (OH)-, formula-C (CF
3)
2(OH) or the polymerizable compound of the group represented of formula-C (O) OH.
[14] as each the described resist-protecting membrane for immersion lithography composition in [11]～[13], wherein, polymerizable compound (b
m) be the compound (b) that is selected from the compound of following formula (b1), following formula (b2), following formula (b3) and following formula (b4) expression;
CF
2＝CF—Q
B1—CH＝CH
2 (b1)
CH
2＝CR
B2—C(O)O—Q
B2(—C(CF
3)
2OH)
b (b2)
CH
2＝CH—Q
B3(—C(CF
3)
2OH)
b (b3)
Mark in the formula is represented following implication,
Q
B1: with formula-CF
2C (CF
3) (OH) (CH
2)
m-expression group, with formula-CH
2CH ((CH
2)
nC (CF
3)
2(OH)) (CH
2)
m-expression group or with formula-CH
2CH (C (O) OH) (CH
2)
mThe group of-expression,
M and n: independently be respectively 0,1 or 2,
R
B2: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
Q
B2And Q
B3: independent respectively is (b+1) valency alkyl of carbon number 1～20,
B:1 or 2,
Q
B4: the divalent alkyl of singly-bound or carbon number 1～10;
In addition, Q
B2, Q
B3Or Q
B4In carbon atom can be combined with fluorine atom.
[15] as each the described resist-protecting membrane for immersion lithography composition in [11]～[14], wherein, polymkeric substance (F) is only by repetitive (F
U) polymkeric substance that forms, described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form.
[16] as each the described resist-protecting membrane for immersion lithography composition in [11]～[14], wherein, polymkeric substance (F) is to comprise repetitive (F
U) and repetitive (B
U) polymkeric substance, comprise the repetitive (F of 1～25 mole of % with respect to all repetitives
U), the repetitive (B of 75～99 moles of %
U), described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form described repetitive (B
U) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and form.
[17], wherein,, comprise the polymkeric substance (F) of 0.1～30 quality % with respect to polymkeric substance (B) as each the described resist-protecting membrane for immersion lithography composition in [11]～[16].
[18], wherein,, comprise more than 30 quality % and be less than the polymkeric substance (F) that equals 200 quality % with respect to polymkeric substance (B) as [16] described resist-protecting membrane for immersion lithography composition.
[19] resist-protecting membrane for immersion lithography forms composition, wherein, comprises [11]～each described resist-protecting membrane for immersion lithography composition and organic solvent in [18].
[20] the formation method of corrosion-resisting pattern, it is the formation method that adopts the corrosion-resisting pattern of immersion lithography process, wherein, carries out following operation successively, forming corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate, the operation of formation photonasty resist film on substrate; [19] described resist-protecting membrane for immersion lithography is formed composition coat the photonasty resist film, on the photonasty resist film, form the operation of resist-protecting membrane layer; The liquid immersion lithography operation; And developing procedure.
If employing the present invention then can provide the resist-protecting membrane for immersion lithography material that the resist-protecting membrane characteristic is good and dynamic liquid-repellant is good especially.The resist-protecting membrane for immersion lithography material of the application of the invention can be realized and can implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
The best mode that carries out an invention
In this instructions, will make compound (f) with the compound note of formula (f) expression, will be with formula-CF
2C (CF
3) (OH) (CH
2)
mThe group note work-CF of-expression
2C (CF
3) (OH) (CH
2)
m-.Other compound and other group are too.
In addition, short of special record, the mark in the group and aforementioned synonym.
The invention provides the resist-protecting membrane for immersion lithography material that comprises the effect by acid of polymkeric substance (F) and alkali solubility and increase (following also claim diaphragm material of the present invention), described polymkeric substance (F) comprises by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U).
The liquid-repellant of diaphragm material of the present invention, particularly dynamic liquid-repellant are good, and especially water repellency, particularly dynamic water repellency are good.Its reason it be unclear that; but think because the contained polymkeric substance (F) of diaphragm material of the present invention is the polymkeric substance with the bulky structure that derives from fluorine-containing bridged ring structure; compare with fluoropolymer with the fluorine-containing structure of non-ring type, form when filming easier be oriented in the most surperficial.Therefore, by the present invention, be difficult for being submerged liquid and invade, the modulation of the resist-protecting membrane material that slides well in immersion liquid becomes easy.
Polymerizable compound (f among the present invention
m) better be compound with 1 valency polymerizable group and the fluorine-containing endocyclic alkyl of 1 valency.
1 valency polymerizable group better is 1 a valency group with two keys of carbon atom-carbon atom of polymerism, preferred vinyl, (methyl) acryloxy, 2-fluorine acryloxy or 2-fluoroalkyl acryloxy, and good especially is (methyl) acryloxy.Wherein, (methyl) acryloxy is meant acryloxy or methacryloxy (down together).
The fluorine-containing endocyclic alkyl of 1 valency better is an aliphatic group, and good especially is saturated aliphatic groups.In addition, can be inserted with between the carbon atom-carbon atom in the fluorine-containing endocyclic alkyl of 1 valency-O-,-C (O) O-or-C (O)-.In addition, the carbon atom in the fluorine-containing endocyclic alkyl of 1 valency can be combined with the group that comprises hydroxyl or carboxyl.
The fluorine-containing endocyclic alkyl of 1 valency better be as the endocyclic saturated hydrocarbon compound remove 1 hydrogen atom and 1 valency group, better be the group that is replaced by fluorine atom more than 50% of remaining hydrogen atom.This remaining hydrogen atom is more preferably more than 80% and is replaced by fluorine atom, and good especially is all to be replaced by fluorine atom.
The endocyclic saturated hydrocarbon compound better is the endocyclic saturated hydrocarbon compound that is selected from following compound (1) and following compound (2).
Polymerizable compound (f among the present invention
m) good especially be the compound (f) that is selected from following compound (f1), following compound (f2), following compound (f3) and following compound (f4).
Have in the asymmetric carbon compound (f), the spatial configuration of asymmetric center can be interior type or external form.
R
FBetter be hydrogen atom or methyl.
X
FIt better is fluorine atom.
As polymerizable compound (f
m) object lesson, can exemplify following compound.
Compound (f2), compound (f3) and compound (f4) are new compounds.Its manufacture method aftermentioned.
The weight-average molecular weight of the polymkeric substance among the present invention (F) better is 1000～100000, and good especially is 1000～50000.
The invention provides alkali-soluble resist-protecting membrane for immersion lithography polymkeric substance (hereinafter referred to as diaphragm polymkeric substance of the present invention), it is to comprise repetitive (F
U) and repetitive (B
U) polymkeric substance (FB), described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form described repetitive (B
U) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and form.
The liquid-repellant of diaphragm polymkeric substance of the present invention, particularly dynamic liquid-repellant are good, and especially water repellency, particularly dynamic water repellency are good.Its reason it be unclear that; but think because diaphragm polymkeric substance of the present invention is formed by the polymkeric substance with the bulky structure that derives from fluorine-containing bridged ring structure (FB); compare with fluoropolymer with the fluorine-containing structure of non-ring type, form when filming easier be oriented in the most surperficial.Therefore, adopt in the immersion lithography process of the resist-protecting membrane of making by diaphragm polymkeric substance of the present invention, immersion liquid well with the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.In addition, diaphragm polymkeric substance of the present invention is owing to comprise repetitive (B
U), be alkali-soluble polymkeric substance therefore.Can easily remove by aqueous slkali by the resist-protecting membrane that diaphragm polymkeric substance of the present invention is made.Therefore, by diaphragm polymkeric substance of the present invention, can realize and to implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
Polymerizable compound (b among the present invention
m) better be polymerizable monomer with hydroxyl or carboxyl.Hydroxyl can be alcohol hydroxyl group or phenol hydroxyl.
From the angle of water repellency and alkali affinity, polymerizable compound (b
m) be more preferably the hydroxyl on the carbon atom with the carbon atom adjacency that is combined in and is combined with Polyfluoroalkyl or the polymerizable compound of carboxyl, good especially is to have-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerizable compound of C (O) OH.
Polymerizable compound (b
m) better be the compound (b) that is selected from following compound (b1), following compound (b2), following compound (b3) and following compound (b4), good especially is compound (b1).
CF
2＝CF—Q
B1—CH＝CH
2 (b1)
CH
2＝CR
B2—C(O)O—Q
B2(—C(CF
3)
2OH)
b (b2)
CH
2＝CH—Q
B3(—C(CF
3)
2OH)
b (b3)
The Q of compound (b1)
B1In m better be 1.Q
B1In n better be 0.
Q
B1Better be-CF
2C (CF
3) (OH) CH
2-,-CH
2CH (C (CF
3)
2(OH)) CH
2-or-CH
2CH (C (O) OH) CH
2-.
As the object lesson of compound (b1), can exemplify following compound.
CF
2＝CFCF
2C(CF
3)(OH)CH
2CH＝CH
2、
CF
2＝CFCH
2CH(C(CF
3)
2(OH))CH
2CH＝CH
2、
CF
2＝CFCH
2CH(CH
2C(CF
3)
2(OH))CH
2CH＝CH
2、
CF
2＝CFCH
2CH(C(O)OH)CH
2CH＝CH
2。
The polymkeric substance that comprises the repetitive that the polymerization by compound (b1) forms is to have-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-CH (C (O) OH)-and main chain in have the polymkeric substance of fluorine-containing ring structure, alkali affinity and dynamically water repellency is good especially.
The Q of compound (b2)
B2And the Q of compound (b3)
B3In (b+1) valency alkyl better be respectively independent (b+1) valency ring type alkyl of carbon number 1～20 that is.Described ring type alkyl can be the group that is only formed by the ring type alkyl, also can be the group that comprises the ring type alkyl in the group.Described ring type alkyl can be aliphatic group or aromatic group.In addition, described ring type alkyl can be monocyclic alkyl or polycycle alkyl.The polycycle alkyl can be the endocyclic alkyl.
The Q of compound (b2)
B2And the Q of compound (b3)
B3Good especially is arbitrary group in following.
As the object lesson of compound (b2), can exemplify following compound.
As the object lesson of compound (b3), can exemplify following compound.
The Q of compound (b4)
B4Better be singly-bound or methylene.
As the object lesson of compound (b4), can exemplify following compound.
Diaphragm polymkeric substance of the present invention can be only by repetitive (F
U) and repetitive (B
U) polymkeric substance that forms, also can be the polymkeric substance that also comprises other unit.In addition, the repetitive (F in the diaphragm polymkeric substance of the present invention
U) can be more than a kind or 2 kinds.In addition, the repetitive (B in the diaphragm polymkeric substance of the present invention
U) can be more than a kind or 2 kinds.
Diaphragm polymkeric substance of the present invention better be comprise 1～50 mole of %, be more preferably 1～20 mole of %, good especially be the repetitive (F of 3～15 moles of %
U).Diaphragm polymkeric substance of the present invention better be comprise 50～99 moles of %, be more preferably 80～99 moles of %, good especially be the repetitive (B of 85～97 moles of %
U).
The weight-average molecular weight of diaphragm polymkeric substance of the present invention better is 1000～100000, and good especially is 1000～50000.
As the preferred configuration of diaphragm polymkeric substance of the present invention, can exemplify only by repetitive (F
U) and repetitive (B
U) form, comprise the repetitive (F of 1～50 mole of % with respect to all repetitives
U), the repetitive (B of 50～99 moles of %
U) polymkeric substance.As more preferably form, can exemplify the repetitive (F that comprises 3～15 moles of % with respect to all repetitives
U), the repetitive (B of 87～99 moles of %
U) polymkeric substance.
Repetitive (B in the described form
U) better be by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or the polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, be more preferably the repetitive that the polymerization of the compound (b) by being selected from compound (b1), compound (b2), compound (b3) and compound (b4) forms, good especially is the repetitive that the polymerization by compound (b1) forms, and preferably passes through CF
2=CFCF
2C (CF
3) (OH) CH
2CH=CH
2, CF
2=CFCH
2CH (C (CF
3)
2(OH)) CH
2CH=CH
2Or CF
2=CFCH
2CH (C (O) OH) CH
2CH=CH
2Polymerization and the repetitive that forms.
The weight-average molecular weight of the polymkeric substance of described form better is 1000～30000.
Diaphragm polymkeric substance of the present invention is coated on the surface of the photonasty resist film that is formed on the substrate usually and uses in to the application of immersion lithography process, better be to be modulated into liquid composition therefore.
The invention provides the resist-protecting membrane for immersion lithography that comprises diaphragm polymkeric substance of the present invention and organic solvent and form composition (the following diaphragm that also claims forms composition (1)).
It better is the organic solvent that comprises 100 quality %～10000 quality % with respect to the gross mass of diaphragm polymkeric substance of the present invention that diaphragm forms composition (1).
As organic solvent,, be not particularly limited so long as get final product for the high solvent of the intermiscibility of diaphragm polymkeric substance of the present invention.Organic solvent can be fluorinated organic solvent or non-fluorinated organic solvent.
As the object lesson of fluorinated organic solvent, can exemplify CCl
2FCH
3, CF
3CF
2CHCl
2, CClF
2CF
2Hydrochlorofluorocarbons classes such as CHClF, CF
3CHFCHFCF
2CF
3, CF
3(CF
2)
5H, CF
3(CF
2)
3C
2H
5, CF
3(CF
2)
5C
2H
5, CF
3(CF
2)
7C
2H
5Deng hydrogen fluorohydrocarbon class, 1, hydrogen fluorobenzene classes such as two (trifluoromethyl) benzene of 3-, hexafluoro m-xylene, hydrogen fluorine ketone, hydrofluoroalkane base benzene class, CF
3CF
2CF
2CF
2OCH
3, (CF
3)
2CFCF (CF
3) CF
2OCH
3, CF
3CH
2OCF
2CHF
2Deng hydrogen fluorine ethers, CHF
2CF
2CH
2Hydrogen fluorine alcohols such as OH.
Object lesson as non-fluorinated organic solvent, can exemplify methyl alcohol, ethanol, diacetone alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, 2-methyl isophthalic acid-propyl alcohol, the 2-ethyl butanol, amylalcohol, hexanol, alcohols such as enanthol, acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, the 2-heptanone, N-Methyl pyrrolidone, ketones such as gamma-butyrolacton, propylene glycol methyl ether acetate, the propylene glycol monomethyl ether propionic ester, propylene glycol monoethyl ether acetate, the carbitol acetic acid esters, 3-methoxypropionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 'beta '-methoxy methyl isobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, acetic acid-2-ethoxy-ethyl ester, isoamyl acetate, methyl lactate, ester classes such as ethyl lactate, toluene, aromatic hydrocarbon such as dimethylbenzene, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dihydroxypropane single-ether, the glycol monomethyl isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, glycol list or dialkyl ethers such as propylene glycol monomethyl ether, N, dinethylformamide, N,N-dimethylacetamide etc.
Diaphragm formation composition (1) can comprise the composition except that diaphragm polymkeric substance of the present invention and organic solvent.As the object lesson of this composition, can exemplify plastifier, stabilizing agent, colorant, antihalation agent etc.
The invention provides alkali-soluble resist-protecting membrane for immersion lithography composition (following also claim diaphragm composition of the present invention); wherein; comprise polymkeric substance (F) and polymkeric substance (B), described polymkeric substance (F) comprises by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U), described polymkeric substance (B) comprises by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and the repetitive (B that forms
U).
The liquid-repellant of diaphragm composition of the present invention, particularly dynamic liquid-repellant are good, and especially water repellency, particularly dynamic water repellency are good.Its reason it be unclear that; but think because the contained polymkeric substance (F) of diaphragm composition of the present invention is the polymkeric substance with the bulky structure that derives from fluorine-containing bridged ring structure; compare with fluoropolymer with the fluorine-containing structure of non-ring type, form when filming easier be oriented in the most surperficial.Therefore, adopt in the immersion lithography process of the resist-protecting membrane of making by diaphragm composition of the present invention, immersion liquid well with the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.In addition, therefore diaphragm composition of the present invention is alkali-soluble composition owing to comprise polymkeric substance (B).Can easily remove by aqueous slkali by the resist-protecting membrane that diaphragm composition of the present invention is made.Therefore, by diaphragm composition of the present invention, can realize and to implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
Polymkeric substance (F) in the diaphragm composition of the present invention (the following polymkeric substance (FS) that also claims) can be only by repetitive (F
U) polymkeric substance that forms, also can be also to comprise except that repetitive (F
U) in addition repetitive (following other unit (FS that also claims
U)) polymkeric substance.No matter be any situation, polymkeric substance (FS) all better be with respect to all repetitives comprise 1 mole more than the %, be more preferably 10 moles more than the %, good especially be 20 moles of repetitive (F more than the %
U).Polymkeric substance (FS) comprises other unit (FS
U) situation under, better be with respect to all repetitives comprise 90 moles below the %, good especially be 50 moles of other unit (FS below the %
U).
Other unit (FS
U) be not particularly limited, better be by polymerizable compound (b
m) polymerization and the repetitive (B that forms
U), be more preferably by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, good especially is the repetitive that the polymerization of the compound (b) by being selected from compound (b1), compound (b2), compound (b3) and compound (b4) forms, preferably the repetitive that forms of the polymerization by compound (b1).
The weight-average molecular weight of polymkeric substance (FS) better is 1000～100000, and good especially is 1000～50000.
As the preferred configuration of polymkeric substance (FS), can exemplify following polymkeric substance (FS
H), following polymkeric substance (FS
C1), following polymkeric substance (FS
C2).
Polymkeric substance (FS
H): only by repetitive (F
U) polymkeric substance that forms.
Polymkeric substance (FS
C1): as by repetitive (F
U) and other unit (FS
U) polymkeric substance that forms, comprise the repetitive (F of 10～70 moles of % with respect to all repetitives
U), other unit (FS of 30～90 moles of %
U) polymkeric substance.
Polymkeric substance (FS
C1) in other unit (FS
U) better be by polymerizable compound (b
m) polymerization and the repetitive (B that forms
U), be more preferably by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, good especially is the repetitive that the polymerization by compound (b1) forms.
Polymkeric substance (FS
C2): as by repetitive (F
U) and other unit (FS
U) polymkeric substance that forms, comprise the repetitive (F of 1～25 mole of % with respect to all repetitives
U), other unit (FS of 75～99 moles of %
U) polymkeric substance.
Polymkeric substance (FS
C2) in other unit (FS
U) better be by polymerizable compound (b
m) polymerization and the repetitive (B that forms
U), be more preferably by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, good especially is the repetitive that the polymerization by compound (b1) forms.
The weight-average molecular weight of the polymkeric substance of these preferred configuration better is 1000～30000.
Pass through polymerizable compound (b in the polymkeric substance (B)
m) polymerization and the repetitive (B that forms
U) preferred configuration and resist-protecting membrane polymer phase of the present invention with.
Polymkeric substance (B) can be only by repetitive (B
U) polymkeric substance that forms, also can be the polymkeric substance that also comprises other unit.In addition, polymkeric substance (B) can be only by a kind of repetitive (B
U) form, also can be by the repetitive (B more than 2 kinds
U) form.Polymkeric substance (B) is good especially to be to comprise 50 moles of repetitive (B more than the % with respect to all repetitives
U).
The weight-average molecular weight of polymkeric substance (B) better is 1000～100000, and good especially is 1000～50000.
As the preferred configuration of polymkeric substance (B), can exemplify as comprising repetitive (B
U) polymkeric substance, comprise the repetitive (B of 70～100 moles of % with respect to all repetitives
U) polymkeric substance.As particularly preferred form, can exemplify only by repetitive (B
U) polymkeric substance that forms.
Repetitive (B in the polymkeric substance of described form
U) better be by polymerizable compound (b
m) polymerization and the repetitive (B that forms
U), be more preferably by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, good especially is the repetitive that the polymerization by compound (b1) forms.
The weight-average molecular weight of the polymkeric substance of described form better is 1000～50000.
Diaphragm composition of the present invention better is to comprise polymkeric substance (FS) and polymkeric substance (B) and comprise the polymkeric substance (FS) of 0.1～30 quality % with respect to polymkeric substance (B), and good especially is the polymkeric substance (FS) that comprises 1～10 quality % with respect to polymkeric substance (B).Under this situation, polymkeric substance (B) and polymkeric substance (FS) easily mix, and have the good effect of film forming of diaphragm.
In addition, as another preferred configuration of diaphragm composition of the present invention, can exemplify with respect to polymkeric substance (B) and comprise more than 30 quality % and be less than the form of the polymkeric substance (FS) that equals 200 quality %.In the described form, better be the polymkeric substance (FS) that comprises 50～150 quality % with respect to polymkeric substance (B).Under this situation, the dynamic water repellency of diaphragm composition of the present invention and alkali solubility become high especially.Polymkeric substance under this situation (FS) better is polymkeric substance (FS
C2).
Diaphragm composition of the present invention is coated on the surface of the photonasty resist film that is formed on the substrate usually and uses in to the application of immersion lithography process, better be to be modulated into liquid composition therefore.The invention provides the resist-protecting membrane for immersion lithography that comprises diaphragm composition of the present invention and organic solvent and form composition (the following diaphragm that also claims forms composition (2)).
It better is the organic solvent that comprises 100 quality %～10000 quality % with respect to the gross mass of diaphragm composition of the present invention that diaphragm forms composition (2).
As organic solvent,, be not particularly limited so long as get final product for the high solvent of the intermiscibility of diaphragm composition of the present invention.As the object lesson of organic solvent, can exemplify the identical organic solvent of organic solvent that forms composition (1) with diaphragm.
Diaphragm of the present invention forms the diaphragm material that composition (diaphragm forms the general designation of composition (1) and diaphragm formation composition (2)) can be used for the photonasty resist in the immersion lithography process.As immersion lithography process, can exemplify and carry out following operation successively, in the method that forms corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate forms the operation of photonasty resist film on substrate; Diaphragm of the present invention is formed composition coat photonasty resist film surface, form the operation of resist-protecting membrane on photonasty resist film surface; The liquid immersion lithography operation; And developing procedure.
The photonasty anticorrosive additive material is not particularly limited so long as comprise polymkeric substance that the effect of alkali solubility by acid increase and the photonasty anticorrosive additive material of photoacid generator gets final product.As the object lesson of photonasty anticorrosive additive material, can exemplify the Jap.P. spy and open the photonasty anticorrosive additive material of putting down in writing in the 2005-234178 communique.More particularly, can exemplify and comprise as the triphenylsulfonium fluoroform sulphonate of photoacid generator and as the photonasty resist composition of the multipolymer of following 3 kinds of compounds of described polymkeric substance.
As the liquid immersion lithography operation, can exemplify following operation: with between projecting lens and resist film with immersion liquid full the time, will to mask shine exposure light source light and the pattern image of mask be situated between with operation in the desired location of the resist film of projecting lens projection on substrate that relatively moves on the resist film.
Exposure light source better is g ray (wavelength 436nm), i ray (wavelength 365nm), KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) or F
2Excimer laser (wavelength 157nm) is more preferably ArF excimer laser or F
2Excimer laser, good especially is the ArF excimer laser.
Immersion liquid can be oil-based liquid medium (naphthalane etc.) or water-based liquid medium (ultrapure water etc.), better is to be the liquid medium of principal ingredient with water, and good especially is ultrapure water.
As developing procedure, can exemplify the operation of removing the exposed portion of resist-protecting membrane and resist film by aqueous slkali.As aqueous slkali, be not particularly limited, can exemplify the alkaline aqueous solution that comprises the alkali compounds that is selected from NaOH, potassium hydroxide, ammonium hydroxide, tetramethyl ammonium hydroxide and triethylamine.
The invention provides immersion exposure resist-protecting membrane polymkeric substance (hereinafter referred to as diaphragm polymkeric substance (P)), it comprises repetitive (F
p) and repetitive (B
p), described repetitive (F
p) pass through with following compound (f
p) expression compound polymerization and form described repetitive (B
p) by having the polymerizable compound (b of the polar group that is selected from hydroxyl, carboxyl, sulfonic group, sulfoamido, amino and phosphate
p) polymerization and form.
CH
2＝CR
fpC(O)O-X
p (f
p)
Wherein, the mark in the formula is represented following implication (down together).
R
Fp: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3.
X
p: the group that comprises the fluorine-containing ring type alkyl of carbon number 5～20.In addition, X
pIn carbon atom can be combined with hydroxyl, carboxyl or be selected from the group of the carbon number 1～10 of alkoxy, alkoxy alkoxy, alkoxy carbonyl group and alkyl-carbonyl.
The water repellency of diaphragm polymkeric substance of the present invention (P) is good, and dynamically water repellency is good especially.Its reason it be unclear that, but thinks because diaphragm polymkeric substance (P) is to have the compound of deriving from (f at side chain
p) bulky fluoro-containing group (with formula-X
pThe group of expression) polymkeric substance.Therefore, think that diaphragm polymkeric substance (P) is difficult for by water intrusion because of high water repellency, dynamically water repellency is good especially, therefore slides well in water.
Compound (f
p) R
FpBetter be hydrogen atom or methyl.
Compound (f
p) X
pSo long as the group that comprises fluorine-containing ring type alkyl of 1 valency gets final product, be not particularly limited, can be the group that only forms by fluorine-containing ring type alkyl, also can be fluorine-containing ring type alkyl is by linking group and CH
2=CR
FpThe group of C (O) O-combination.
Fluorine-containing ring type alkyl in the diaphragm polymkeric substance (P) can be fluorine-containing monocyclic alkyl or fluorine-containing polycycle alkyl, and the dynamic better angle of water repellency better is fluorine-containing polycycle alkyl from three-dimensional upper volume is big.
In addition, fluorine-containing ring type alkyl can be aliphatic group or aromatic group, from the angle of water repellency, better is aliphatic group, and good especially is saturated aliphatic groups.
From the angle of water repellency, the fluorinated volume of fluorine-containing ring type alkyl better is more than the 30 quality %, and good especially is more than the 50 quality %.The upper limit of described fluorinated volume is not particularly limited, and better is below the 76 quality %.
In addition, the carbon atom in the fluorine-containing ring type alkyl is combined with hydroxyl, carboxyl or is selected under the situation of group of carbon number 1～10 of alkoxy, alkoxy alkoxy, alkoxy carbonyl group and alkyl-carbonyl, described carbon atom better be combined with hydroxyl or-OCH
2OX
Fpp(wherein, X
FppThe expression carbon number 1～9 alkyl), good especially be combined with hydroxyl ,-OCH
2OCH
2CH
3,-OCH
2OCH
3Or-OCH
2OC (CH
3)
3
Fluorine-containing polycycle alkyl better is the fluorine-containing fused polycyclic alkyl of carbon number 5～20, and from the bigger angle of three-dimensional upper volume, good especially is the fluorine-containing endocyclic alkyl of carbon number 5～20.
Fluorine-containing endocyclic alkyl better is the group that comprises the group of fluoroadamantane base or comprise fluoro norborneol alkyl, from the big angle of three-dimensional upper volume, is more preferably the former, and good especially is arbitrary group in the group of representing with following formula.
Compound (f
p) better be following compound (f1
p), good especially is following compound (f1
0p) or following compound (f1
0p).
Wherein, the mark in the formula is represented following implication (down together).
R
Flp: hydrogen atom, fluorine atom, methyl or trifluoromethyl.
Pp:0 or 1.
X
Flp: pp be 0 o'clock be fluorine atom or hydroxyl, pp be 1 o'clock be fluorine atom or methylol.
Pp is 1 compound (f1
p) be new compound.Compound (f1
p) can make by following method: make following compound (f1-3
p) and water reaction and obtain following compound (f1-2
p), make compound (f1-2 again
p) and H-CHO reaction and obtain following compound (f1-1
p), make compound (f1-1 again
p) and CH
2=CR
FlpThe COCl reaction.
Wherein, X
BpAt X
1pRepresent fluorine atom during for fluorine atom, at X
1pRepresent the fluoro carbonyl during for methylol, X
ApAt X
1pRepresent fluorine atom during for fluorine atom, at X
1pRepresent hydrogen atom during for methylol.
As compound (f
p) object lesson, can exemplify polymerizable compound (f
m) object lesson in the compound put down in writing.
Diaphragm polymkeric substance of the present invention (P) is owing to comprise repetitive (B
p), therefore interact with alkali and be dissolved in aqueous slkali.Therefore, diaphragm polymkeric substance (P) can easily be removed by aqueous slkali after the immersion exposure operation in immersion lithography process.
Polymerizable compound (b
p) in hydroxyl can be alcohol hydroxyl group or phenol hydroxyl.
From the angle of the affinity of the water repellency of polymkeric substance and aqueous slkali, polymerizable compound (b
p) be more preferably the hydroxyl on the carbon atom with the carbon atom adjacency that is combined in and is combined with Polyfluoroalkyl or the polymerizable monomer of carboxyl, be-C (C well especially
qF
2qp+1) (OH)-,-C (C
QpF
2qp+1)
2(OH) (wherein, qp represents 1～6 integer) or carboxyl preferably have-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerizable compound of C (O) OH.
As polymerizable compound (b
p) preferred configuration, can exemplify following compound (b1
p)～(b4
p).
CF
2＝CF-Q
Bp-CR
B1p＝CH
2(b1
p)、
CH
2＝CR
B2pC(O)O-Q
B2p(-C(CF
3)
2OH)
bp(b2
p)、
CH
2＝CH-Q
B3p(-C(CF
3)
2OH)
bp(b3
p)。
Wherein, the mark in the formula is represented following implication (down together).
R
B1p: the alkyl of hydrogen atom or carbon number 1～12.
Q
Bp:-CF
2C (CF
3) (OH) (CH
2)
Mp-,-CH
2CH ((CH
2)
PpC (CF
3)
2(OH)) (CH
2)
Np-or-CH
2CH ((CH
2)
PppC (CF
3)
2(C (O) OH)) (CH
2)
Np-.
Mp, np and ppp: independently be respectively 0,1 or 2.
R
B2p: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3.
Q
B2pAnd Q
B3p: respectively independent is (bp+1) valency alkyl of carbon number 1～20 that can contain fluorine atoms.
Bp:1 or 2.
Q
B4p: the divalent alkyl of singly-bound or carbon number 1～10 that can contain fluorine atoms.
As polymerizable compound (b
p) object lesson, can exemplify polymerizable compound (b
m) object lesson in the compound put down in writing.
Diaphragm polymkeric substance of the present invention (P) can be only by repetitive (F
p) and repetitive (B
p) polymkeric substance that forms, also can be by repetitive (F
p) and repetitive (B
p) and remove repetitive (F
p) and repetitive (B
p) in addition repetitive (following other unit (F that also claims
p)) polymkeric substance that forms.
Repetitive (F
p) can only form by a kind, also can be by forming more than 2 kinds.In addition, repetitive (B
p) can only form by a kind, also can be by forming more than 2 kinds.
Other unit (F
p) be not particularly limited, better be the repetitive that the polymerization of the polymerizable compound by having anhydride group forms, good especially is the repetitive that the polymerization by following compound forms.
Diaphragm polymkeric substance of the present invention (P) better be with respect to all repetitives comprise 1～25 mole of %, good especially be the repetitive (F of 3～15 moles of %
p).Diaphragm polymkeric substance (P) better be with respect to all repetitives comprise 50～99 moles of %, be more preferably 75～99 moles of %, good especially be the repetitive (B of 85～97 moles of %
p).
Diaphragm polymkeric substance (P) comprises other unit (F
p) situation under, diaphragm polymkeric substance (P) better is other unit (F that comprises 5～20 moles of % with respect to all repetitives
p).
The weight-average molecular weight of diaphragm polymkeric substance (P) better is 1000～50000, and good especially is 3000～30000.
As the preferred configuration of diaphragm polymkeric substance (P), can exemplify as comprising repetitive (F
p) and repetitive (B
p) polymkeric substance, comprise the repetitive (F of 3～15 moles of % with respect to all repetitives
p) and the repetitive (B of 85～97 moles of %
p), and weight-average molecular weight is 3000～30000 polymkeric substance.
Repetitive (F in the described preferred configuration
p) better be by compound (f1
0p) or compound (f1
1 p) polymerization and the repetitive that forms.Repetitive (B
p) better be by compound (b1
p) or compound (b3
p) polymerization and the repetitive that forms be more preferably by compound (b1
p) cyclopolymerization and the repetitive that forms, good especially is to pass through CF
2=CF-CF
2C (CF
3) (OH) CH
2-CH=CH
2, CF
2=CF-CH
2CH (C (CF
3)
2(OH)) CH
2-CH=CH
2, CF
2=CF-CH
2CH (CH
2C (CF
3)
2(OH)) CH
2-CH=CH
2, or CF
2=CF-CH
2CH (C (O) OH) CH
2-CH=CH
2Cyclopolymerization and the repetitive that forms.
The manufacture method of diaphragm polymkeric substance (P) is not particularly limited, and can exemplify to make compound (f
p) and polymerizable compound (b
p) method of in the presence of radical initiator, carrying out free radical polymerization.
Radical initiator is not particularly limited, can exemplify superoxide such as benzoyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate di tert butyl carbonate, t-butylperoxy pivarate, perfluor tert-butyl peroxide, perfluor benzoyl peroxide, azo-compounds such as azoisobutyronitrile, persulfate etc.
The method of free radical polymerization is not particularly limited, and can use mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization.
Fashionable solvent is not particularly limited to carry out radical polymerization in the presence of solvent, can exemplify pentane, hexane, aliphatic hydrocarbons such as heptane, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, hydro carbons alcohols such as the tert-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl ether, ether, methyl ethyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether, hydro carbons ethers such as tetraethylene glycol dimethyl ether, tetrahydrofuran, 1, annular aliphatic hydro carbons ethers such as 4-diox, nitriles such as acetonitrile, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, tert-butyl acetate, methyl propionate, hydro carbons ester classes such as ethyl propionate, toluene, arenes such as dimethylbenzene, chloroform, chlorinated hydrocarbons such as phenixin, CCl
2FCClF
2, CCl
2FCH
3, CF
3CF
2CHCl
2, CClF
2CF
2Chloro-fluoro-carbon kinds such as CHClF, CF
3(CF
2)
5H, CF
3(CF
2)
3C
2H
5Deng hydrogen fluorohydrocarbon class, CHF
2CF
2OCH
3Deng hydrogen fluorine ethers, CHF
2CF
2CH
2OH, CF
3CF
2CF
2CFHCF
2CH
2OH, CFHCF
2CF
2CF
2CH
2OH, CF
3CH
2OH, CF
3CH (OH) CF
3Deng the fluoro alcohols.
The temperature of reaction of free radical polymerization is not particularly limited, and better is 0 ℃～200 ℃, and good especially is 25 ℃～100 ℃.In addition, the reaction pressure of free radical polymerization can be any in reduced pressure, atmospheric pressure, the pressurized conditions, better is 1kPa～100MPa, and good especially is 10kPa～10MPa.
Diaphragm polymkeric substance of the present invention (P) is applied usually to come film forming in going up the photonasty resist surface that forms at substrate (silicon wafer etc.), from the angle of film forming, better is to make liquid composition therefore.
The invention provides the immersion exposure that comprises diaphragm polymkeric substance (P) and organic solvent with resist-protecting membrane composition (the following diaphragm that also claims forms composition (P)).
Diaphragm forms the organic solvent in the composition (P) so long as get final product for the high solvent of intermiscibility of diaphragm polymkeric substance (P), is not particularly limited.As the object lesson of organic solvent, the organic solvent that forms in the composition (1) with diaphragm is identical.Organic solvent can use a kind, also can use more than 2 kinds.
The organic solvent that diaphragm forms in the composition (P) better is that the alcohols (for example aforementioned hydrogen fluorine alcohols, aforementioned alcohols etc.) that can contain fluorine atom is the organic solvent of neccessary composition, and good especially is the organic solvent that comprises the alcohols of 0.01～100 quality % with respect to the gross mass of organic solvent.
It better is the organic solvent that comprises 100 quality %～10000 quality % with respect to the gross mass of diaphragm polymkeric substance (P) that diaphragm forms composition (P).
In addition, diaphragm formation composition (P) can comprise the composition except that diaphragm polymkeric substance (P) and organic solvent.As the object lesson of this composition, can exemplify plastifier, stabilizing agent, colorant, antihalation agent.
Diaphragm forms composition (P) and can be used for immersion lithography process.Immersion lithography process is not particularly limited, and can exemplify the immersion lithography process that carries out following operation successively: go up coating photonasty anticorrosive additive material at substrate (silicon wafer etc.), form the operation of resist film on this substrate; Diaphragm is formed composition (P) coat on this resist film, on this resist film, form the operation of resist-protecting membrane; The immersion exposure operation; Developing procedure; Etching work procedure; And resist stripping process.
As the photonasty anticorrosive additive material, can exemplify with diaphragm of the present invention and form the photonasty anticorrosive additive material identical materials of putting down in writing in the composition.
Exposure light source among the present invention also can exemplify with diaphragm of the present invention and form the identical light source of putting down in writing in the composition of exposure light source.
As the immersion exposure operation; can exemplify following operation: with between projecting lens and resist-protecting membrane with liquid medium full the time, will to mask shine exposure light source light and the pattern image of mask be situated between with operation in the desired location of the resist film of projecting lens projection on substrate that relatively moves on the resist-protecting membrane.Liquid medium better is to be the liquid medium of principal ingredient with water, and good especially is ultrapure water.
In the immersion exposure operation, diaphragm and liquid medium (water etc.) partition that resist film forms by formed composition (P) by diaphragm be difficult for being invaded by liquid medium, and the composition in the resist film are difficult for stripping to liquid medium.Therefore, in the immersion exposure operation of the present invention, resist film is difficult for swelling, not the optical characteristics such as refractive index of malleable liquid medium.In addition, in the immersion exposure operation of the present invention, therefore water and the projecting lens servo-actuated well that relatively moves on resist-protecting membrane can stably implement the immersion exposure operation.
As developing procedure, can exemplify with diaphragm of the present invention and form the same form of putting down in writing in the composition of developing procedure.
The invention provides immersion exposure resist-protecting membrane composition (hereinafter referred to as diaphragm composition (Q)), it comprises following polymkeric substance (F
q) and following polymkeric substance (B
q), and with respect to polymkeric substance (B
q) comprise the polymkeric substance (F of 0.1～30 quality %
q).
Polymkeric substance (F
q): as comprising by compound (f
p) polymerization and the repetitive (F that forms
p) polymkeric substance, comprise 10 moles of repetitive (F more than the % with respect to all repetitives
p) polymkeric substance.
Polymkeric substance (B
q): comprise by polymerizable compound (b
q) polymerization and the repetitive (B that forms
p) alkali-soluble polymer.
Polymkeric substance (F in the diaphragm composition of the present invention (Q)
q) water repellency good, dynamically water repellency is good especially.Its reason it be unclear that, but thinks because polymkeric substance (F
q) be to have the compound of deriving from (f at side chain
p) bulky fluoro-containing group (with formula-X
pThe group of expression) polymkeric substance.Therefore, think and comprise polymkeric substance (F
q) diaphragm composition (Q) form because of high water repellency is difficult for by the submergence diaphragm of water intrusion, and because dynamically water repellency is good especially, so be formed on the submergence diaphragm that slides well in the water.
Polymkeric substance (F
q) can be only by repetitive (F
p) polymkeric substance that forms, also can be to comprise repetitive (F
p) and remove repetitive (F
p) in addition repetitive (following other unit (F that also claims
q)) polymkeric substance.In addition, repetitive (F
p) can only form by a kind, also can be by forming more than 2 kinds.
No matter be any situation, polymkeric substance (F
q) all comprise 10 moles more than the %, better be 50 moles of repetitive (F more than the % with respect to all repetitives
p).Polymkeric substance (F
q) comprise other unit (F
q) situation under, polymkeric substance (F
q) better be with respect to all repetitives comprise 90 moles below the %, good especially be 50 moles of other unit (F below the %
q).Other unit (F
q) be not particularly limited.
Polymkeric substance (F
q) weight-average molecular weight better be 1000～30000, good especially is 3000～20000.
As polymkeric substance (F
q) preferred configuration, can exemplify as only by by compound (f1
p) polymerization and polymkeric substance that the repetitive that forms forms, weight-average molecular weight is 1000～30000, better be 3000～20000 polymkeric substance.
Diaphragm composition of the present invention (Q) comprises alkali-soluble polymer (polymkeric substance (B
q)), this polymkeric substance comprises by polymerizable compound (b
q) polymerization and the repetitive (b that forms
q).Diaphragm composition (Q) is because polymkeric substance (B
q) interact with alkali and be dissolved in aqueous slkali, all can easily be removed by aqueous slkali.
Polymkeric substance (B
q) better be with respect to all repetitives comprise 10 moles more than the %, good especially be 50 moles of repetitive (B more than the %
p).Polymkeric substance (B
q) can be only by repetitive (b
p) polymkeric substance that forms, also can be to comprise repetitive (b
p) and remove repetitive (b
p) in addition repetitive (following other unit (B that also claims
q)) polymkeric substance.In addition, repetitive (b
p) can only form by a kind, also can be by forming more than 2 kinds.Polymkeric substance (B
q) comprise other unit (B
q) situation under, polymkeric substance (B
q) better be with respect to all repetitives comprise 90 moles below the %, good especially be 50 moles of other unit (B below the %
q).
Polymkeric substance (B
q) in repetitive (B
p) preferred configuration and the repetitive (B in the diaphragm polymkeric substance (P)
p) identical.
Polymkeric substance (B
q) other unit (B of comprising
q) time other unit (B
q) with diaphragm polymkeric substance (P) in other unit (B
p) in the record polymerizable compound identical.
Polymkeric substance (B
q) weight-average molecular weight better be 1000～100000, good especially is 1000～50000.
As polymkeric substance (B
q) preferred configuration, can exemplify as what comprise 70～100 moles of % with respect to all repetitives and pass through compound (b1
p) or compound (b2
p) polymerization and the polymkeric substance of the repetitive that forms, weight-average molecular weight is 1000～100000 polymkeric substance.As preferred form, can exemplify only by passing through compound (b1
p) cyclopolymerization and the repetitive that forms forms, weight-average molecular weight is 1000～50000 polymkeric substance.
Diaphragm composition (Q) comprises polymkeric substance (F
q) and polymkeric substance (B
q), and with respect to polymkeric substance (F
q) comprise the polymkeric substance (B of 0.1～30 quality %
q).Be more preferably with respect to polymkeric substance (B
q) comprise the polymkeric substance (F of 1～10 quality %
q).Under this situation, polymkeric substance (F
q) and polymkeric substance (B
q) easily mix, have the good effect of film forming of submergence diaphragm.
Diaphragm composition (Q) can comprise except that polymkeric substance (F
q) and polymkeric substance (B
q) in addition composition.As this composition, can exemplify organic solvent, plastifier, stabilizing agent, colorant, antihalation agent etc.
Diaphragm composition (Q) is applied usually to be used in film forming on the last resist film that forms of substrate (silicon wafer etc.), from the angle of film forming, better is aqueous therefore.Diaphragm composition (Q) better is to comprise organic solvent.
The invention provides the diaphragm composition (the following diaphragm that also claims forms composition (Q)) that comprises diaphragm composition (Q) and organic solvent.
Organic solvent in the diaphragm formation composition (Q) is so long as for polymkeric substance (F
q) and polymkeric substance (B
q) the high solvent of intermiscibility get final product, be not particularly limited.Organic solvent can use a kind, also can use more than 2 kinds.
For polymkeric substance (F
q) the high organic solvent of intermiscibility better be the fluorine-containing organic solvent that forms by fluorochemicals, from for polymkeric substance (B
q) the also high angle of intermiscibility, good especially is fluorine-containing organic solvent by the fluorochemicals with the hydrogen atom that combines with carbon atom.Fluorine-containing organic solvent can use a kind, also can use more than 2 kinds.
For polymkeric substance (B
q) the high organic solvent of intermiscibility can be the fluorine-containing organic solvent that the fluorochemicals by contain fluorine atoms forms, also can be the organic solvent that forms by the compound of contain fluorine atoms not.
Also have, the object lesson of organic solvent can exemplify the organic solvent that diaphragm forms record in the composition (1), and the object lesson of fluorine-containing organic solvent also can exemplify the fluorine-containing organic solvent that diaphragm forms record in the composition (1).
Angle from the intermiscibility of diaphragm composition (Q); the organic solvent that diaphragm forms in the composition (Q) better is to be the organic solvent of neccessary composition with fluorine-containing organic solvent, and good especially is that gross mass with respect to organic solvent comprises more than the 50 quality % and the organic solvent of the fluorine-containing organic solvent of less than 100 quality %.In addition, from making polymkeric substance (F
q) and polymkeric substance (B
q) equably the dissolving angle, organic solvent among the present invention better is to be the organic solvent of neccessary composition with the alcohol organic solvent that formed by the alcohol of contain fluorine atoms (alcohols in for example aforesaid fluorine-free organic solvent) not, and good especially is the organic solvent that comprises the alcohol organic solvent of 0.01～10 quality % with respect to the gross mass of organic solvent.In addition, the content of organic solvent better is with respect to polymkeric substance (F
q) and polymkeric substance (B
q) gross mass be 100 quality %～10000 quality %.
The manufacture method that diaphragm forms composition (Q) is not particularly limited, and can exemplify following method: modulation makes polymkeric substance (F respectively
q) be dissolved in fluorine-containing organic solvent and solution (hereinafter referred to as resin solution (F
q)) and make polymkeric substance (B
q) be dissolved in organic solvent and solution (hereinafter referred to as resin solution (B
q)), again with resin solution (F
q) and resin solution (B
q) mix.Resin solution (F
q) better be the polymkeric substance (F that comprises 0.1～10 quality %
q).In addition, resin solution (B
q) better be the polymkeric substance (B that comprises 0.1～20 quality %
q).
Diaphragm forms composition (Q) and can be used for immersion lithography process.The form of immersion lithography process is identical with the immersion lithography process that adopts diaphragm formation composition (P).
In the immersion exposure operation of the immersion lithography process of employing diaphragm composition (Q); resist film cuts off by diaphragm and the liquid medium (water etc.) that is formed by diaphragm composition (Q); be difficult for being invaded, and the composition in the resist film is difficult for stripping to liquid medium by liquid medium.Therefore, in the immersion exposure operation, resist film is difficult for swelling, not the optical characteristics such as refractive index of malleable liquid medium.In addition, in the immersion exposure operation, therefore water and the projecting lens servo-actuated well that relatively moves on resist-protecting membrane can stably implement the immersion exposure operation.
In addition, the invention provides to comprise and have repetitive (F
w) the photoetching of polymkeric substance with anticorrosive additive material (the following anticorrosive additive material (W) that also claims), described repetitive (F
w) by having the polymerizable compound (f of fluorine-containing two ring type bridged ring structures
w) polymerization and form.
Polymerizable compound (f
w) better be following compound (f1
w) or following compound (f2
w).
Mark in the formula is represented following implication.
W
Fw: fluorine atom or trifluoromethyl.
R
Fw: the perfluoroalkyl of fluorine atom or carbon number 1～16,2 R
FwCan be identical or different.
Q
Fw:-CF
2-or-C (CF
3)
2-, 2 Q
FwCan be identical or different.
R
Aw: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3.
J
Aw: the alkylidene that can contain the carbon number 1～10 of etheric oxygen atom.
The water repellency of anticorrosive additive material of the present invention (W), particularly dynamic water repellency are good.Its reason it be unclear that, and derives from polymerizable compound (f but think that anticorrosive additive material (W) comprises
w) the bulky fluoropolymer of fluorine-containing two ring type bridged ring structures.Therefore, by anticorrosive additive material (W), can easily make be difficult for being submerged the anticorrosive additive material that liquid is invaded and slided well in immersion liquid.
Polymerizable compound (f
w) so long as the carbon atom that has the compound of polymerizable group and fluorine-containing two ring type bridged ring structures and constitute these fluorine-containing two ring type bridged ring structures is combined with the compound of fluorine atom gets final product, be not particularly limited.
Polymerizable group better is the group with two keys of carbon atom-carbon atom of polymerism.
Fluorine-containing two ring type bridged ring structures better are aliphatic groups, and good especially is saturated aliphatic groups.In addition, can be inserted with between the carbon atom-carbon atom in the fluorine-containing two ring type bridged ring structures-O-,-C (O) O-or-C (O)-.In addition, the carbon atom in the fluorine-containing two ring type bridged ring structures can be combined with hydroxyl or carboxyl.
Polymerizable compound (f
w) fluorinated volume better be more than the 30 quality %, good especially is more than the 50 quality %.The upper limit of described fluorinated volume better is below the 76 quality %.Polymerizable compound (f
w) carbon number better be 8～20.
Polymerizable compound (f
w) better be compound (f1
w) or compound (f2
w).Compound (f1
w) or compound (f2
w) mother's ring on the spatial configuration of asymmetric center can be interior type or external form.
R
AwBetter be hydrogen atom, fluorine atom, methyl or trifluoromethyl, good especially is hydrogen atom or methyl.
R
FwBetter be all to be fluorine atom, perhaps a side is the perfluoroalkyl of carbon number 1～16 for fluorine atom the opposing party, and good especially is all to be fluorine atom.
J
AwIt better is methylene.
As polymerizable compound (f
w) object lesson, with polymerizable compound (f
m) object lesson in the compound put down in writing identical.
Compound (f1
w) be new compound.Compound (f1
w) can make by following method: make following compound (f1
51w) and R
FPw-COF carries out esterification and obtains following compound (f1
41w), again by compound (f1
41w) liquid phase fluorination reaction obtain following compound (f1
3w), again with compound (f1
3w) under KF exists, carry out pyrolysis and obtain following compound (f1
2w), again with compound (f1
2w) carry out reduction reaction and obtain following compound (f1
1w), make compound (f1 again
1w) and CH
2=CR
AwC (O) Cl reaction.
Wherein, the mark in the formula is represented following implication.
R
FPw: the perfluoroalkyl that can comprise the carbon number 1～20 of etheric oxygen atom.
W
Pw: corresponding to W
FwGroup, hydrogen atom or methyl.
R
Pw: corresponding to R
FwGroup, the alkyl of carbon atom or carbon number 1～16.2 R
PwCan be identical or different.
Q
Pw: corresponding to Q
FwGroup ,-CH
2-or-C (CH
3)
2-.2 Q
PwCan be identical or different.
Compound (f1
3w) can be by except using following compound (f1
52w) replacement compound (f1
51w) similarly operate in addition and the following compound (f1 that obtains
42w) liquid phase fluorination reaction obtain.
Compound (f2
w) be new compound.Compound (f2
w) can use following compound (f2
2w) make compound (f2
2w) can followingly obtain: make following compound (f2
51w) and R
FPw-COF carries out esterification and obtains following compound (f2
41w), again by compound (f2
41w) liquid phase fluorination reaction obtain following compound (f2
3w), again with compound (f2
3w) under KF exists, carry out pyrolysis and obtain.
For example, can be by making compound (f2
2w) and methyl alcohol reaction and obtain following compound (f2
2Mw), again with compound (f2
2Mw) carry out reduction reaction and obtain following compound (f21
1Mw), make compound (f21 again
1Mw) and CH
2=CR
wC (O) Cl reaction, thus manufacture following compound (f2
Mw).
Compound (f2
3w) can be by except using following compound (f2
52w) replacement compound (f2
51w) similarly operate in addition and the following compound (f2 that obtains
42w) liquid phase fluorination reaction obtain.
As making polymerizable compound (f
w) method of polymerization, can exemplify and in the presence of polymerization initiator, make polymerizable compound (f
w) method of polymerization.As polymerization initiator, can exemplify organic peroxide, inorganic peroxide, azo-compound.The temperature of polymerization, pressure, time are not particularly limited.
The invention provides resist-protecting membrane for immersion lithography polymkeric substance (hereinafter referred to as diaphragm polymkeric substance (W)), it is to comprise repetitive (F
w) and repetitive (B
w) alkali-soluble polymkeric substance, described repetitive (B
w) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
w) polymerization and form, comprise the repetitive (F of 1～70 mole of % with respect to all repetitives
w), the above repetitive (B of 10 moles of %
w) polymkeric substance.
Diaphragm polymkeric substance of the present invention (W) is owing to comprise repetitive (F
w), therefore dynamically water repellency is good especially.In the immersion lithography process of the resist-protecting membrane that setting is made by diaphragm polymkeric substance (W), immersion liquid well with the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.In addition, diaphragm polymkeric substance (W) is owing to comprise repetitive (B
w), be alkali-soluble polymkeric substance therefore.Described resist-protecting membrane can easily be removed by aqueous slkali.Therefore, by diaphragm polymkeric substance of the present invention (W), can realize and to implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
Polymerizable compound (f in the diaphragm polymkeric substance (W)
w) better be compound (f1
w) or compound (f2
w).
Polymerizable compound (b in the diaphragm polymkeric substance (W)
w) better be polymerizable compound with hydroxyl or carboxyl.Hydroxyl can be alcohol hydroxyl group or phenol hydroxyl.
From the water repellency of diaphragm polymkeric substance (W) and the angle of alkali affinity, polymerizable compound (b
w) be more preferably the hydroxyl on the carbon atom with the carbon atom adjacency that is combined in and is combined with Polyfluoroalkyl or the polymerizable compound of carboxyl, good especially is to have-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerizable compound of C (O) OH.
Polymerizable compound (b
w) better be compound (b1)～compound (b4), good especially is compound (b1).
Diaphragm polymkeric substance of the present invention (W) can be only by repetitive (F
w) and repetitive (B
w) polymkeric substance that forms, also can be the polymkeric substance that also comprises other unit.In addition, the repetitive (F in the diaphragm polymkeric substance (W)
w) can be more than a kind or 2 kinds.In addition, the repetitive (B in the diaphragm polymkeric substance (W)
w) can be more than a kind or 2 kinds.
Diaphragm polymkeric substance (W) better is the repetitive (F that comprises 1～50 mole of % with respect to all repetitives
w).Diaphragm polymkeric substance (W) better is the repetitive (B that comprises 50～99 moles of % with respect to all repetitives
w).
The weight-average molecular weight of diaphragm polymkeric substance (W) better is 1000～100000, and good especially is 1000～50000.
As the preferred configuration of diaphragm polymkeric substance (W), can exemplify only by repetitive (F
w) and repetitive (B
w) form, comprise the repetitive (F of 1～50 mole of % with respect to all repetitives
w), the repetitive (B of 50～99 moles of %
w) polymkeric substance.
Repetitive (B in the described form
w) better be the repetitive that the polymerization by compound (b1) forms, good especially is to pass through CF
2=CFCF
2C (CF
3) (OH) CH
2CH=CH
2, CF
2=CFCH
2CH (C (CF
3)
2(OH)) CH
2CH=CH
2Or CF
2=CFCH
2CH (C (O) OH) CH
2CH=CH
2Polymerization and the repetitive that forms.
The weight-average molecular weight of the polymkeric substance of described preferred configuration better is 1000～30000.
Diaphragm polymkeric substance (W) is coated on the surface of the photonasty resist film that is formed on the substrate usually and uses in to the application of immersion lithography process, better be to be modulated into liquid composition therefore.
The invention provides the resist-protecting membrane for immersion lithography composition (the following diaphragm that also claims forms composition (W)) that comprises diaphragm polymkeric substance (W) and organic solvent.
It better is the organic solvent that comprises 100 quality %～10000 quality % with respect to the gross mass of diaphragm polymkeric substance (W) that diaphragm forms composition (W).
As organic solvent,, be not particularly limited so long as get final product for the high solvent of intermiscibility of diaphragm polymkeric substance (W).As the object lesson of organic solvent, the organic solvent that forms record in the composition (1) with diaphragm is identical.
Diaphragm formation composition (W) can comprise the composition except that diaphragm polymkeric substance (W) and organic solvent.As the object lesson of this composition, can exemplify plastifier, stabilizing agent, colorant, antihalation agent.
The invention provides and carry out following operation successively, in the formation method of the corrosion-resisting pattern that forms corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate forms the operation of resist film on substrate; Diaphragm is formed composition (W) coat on this resist film, on resist film, form the operation of resist-protecting membrane; The liquid immersion lithography operation; Developing procedure.
The concrete form of immersion lithography process is identical with the immersion lithography process that adopts diaphragm formation composition (1).
The invention provides resist-protecting membrane for immersion lithography composition (hereinafter referred to as diaphragm composition (V)), comprise and have repetitive (F
w) polymkeric substance (FB
w) and alkali-soluble polymkeric substance (B
w), and with respect to polymkeric substance (B
w) comprise the polymkeric substance (FB of 0.1～30 quality %
w), described polymkeric substance (FB
w) comprise 10 moles of repetitive (F more than the % with respect to all repetitives
w).
Diaphragm composition of the present invention (V) has repetitive (F owing to comprising
w) polymkeric substance (FB
w), therefore dynamically water repellency is good especially.In the immersion lithography process of the resist-protecting membrane that setting is made by diaphragm composition (V), immersion liquid well with the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.In addition, diaphragm composition (V) is owing to comprise polymkeric substance (B
w), be alkali-soluble polymkeric substance therefore.Described resist-protecting membrane can easily be removed by aqueous slkali.Therefore, by diaphragm composition (V), can realize and to implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
Polymerizable compound (f in the diaphragm composition (V)
w) better be compound (f1
w) or compound (f2
w).
Polymkeric substance (FB in the diaphragm composition (V)
w) can be only by repetitive (F
w) polymkeric substance that forms, also can be to comprise except that repetitive (F
w) in addition repetitive (following other unit (FB that also claims
w)) polymkeric substance.No matter be any situation, polymkeric substance (FB
w) all comprise 10 moles more than the %, better be 20 moles of repetitive (F more than the % with respect to all repetitives
w).Polymkeric substance (FB
w) comprise other unit (FB
w) situation under, better be with respect to all repetitives comprise 90 moles below the %, good especially be 50 moles of other unit (FB below the %
w).
Other unit (FB
w) be not particularly limited, better be by polymerizable compound (b
w) polymerization and the repetitive (FB that forms
w).
Polymerizable compound (b in the diaphragm composition (V)
w) preferred configuration and the polymerizable compound (b in the diaphragm polymkeric substance (W)
w) identical.
Polymkeric substance (FB
w) weight-average molecular weight better be 1000～100000, good especially is 1000～50000.
As polymkeric substance (FB
w) preferred configuration, can exemplify following polymkeric substance (FB
WH) and following polymkeric substance (FB
WC).
Polymkeric substance (FB
WH): only by repetitive (F
w) polymkeric substance that forms.
Polymkeric substance (FB
WC): as by repetitive (F
w) and other unit (FB
w) polymkeric substance that forms, comprise the repetitive (F of 10～70 moles of % with respect to all repetitives
w), other unit (FB of 50～90 moles of %
w) polymkeric substance.
Polymkeric substance (FB
WC) other unit (FB
w) better be by having-C (CF
3) (OH)-,-C (CF
3)
2(OH) or-polymerization of the polymerizable compound of C (O) OH and the repetitive that forms, good especially is the repetitive that the polymerization by compound (b1) forms.
The weight-average molecular weight of the polymkeric substance of described preferred configuration better is 1000～30000.
Polymkeric substance (B
w) better be to comprise by polymerizable compound (b
w) polymerization and the repetitive (B that forms
w) polymkeric substance.Polymkeric substance (B
w) in polymerizable compound (b
w) preferred configuration and the polymerizable compound (b in the resist-protecting membrane polymkeric substance (W)
w) identical.
In addition, the polymkeric substance (B under this situation
w) can be only by repetitive (B
w) polymkeric substance that forms, also can be the polymkeric substance that also comprises other unit.In addition, repetitive (B
w) can only form by a kind, also can be by forming more than 2 kinds.Polymkeric substance (B
w) good especially be to comprise 50 moles of repetitive (B more than the % with respect to all repetitives
w).
Polymkeric substance (B
w) weight-average molecular weight better be 1000～100000, good especially is 1000～50000.
As polymkeric substance (B
w) preferred configuration, can exemplify as comprising repetitive (B
w) polymkeric substance, comprise the repetitive (B of 70～100 moles of % with respect to all repetitives
w) polymkeric substance.As particularly preferred form, can exemplify only by repetitive (B
w) polymkeric substance that forms.
Repetitive (the B of the polymkeric substance of described preferred configuration
w) better be the repetitive that the polymerization by compound (b1) forms.
The weight-average molecular weight of the polymkeric substance of described preferred configuration better is 1000～50000.
Diaphragm composition (V) comprises polymkeric substance (FB
w) and polymkeric substance (B
w) and with respect to polymkeric substance (B
w) comprise the polymkeric substance (FB of 0.1～30 quality %
w).Be more preferably with respect to polymkeric substance (B
w) comprise the polymkeric substance (FB of 1～10 quality %
w).Under this situation, polymkeric substance (FB
w) and polymkeric substance (B
w) easily mix, have the good effect of film forming of diaphragm.
Diaphragm composition (V) is coated on the surface of the photonasty resist film that is formed on the substrate usually and uses in to the application of immersion lithography process, better be to be modulated into liquid composition therefore.
The invention provides the resist-protecting membrane for immersion lithography composition (the following diaphragm that also claims forms composition (V)) that comprises diaphragm composition (V) and organic solvent.
It better is the organic solvent that comprises 100 quality %～10000 quality % with respect to the gross mass of diaphragm composition (V) that diaphragm forms composition (V).
As organic solvent,, be not particularly limited so long as get final product for the high solvent of intermiscibility of diaphragm polymkeric substance (V).As the object lesson of organic solvent, the organic solvent that forms record in the composition (1) with diaphragm is identical.
The invention provides and carry out following operation successively, in the formation method of the corrosion-resisting pattern that forms corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate forms the operation of resist film on substrate; Diaphragm is formed composition (V) coat on this resist film, on resist film, form the operation of resist-protecting membrane; The liquid immersion lithography operation; Developing procedure.
The concrete form of immersion lithography process is identical with the immersion lithography process that adopts diaphragm formation composition (1).
Embodiment
By embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.
Among the embodiment, the gel permeation chromatography note is made the GPC method, and the weight-average molecular weight note is made Mw, and the number-average molecular weight note is made Mn, and the glass temperature note is made Tg.
In addition, dichloro pentafluoropropane (CF
3CF
2CHCl
2And CF
2ClCF
2The potpourri of CHFCl) note is made R225, and 1,1,2-three chloro-1,2,2-HFC-143a note is made R113, and the di-isopropyl peroxydicarbonate note is made IPP, and the tetramethylsilane note is made TMS, the tetrahydrofuran note is made THF, and 2-propyl alcohol note is made IPA, and perfluor benzoyl peroxide note is made PFBPO.
The Mw of polymkeric substance and Mn use gel permeation chromatography (to launch solvent: THF, interior mark: polystyrene) measure.In addition, the composition of each polymkeric substance passes through
19F-NMR and
1The mensuration of H-NMR is determined.The Tg of polymkeric substance uses DSC to measure.
In order to make polymkeric substance (F), use compound (f
1), compound (f
2), compound (f
3), compound (f
4), compound (b
1) or compound (b
2).
In addition, by compound (f
1) polymerization and the repetitive that forms note is made unit (F
1), by compound (f
2) polymerization and the repetitive that forms note is made unit (F
2), by compound (f
3) polymerization and the repetitive that forms note is made unit (F
3), by compound (f
4) polymerization and the repetitive that forms note is made unit (F
4).
In addition, by compound (b
1) polymerization and form with following formula (B
1) the repetitive note of expression makes unit (B
1), by compound (b
2) polymerization and form with following formula (B
1) the repetitive note of expression makes unit (B
2).
The Production Example of [example 1 (with reference to synthesis example)] compound (f)
[routine 1-1] compound (f
2) Production Example
In remaining in 0 ℃ flask, add following compound (pf
2) (27.46g), NaF (3.78) and acetone (100mL), stir.Then, in flask, drip water (1.14g), to fully stirring in the flask.With solution sublimation purification in the flask, obtain following compound (qf
2) (22.01g).
Compound (qf in flask
2) (2.03g) and the potpourri of dimethyl sulfoxide (50mL) add potassium hydroxide (1.00g) and formalin (20mL), under this state, it was reacted 6.5 hours in 75 ℃.After reaction finishes, reactant liquor with R225 (40mL) extraction, is heated up in a steamer R225 again, obtain following compound (rf
2) (1.58g).
With the compound (rf that obtains equally
2) (6.01g) and R225 (103g) join in the flask, add triethylamine (1.68g) and CH more one by one on a small quantity
2=C (CH
3) COCl (1.58g), stirring 2 hours in 25 ℃ under this state flask.Liquid water (50mL) washing that to filter solution in the flask and get 2 times.Then, with solution in the flask with dried over mgso after, concentrate, obtain lurid solid (6.19g).Solid by the column chromatography purifying, is obtained compound (f
2).
Compound (f
2) the NMR data as follows.
1H-NMR (300.4MHz, CDCl
3, interior mark: Si (CH
3)
4) δ (ppm): 1.96 (s, 3H), 5.06 (s, 2H), 5.71 (s, 1H), 6.19 (s, 1H).
19F-NMR (282.7MHz, CDCl
3, interior mark: CFCl
3) δ (ppm) :-113.6 (6F) ,-121.1 (6F) ,-219.4 (3F).
[routine 1-2] compound (f
3) Production Example
According to the manufacturing route of representing with following formula, by following compound (nf
3) make compound (f
3).Wherein, R
F1-expression F (CF
2)
3OCF (CF
3) CF
2OCF (CF
3)-.
Add compound (nf in the flask under nitrogen atmosphere
3) (15g), chloroform (100g) and NaF (7.02g), when carrying out ice-cold stirring in the flask, drip R
F1-COF (79g) is after dropping finishes, again to stirring in the flask.Remove the insoluble solids of flask contents by pressure filtration after, in flask, add saturated sodium bicarbonate aqueous solution (103g), reclaim and concentrate organic layer, obtain compound (of
3) (74g).
In the autoclave that is provided with the particles filled layer of NaF at gas vent, add R113 (313g), when 25 ℃ are stirred in to autoclave, in autoclave, feed nitrogen after 1 hour, feed fluorine gas with nitrogen dilution to 20% volume.Under this state, feed in this 20% fluorine gas, under the pressure of 0.1MPa, in autoclave, import and make compound (of
3) (67g) be dissolved in R113 (299g) and solution.After importing end, the autoclave contents recovery is concentrated, obtain compound (pf
3).
Add compound (pf in the flask under nitrogen atmosphere
3) (80g) and Powdered KF (0.7g), to heating is after 6 hours in the flask, the purifying flask contents obtains compound (qf
3) (38g).
Add NaBH in the round-bottomed flask under nitrogen atmosphere
4(1.1g) and THF (30g).When carrying out ice-cold stirring in the flask, in flask, drip the compound (qf that contains 22 quality %
3) R225 solution (48g).After dripping end, after stirring again in the flask, will be, to carry out distillation purifying, thereby to obtain compound (rf after the solution that the gets washing with the flask content liquid in the aqueous hydrochloric acid solution (150mL)
3).
In flask, add compound (rf
3) (2.2g), the aluminium salt (2mg) and the triethylamine (1.2g) of THF (10g), N-nitroso-phenyl hydramine.When carrying out ice-cold stirring in the flask, in flask, drip and make CH
2=C (CH
3) C (O) Cl (1.2g) be dissolved in THF (7.3g) and solution.After dripping end, after stirring again in the flask, add sodium bicarbonate aqueous solution.Will with R225 extract solution in the flask and dry the concentrating of extract, the concentrate of gained by the silica gel column chromatography purifying, is obtained compound (f
3) (2.7g).
Compound (f
3) the NMR data as follows.
1H-NMR (300.4MHz, solvent: CDCl
3, benchmark: TMS) δ (ppm): 6.31 (1H), 5.88 (1H), 5.84 (1H), 2.01 (3H).
19F-NMR (282.7MHz, solvent: CDCl
3, benchmark: CFCl
3) δ (ppm) :-104.6 (1F) ,-120.5 (1F) ,-122.4 (1F) ,-124.2 (1F) ,-124.6 (1F) ,-126.5 (1F) ,-132.7～-132.8 (2F) ,-214.8 (1F) ,-223.2 (1F).
[routine 1-3] compound (f
4) Production Example
According to the manufacturing route of representing with following formula, by following compound (nf
4) make compound (f
4).Wherein, R
F2-expression F (CF
2)
3OCF (CF
3)-.
Add compound (nf in the flask under nitrogen atmosphere
4) (26g) and R225 (100g), when carrying out ice-cold stirring in the flask, drip R
F2-COF (91g) is after dropping finishes, again to stirring in the flask.With the flask contents thickening filtration, obtain compound (of
4) (88g).
In the autoclave that is provided with the particles filled layer of NaF at gas vent, add R113 (326g), when 25 ℃ are stirred in to autoclave, in autoclave, feed nitrogen after 1 hour, feed fluorine gas with nitrogen dilution to 20% volume.Under this state, feed in this 20% fluorine gas, under the pressure of 0.1MPa, in autoclave, import and make compound (of
4) (75g) be dissolved in R113 (346g) and solution.After importing end, the autoclave contents recovery is concentrated, obtain compound (pf
4).
Ice-cold following to making compound (pf
4) (106g) be dissolved in R225 (100mL) and solution in drip methyl alcohol (20g), obtain solution.After dripping end, behind 25 ℃ of agitating solutions, heat up in a steamer R225 and F (CF from solution
2)
3OCF (CF
3) COOCH
3, obtain resultant of reaction (42g).In the solution of the THF that contains resultant of reaction (100mL), drip the ((CH that contains 79 quality %
3)
2CHCH
2)
2The hexane solution of AlH (20g) obtains solution.After dripping end, agitating solution neutralizes solution again with the 0.2mol/L aqueous hydrochloric acid solution, obtain crude reaction liquid.Will with R225 extract crude reaction liquid and the low boiling point component of extract heat up in a steamer after, again with crude reaction liquid recrystallization in hexane, obtain compound (rf
4).
In flask, add compound (rf
4) (16.3g), t-butyl methyl ether (82mL), quinhydrones (5mg) and triethylamine (8.1g).When carrying out ice-cold stirring in the flask, in flask, drip CH
2=C (CH
3) C (O) Cl (8.4g).After dripping end, after stirring in the flask, in flask, add pure water (50mL), obtain two layers of parting liquid.Reclaim the upper strata of two layers of parting liquid, dry concentrating and obtain concentrate.This concentrate by the silica gel column chromatography purifying, is obtained compound (f
4) (14g).
Compound (f
4) the NMR data as follows.
1H-NMR (300.4MHz, solvent: CDCl
3, benchmark: TMS) δ (ppm): 6.20 (1H), 5.70 (1H), 4.75 (2H), 1.98 (3H).
19F-NMR (282.7MHz, solvent: CDCl
3, benchmark: CFCl
3) δ (ppm) :-118.6 (1F) ,-120.6 (1F) ,-123.8 (2F) ,-124.5 (1F) ,-124.9 (1F) ,-128.6 (1F) ,-131.4 (1F) ,-179.1 (1F) ,-219.8 (1F) ,-227.0 (1F).
The Production Example (its 1) of [example 2] resist-protecting membrane for immersion lithography polymkeric substance
[routine 2-1] polymkeric substance (F
1) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
1) (0.54g), compound (b
1) (4.0g), behind R225 (19.9g) and the IPA (0.4g), the IPP (0.76g) that adds the R225 solution of making 50 quality % is as polymerization initiator.Then,, temperature in the reactor is remained on 40 ℃, carry out 18 hours polyreaction the degassing of reducing pressure in the reactor.Then, the reactor content liquid is added drop-wise in the hexane, reclaims the solid constituent that precipitates again and get,, obtain polymkeric substance (F 100 ℃ of vacuum drying 24 hours
1) (4.11g).
Polymkeric substance (F
1) at 25 ℃ of pulverous amorphism polymkeric substance (Tg106 ℃) that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
1) Mn be 7200, Mw is 13900.In addition, polymkeric substance (F
1) for comprising the unit (F of 7 moles of %
1) and the unit (B of 93 moles of %
1) polymkeric substance.
[routine 2-2] polymkeric substance (F
2) Production Example
In voltage-resistant reactor (internal volume 100mL, glass), add compound (b
1) (6.0g), behind R225 (27.7g) and the IPA (0.56g), the IPP (1.15g) that adds the R225 solution of making 50 quality % is as polymerization initiator.
Then, when temperature in the reactor is remained on 40 ℃, with 6 hour to reactor in drip by compound (f on one side
1) (1.02g), the mixed liquor that forms of R225 (3.08g) and IPA (0.06g), Yi Bian carry out polyreaction.After the dropping of this mixed liquor finishes, under this state, carry out 12 hours polyreaction.Then, the reactor content liquid is added drop-wise in the hexane, reclaims the solid constituent that precipitates again and get,, obtain polymkeric substance (F 90 ℃ of vacuum drying 24 hours
2) (5.77g).
Polymkeric substance (F
2) at 25 ℃ of pulverous amorphism polymkeric substance that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
2) Mn be 5600, Mw is 11600.In addition, polymkeric substance (F
2) for comprising the unit (F of 9 moles of %
1) and the unit (B of 91 moles of %
1) polymkeric substance.
[routine 2-3] polymkeric substance (F
3) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
1) (0.35g), compound (b
1) (4.0g), behind R225 (14.3g) and the IPA (2.80g), the IPP (0.65g) that adds the R225 solution of making 50 quality % is as polymerization initiator.Then,, temperature in the reactor is remained on 40 ℃, carry out 18 hours polyreaction the degassing of reducing pressure in the reactor.Then, the reactor content liquid is concentrated, after the R225 dilution, be added drop-wise in the hexane, reclaim the solid constituent that precipitates again and get,, obtain polymkeric substance (F 90 ℃ of vacuum drying 24 hours
3) (2.72g).
Polymkeric substance (F
3) at 25 ℃ of pulverous amorphism polymkeric substance (Tg92 ℃) that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
3) Mn be 4300, Mw is 6400.In addition, polymkeric substance (F
3) for comprising the unit (F of 5.6 moles of %
1) and the unit (B of 94.4 moles of %
1) polymkeric substance.
[routine 2-4] polymkeric substance (F
4) Production Example
In voltage-resistant reactor (internal volume 100mL, glass), add compound (b
1) (6.0g), behind R225 (25.5g) and the IPA (4.14g), the IPP (1.38g) that adds the R225 solution of making 50 quality % is as polymerization initiator.
Then, when temperature in the reactor is remained on 40 ℃, with 6 hour to reactor in drip by compound (f on one side
1) (1.02g), the mixed liquor that forms of R225 (1.34g) and IPA (0.22g), Yi Bian carry out polyreaction.After the dropping of this mixed liquor finishes, under this state, carry out 12 hours polyreaction.Then, the reactor content liquid is concentrated, after the R225 dilution, be added drop-wise in the hexane, reclaim the solid constituent that precipitates again and get,, obtain polymkeric substance (F 90 ℃ of vacuum drying 24 hours
4) (4.25g).
Polymkeric substance (F
4) at 25 ℃ of pulverous amorphism polymkeric substance (Tg86 ℃) that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
4) Mn be 2700, Mw is 4900.In addition, polymkeric substance (F
4) for comprising the unit (F of 9 moles of %
1) and the unit (B of 91 moles of %
1) polymkeric substance.
[routine 2-5] polymkeric substance (F
5) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
1) (0.7g), compound (b
1) (4.0g), ethyl acetate (12.3g) and 1, behind the 4-diox (6.19g), the IPP (0.71g) that adds the R225 solution make 50 quality % is as polymerization initiator.Then,, temperature in the reactor is remained on 40 ℃, carry out 18 hours polyreaction the degassing of reducing pressure in the reactor.Then, the reactor content liquid is concentrated, after the R225 dilution, be added drop-wise in the hexane, reclaim the solid constituent that precipitates again and get,, obtain polymkeric substance (F 90 ℃ of vacuum drying 24 hours
5) (3.51g).
Polymkeric substance (F
5) at 25 ℃ of pulverous amorphism polymkeric substance that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
5) Mn be 3200, Mw is 6700.In addition, polymkeric substance (F
5) for comprising the unit (F of 10 moles of %
1) and the unit (B of 90 moles of %
1) polymkeric substance.
[routine 2-6] polymkeric substance (F
6) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
1) (0.25g), compound (b
1) (3.0g), ethyl acetate (8.4g) and 1, behind the 4-diox (4.49g), add PFBPO (0.49g) as polymerization initiator.Then,, temperature in the reactor is remained on 40 ℃, carry out 18 hours polyreaction the degassing of reducing pressure in the reactor.Then, the reactor content liquid is concentrated, after the R225 dilution, be added drop-wise in the hexane, reclaim the solid constituent that precipitates again and get,, obtain polymkeric substance (F 90 ℃ of vacuum drying 24 hours
6) (1.98g).
Polymkeric substance (F
6) at 25 ℃ of pulverous amorphism polymkeric substance that are white in color, dissolve in acetone, THF, ethyl acetate, methyl alcohol, R225 respectively.Polymkeric substance (F
6) Mn be 3200, Mw is 6500.In addition, polymkeric substance (F
6) for comprising the unit (F of 7 moles of %
1) and the unit (B of 93 moles of %
1) polymkeric substance.
The evaluation Example (its 1) of [example 3] resist-protecting membrane for immersion lithography polymkeric substance
[routine 3-1] water repellency evaluation Example
Spin coating makes 5 parts of polymkeric substance (F on silicon substrate
1) be dissolved in 95 parts of 2-methyl isophthalic acid-propyl alcohol and resin solution, after the coating with silicon substrate 130 ℃ of heat treated of carrying out 90 seconds, obtain being formed with by polymkeric substance (F
1) silicon substrate of the film (thickness 130nm) that forms.Measure the water repellency (static contact angle, roll angle and receding angle, unit all degree of being (°) of this film, down with).Also have, make roll angle, make receding angle (down together) by the receding contact angle note that the landing method records by the roll angle note that the landing method records.
In addition, except using polymkeric substance (F
2)～(F
6) replacement polymkeric substance (F
1) in addition, similarly measure.The result gathers and is shown in table 1.
[table 1]
| Film forms material | Static contact angle | Roll angle | Receding angle |
| Polymkeric substance (F 1) | 94 | 13 | 82 |
| Polymkeric substance (F 2) | 81 | 21 | 67 |
| Polymkeric substance (F 3) | 89 | 17 | 72 |
| Polymkeric substance (F 4) | 81 | 18 | 68 |
| Polymkeric substance (F 5) | 90 | 18 | 76 |
| Polymkeric substance (F 6) | 82 | 21 | 70 |
By above result also as can be known, polymkeric substance (F
1)～(F
6) because of the big water repellency of contact angle is good, big dynamically water repellency is good especially for little and receding angle because of roll angle.Therefore, use under the situation of resist-protecting membrane for immersion lithography polymkeric substance of the present invention, therefore liquid medium (water etc.) and the projecting lens servo-actuated well of moving on resist-protecting membrane realize immersion lithography process efficiently.
[routine 3-2] developing powder evaluation Example
After being spun on the resin solution that obtains among the routine 3-1 on the quartz crystal unit,, on quartz crystal unit, form by polymkeric substance (F 130 ℃ of heat treated of carrying out 90 seconds
1) film (thickness 130nm) that forms.Then, this quartz crystal unit be impregnated in the aqueous solution of the tetramethylammonium hydroxide (following note is made TMAH) that contains 2.38 quality %, use the little balance of quartz crystal unit (QCM) method, measure film in the TMAH aqueous solution of this film and reduce speed (unit: nm/s) as the developing powder (unit: nm/s) of this film.In addition, measure polymkeric substance (F too
2)～(F
6) developing powder.The result gathers and is shown in table 2.
[table 2]
| Film forms material | Developing powder |
| Polymkeric substance (F 1) | 133 |
| Polymkeric substance (F 2) | 42 |
| Polymkeric substance (F 3) | 368 |
| Polymkeric substance (F 4) | 92 |
| Polymkeric substance (F 5) | 210 |
| Polymkeric substance (F 6) | 191 |
By above result also as can be known, polymkeric substance (F
1)～(F
6) owing to be dissolved in aqueous slkali easily, therefore can easily remove by aqueous slkali.Therefore; use under the situation of resist-protecting membrane for immersion lithography polymkeric substance of the present invention; can therefore realize immersion lithography process efficiently by the disposable sensitization part of removing resist-protecting membrane and photonasty resist of aqueous slkali after the liquid immersion lithography operation.
The formation example of [routine 3-3] corrosion-resisting pattern
Make 5 parts of polymkeric substance (F
1) be dissolved in 95 parts of 2-methyl isophthalic acid-propyl alcohol, make resin solution.Carrying out (Sumitomo Chemical Company Ltd (Sumitomo Chemical society) system of spin-coating erosion resistant agent composition on the surface-treated silicon substrate by organic anti-reflective film (BARC), trade name PAR715), carry out heat treated again, then obtain being formed with the silicon wafer of resist film (thickness 150nm).Then, the described resin solution of resist film surface spin coating at silicon wafer carries out heat treated again, then obtains being formed with by polymkeric substance (F
1) silicon wafer of the resist-protecting membrane (thickness 30nm) that forms.
Use two beam interference exposure devices (optical source wavelength 193nm), carry out the immersion exposure operation (immersing medium: ultrapure water) of the 90nmL/S of described silicon wafer.After the immersion exposure operation, carry out successively at 130 ℃ with 60 seconds operation (heating process) of silicon wafer heating, and 23 ℃ of operations (developing procedure) of silicon wafer being flooded 60 seconds in the aqueous solution of the TMAH that contains 2.38 quality %.
Can confirm that the silicon substrate surface behind developing procedure is formed with good corrosion-resisting pattern by the SEM image.In addition, except using polymkeric substance (F
2)～(F
6) replacement polymkeric substance (F
1) similarly carry out in addition under the situation of immersion exposure test, also can confirm to be formed with good corrosion-resisting pattern by the SEM image on the silicon substrate surface.
The Production Example (its 2) of [example 4] resist-protecting membrane for immersion lithography polymkeric substance
[routine 4-1] polymkeric substance (F
7) Production Example
In reactor (glass, internal volume 30mL), add compound (b
1) (2.0g), compound (f
3) (0.19g), R225 (8.3g) and IPA (0.29g).Then, the R225 solution that adds the IPP as polymerization initiator (0.33g) that contains 50 quality %.After atmosphere in the reactor is replaced into the nitrogen and the degassing, when stirring in the reactor, 40 ℃ of polyreactions of carrying out 18 hours.
After the polymerization, drips of solution in the reactor is added in the hexane, reclaims the agglutinator of gained,, obtain 25 ℃ of pulverous polymkeric substance (F that are white in color 100 ℃ of vacuum drying 24 hours
7) (2.03g).
Polymkeric substance (F
7) Mn be 6700, Mw is 12800, Tg is 100 ℃.Polymkeric substance (F
7) confirm to comprise the unit (B of 94 moles of %
1) and the unit (F of 6 moles of %
3).In addition, polymkeric substance (F
7) dissolve in acetone, THF, ethyl acetate, methyl alcohol and R225 respectively.
[routine 4-2] polymkeric substance (F
8) Production Example
In reactor (glass, internal volume 30mL), add compound (b
1) (1.0g), compound (f
3) (0.13g), R225 (4.3g) and IPA (0.11g).Then, the R225 solution that adds the IPP as polymerization initiator (0.17g) that contains 50 quality %.After atmosphere in the reactor is replaced into the nitrogen and the degassing, when stirring in the reactor, 40 ℃ of polyreactions of carrying out 18 hours.
After the polymerization, drips of solution in the reactor is added in the hexane, reclaims the agglutinator of gained,, obtain 25 ℃ of pulverous polymkeric substance (F that are white in color 100 ℃ of vacuum drying 24 hours
8) (0.9g).
Polymkeric substance (F
8) Mn be 7900, Mw is 14200, Tg is 106 ℃.Polymkeric substance (F
8) confirm to comprise the unit (B of 92 moles of %
1) and the unit (F of 8 moles of %
3).In addition, polymkeric substance (F
8) dissolve in THF, ethyl acetate, methyl alcohol and R225 respectively.
[routine 4-3] polymkeric substance (F
9) Production Example
In reactor (glass, internal volume 30mL), add compound (b
1) (2.0g), compound (f
4) (0.26g), R225 (9.9g) and IPA (0.21g).Then, the R225 solution that adds the IPP as polymerization initiator (0.38g) that contains 50 quality %.After atmosphere in the reactor is replaced into the nitrogen and the degassing, when stirring in the reactor, 40 ℃ of polyreactions of carrying out 18 hours.
After the polymerization, drips of solution in the reactor is added in the hexane, reclaims the agglutinator of gained,, obtain 25 ℃ of pulverous polymkeric substance (F that are white in color 100 ℃ of vacuum drying 24 hours
9) (1.99g).
Polymkeric substance (F
9) Mn be 7200, Mw is 13000, Tg is 105 ℃.Polymkeric substance (F
9) confirm to comprise the unit (B of 94 moles of %
1) and the unit (F of 6 moles of %
4).In addition, polymkeric substance (F9
8) dissolve in THF, ethyl acetate, methyl alcohol and R225 respectively.
The evaluation Example (its 1) of [example 5] resist-protecting membrane for immersion lithography polymkeric substance
[routine 5-1] water repellency evaluation Example
To make polymkeric substance (F
7) be dissolved in 2-methyl isophthalic acid-propyl alcohol and solution filter by filtrator, obtain containing the polymkeric substance (F of 5 quality %
7) resin solution.
Described resin solution is spun on the silicon substrate that the surface is formed with antireflection film, carries out heat treated, on silicon substrate, form polymkeric substance (F
7) resin film.Then, measure static contact angle, roll angle, the receding angle of this resin film respectively to water.
Except using polymkeric substance (F
8) or (F
9) replacement polymkeric substance (F
7) in addition, similarly measure.The result gathers and is shown in table 3.
[table 3]
| Film forms material | Static contact angle | Roll angle | Receding angle |
| Polymkeric substance (F 7) | 90 | 19 | 74 |
| Polymkeric substance (F 8) | 94 | 17 | 85 |
| Polymkeric substance (F 9) | 99 | 20 | 84 |
[routine 5-2] developing powder evaluation Example
After being spun on the resin solution that obtains among the routine 5-1 on the quartz crystal unit, carry out heat treated, on quartz crystal unit, form polymkeric substance (F
7) resin film.Use that little balancing method measures impregnated in this quartz crystal unit in the tetramethylammonium hydroxide aqueous solution time the film of this resin film reduce speed and be 450nm/s.
The formation example of [routine 5-3] corrosion-resisting pattern
With photonasty resist composition (Sumitomo Chemical Company Ltd (Sumitomo Chemical society) system, trade name PAR715) is spun on the silicon substrate that is formed with antireflection film, carry out heat treated, obtain being formed with the substrate of the resist film that forms by described photonasty resist composition.Then, the resin solution at described resist film surface spin coating example 5-1 carries out heat treated, obtains forming by polymkeric substance (F on described resist film surface
7) the resist-protecting membrane layer that forms.
Then, use, carry out the immersion exposure test (immersion liquid: ultrapure water, developer solution: tetramethylammonium hydroxide aqueous solution) of the 90nmL/S of silicon substrate with the two beam interference exposure devices of ArF laser (wavelength 193nm) as light source.Consequently, can confirm that the resist film on silicon substrate is formed with good corrosion-resisting pattern by the SEM image.
By above result also as can be known, if use resist-protecting membrane for immersion lithography polymkeric substance of the present invention, then can form alkali solubility and water repellency well, the dynamic good resist-protecting membrane of water repellency particularly.Therefore, in immersion lithography process, the water capacity is changed places and the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.
The Production Example (its 1) of [example 6] resist-protecting membrane for immersion lithography composition
Polymkeric substance (B
1) use by unit (B
1) polymkeric substance of the Mw11000 that forms, polymkeric substance (B
2) use by unit (B
1) polymkeric substance of the Mw6000 that forms, polymkeric substance (B
3) use by unit (B
2) polymkeric substance (down with) of the Mw5000 that forms.
[routine 6-1] polymkeric substance (F
10) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
1) (2.5g) and CF
3(CF
2)
5H (5.25g).Then, add the R225 solution of the IPP (1.17g) that contains 50 quality % as polymerization initiator.After carrying out the freezing degassing in the reactor, 40 ℃ of polyreactions of carrying out 18 hours.After the polyreaction, drips of solution in the reactor is added in the methyl alcohol, reclaim aggegation and solid, this solid 90 ℃ of vacuum drying 24 hours, is obtained polymkeric substance (F
10) (2.05g).Polymkeric substance (F
10) be at 25 ℃ of pulverous amorphism polymkeric substance that are white in color.Polymkeric substance (F
10) Mn be 2900, Mw is 6300.
[routine 6-2] polymkeric substance (F
11) Production Example
In voltage-resistant reactor (internal volume 30mL, glass), add compound (f
2) (0.8g) and CF
3(CF
2)
5H (1.06g).Then, add the R225 solution of the IPP (0.28g) that contains 50 quality % as polymerization initiator.After carrying out the freezing degassing in the reactor, 40 ℃ of polyreactions of carrying out 18 hours.After the polyreaction, drips of solution in the reactor is added in the methyl alcohol, reclaim aggegation and solid, this solid 90 ℃ of vacuum drying 24 hours, is obtained polymkeric substance (F
11) (0.62g).Polymkeric substance (F
11) be at 25 ℃ of pulverous amorphism polymkeric substance that are white in color.Polymkeric substance (F
11) Mn be 7000, Mw is 20000.
The Production Example of [routine 6-3] composition (1)
Make polymkeric substance (F
10) be dissolved in the hexafluoro m-xylene, obtain containing the polymkeric substance (F of 0.36 quality %
10) solution (F
10).Make polymkeric substance (B
1) be dissolved in the solution of 2-methyl isophthalic acid-propyl alcohol of the hexafluoro m-xylene that contains 99.5 quality % and 0.5 quality %, obtain containing the polymkeric substance (B of 5.8 quality %
1) solution (B
1).With 1.149g solution (F
10) and 1.827g solution (B
1) mix, obtain transparent and uniform solution.The filtrator (PTFE system) of this solution by aperture 0.2 μ m filtered, obtain with respect to polymkeric substance (F
10) and polymkeric substance (B
1) total amount comprise the polymkeric substance (F of 3.9 quality %
10) composition (1).
The Production Example of [routine 6-4] composition (2)
Among the example 6-3, except making polymkeric substance (B
1) be dissolved in beyond the solution of 2-methyl isophthalic acid-propyl alcohol of the hexafluoro m-xylene that contains 98.9 quality % and 1.1 quality %, similarly operate, obtain with respect to polymkeric substance (B
1) total amount comprise the polymkeric substance (F of 3.5 quality %
10) composition (2).
The Production Example of [routine 6-5] composition (3)
Make polymkeric substance (F
11) be dissolved in the hexafluoro m-xylene, obtain containing the polymkeric substance (F of 0.35 quality %
11) solution (F
11).Make polymkeric substance (B
2) be dissolved in the solution of 2-methyl isophthalic acid-propyl alcohol of the hexafluoro m-xylene that contains 99.3 quality % and 0.7 quality %, obtain containing the polymkeric substance (B of 5.5 quality %
2) solution (B
2).With 1.146g solution (F
11) and 1.824g solution (B
2) mix, obtain transparent and uniform solution.The filtrator (PTFE system) of this solution by aperture 0.2 μ m filtered, obtain with respect to polymkeric substance (F
11) and polymkeric substance (B
2) total amount comprise the polymkeric substance (F of 4.0 quality %
11) composition (3).
The Production Example of [routine 6-6] composition (4)
Similarly operate with routine 6-5, obtain with respect to polymkeric substance (B
2) total amount comprise the polymkeric substance (F of 8.0 quality %
11) composition (4).
The Production Example of [routine 6-7] composition (5)
Except using polymkeric substance (B
1) replace the polymkeric substance (B among the routine 6-5
2) similarly operate in addition, obtain with respect to polymkeric substance (B
1) total amount comprise the polymkeric substance (F of 4.0 quality %
11) composition (5).
The Production Example of [routine 6-8] composition (6)
Except using polymkeric substance (B
1) replace the polymkeric substance (B among the routine 6-5
2) similarly operate in addition, obtain with respect to polymkeric substance (B
1) total amount comprise the polymkeric substance (F of 8.0 quality %
11) composition (6).
The Production Example of [routine 6-9] composition (7)
Make polymkeric substance (F
10) be dissolved in the hexafluoro m-xylene, obtain containing the polymkeric substance (F of 0.69 quality %
10) solution (F
12).Make polymkeric substance (B
3) be dissolved in the solution of the ten fluoro-1-hexanols of the hexafluoro m-xylene that contains 37.5 quality % and 62.5 quality %, obtain containing the polymkeric substance (B of 4.2 quality %
3) solution (B
3).With 0.577g solution (F
12) and 2.394g solution (B
3) mix, obtain transparent and uniform solution.The filtrator (PTFE system) of this solution by aperture 0.2 μ m filtered, obtain with respect to polymkeric substance (F
10) and polymkeric substance (B
3) total amount comprise the polymkeric substance (F of 4.0 quality %
10) composition (7).
The Production Example of [routine 6-10] composition (C)
Solution dissolving at 2-methyl isophthalic acid-propyl alcohol of the hexafluoro m-xylene of 99.2 quality % and 0.8 quality % makes CH
2=C (CH
3) CH
2CH
2(CF
2)
6The F homopolymerization and the polymkeric substance (hereinafter referred to as polymkeric substance (C)) of Mw100000, obtain containing the solution of the polymkeric substance (C) of 0.35 quality %.With 1.152g solution (C) and 1.817g solution (B
1) mix, obtain transparent and uniform solution.The filtrator (PTFE system) of this solution by aperture 0.2 μ m filtered, obtain with respect to polymkeric substance (C) and polymkeric substance (B
1) total amount comprise the composition (C) of the polymkeric substance (C) of 4.0 quality %.
The evaluation Example (its 1) of [example 7] resist-protecting membrane for immersion lithography composition
[routine 7-1] water repellency evaluation Example
Be formed with spin coating composition (1) on the silicon substrate of antireflection film (ROHM AND HAAS electronic material company (ROHM AND HAAS Electronic Materials society) system, trade name AR26) on the surface.Then, 100 ℃ of heat treated of carrying out 90 seconds, again 130 ℃ of heat treated of carrying out 120 seconds, formation contains polymkeric substance (F on silicon substrate with silicon substrate
10) and polymkeric substance (B
1) resin film (thickness 150nm).Then, measure static contact angle, roll angle, the receding angle of this resin film respectively to water.
Except using composition (2)～composition (7) and composition (C) replacement composition (1) respectively, similarly measure.In addition, static contact angle, roll angle and the receding angle of the resin film that forms by polymkeric substance (B1) or polymkeric substance (B3) have only also been measured.The result gathers and is shown in table 4.
[table 4]
| Form the material of resin film | Static contact angle | Roll angle | Receding angle |
| Composition (1) | 109 | 11 | 98 |
| Composition (2) | 108 | 11 | 100 |
| Composition (3) | 96 | 16 | 86 |
| Composition (4) | 100 | 14 | 91 |
| Composition (5) | 98 | 16 | 83 |
| Composition (6) | 100 | 13 | 90 |
| Composition (7) | 97 | 18 | 83 |
| Composition (C) | 100 | 29 | 75 |
| Polymkeric substance (B 1) | 70 | 19 | 61 |
| Polymkeric substance (B 3) | 64 | 25 | 50 |
By above result also as can be known, compare with the resin film that is only formed by polymkeric substance (B) by containing the resin film that the composition of polymkeric substance (F) with polymkeric substance (B) form, water repellency is better.In addition, described resin film is compared with the resin film of the polymkeric substance with linear fluoro-alkyl (C) with containing polymkeric substance (B), and roll angle is little and receding angle is big, so dynamically water repellency is good.Therefore, the resist-protecting membrane for immersion lithography composition of the application of the invention, therefore liquid medium (water etc.) and the projecting lens servo-actuated well of moving on resist-protecting membrane can stably implement immersion lithography process.
[routine 7-2] developing powder evaluation Example
Operate equally with routine 7-1, coating composition on the silicon substrate (1), formation contains polymkeric substance (F on silicon substrate
10) and polymkeric substance (B
1) resin film (thickness 158nm).This silicon substrate be impregnated in the aqueous solution of the tetramethylammonium hydroxide that contains 2.38 quality %, use the little balance of quartz crystal unit (QCM) method, measure the dissolution velocity (following note make developing powder) of resin film for this aqueous solution.
Except using composition (3) or composition (4) replacement composition (1) respectively, similarly on silicon substrate, form resin film, measure the developing powder (nm/s) of each resin film for described aqueous solution.The result gathers and is shown in table 5.
[table 5]
| Form the material of resin film | Developing powder |
| Composition (1) | 735 |
| Composition (3) | 878 |
| Composition (4) | 878 |
By above result also as can be known, the resin film that is formed by the composition that contains polymkeric substance (F) and polymkeric substance (B) can easily be removed by aqueous slkali.Therefore; use under the situation of resist-protecting membrane for immersion lithography composition of the present invention; can therefore can implement immersion lithography process efficiently by the disposable sensitization part of removing resist-protecting membrane and photonasty resist of aqueous slkali after the liquid immersion lithography operation.
The formation example of [routine 7-3] corrosion-resisting pattern
Be formed with (Sumitomo Chemical Company Ltd (Sumitomo Chemical society) system of spin coating photonasty resist composition on the silicon substrate of antireflection film, trade name PAR715), carry out heat treated, obtain being formed with the substrate of the resist film that forms by described photonasty resist composition.Then,, carry out heat treated, form by polymkeric substance (F on described resist film surface at described resist film surface spin coating composition (1)
10) and polymkeric substance (B
1) the resist-protecting membrane layer that forms.
Then, use, carry out the immersion exposure test (immersion liquid: ultrapure water, developer solution: tetramethylammonium hydroxide aqueous solution) of the 90nmL/S of silicon substrate with the two beam interference exposure devices of ArF laser (wavelength 193nm) as light source.Consequently, can confirm that the resist film on silicon substrate is formed with good corrosion-resisting pattern by the SEM image.
The Production Example (its 2) of [example 8] resist-protecting membrane for immersion lithography composition
The Production Example of [routine 8-1] composition (8)
To make compound (f
3) homopolymerization and polymkeric substance (F
12) (Mw12000) being dissolved in 1, two (trifluoromethyl) benzene of 3-are made the polymkeric substance (F that contains 0.36 quality %
12) resin solution (being called solution (11)).
Make polymkeric substance (B
1) be dissolved in by 1, the solvent that two (trifluoromethyl) benzene (95.1 quality %) of 3-and 2-methyl isophthalic acid-propyl alcohol (4.9 quality %) form is made the polymkeric substance (B that contains 5.4 quality %
1) resin solution (being called solution (21)).
With solution (11) (1.117g) and solution (21) (1.855g) mix, obtain with respect to polymkeric substance (B
1) gross mass comprise the polymkeric substance (F of 4 quality %
12) composition (8).
The Production Example of [routine 8-2] composition (9)
With polymkeric substance (F
12) being dissolved in 1, two (trifluoromethyl) benzene of 3-are made the polymkeric substance (B that contains 0.18 quality %
1) resin solution (being called solution (12)).
Make polymkeric substance (B
1) be dissolved in by 1, the solvent that 2-methyl isophthalic acid-propyl alcohol (3.4 quality %) of two (trifluoromethyl) benzene (96.6 quality %) of 3-and 3.4 quality % forms is made the polymkeric substance (B that contains 3.9 quality %
1) resin solution (being called solution (22)).
With solution (12) (1.093g) and solution (22) (2.580g) mix, obtain with respect to polymkeric substance (B
1) gross mass comprise the polymkeric substance (F of 2 quality %
12) composition (9).
The evaluation Example (its 2) of [example 9] resist-protecting membrane for immersion lithography composition
[routine 9-1] water repellency evaluation Example
Composition (8) is spin-coated on the silicon substrate that the surface is formed with antireflection film, carries out heat treated (100 ℃, 60 seconds), on silicon substrate, form and contain polymkeric substance (B
1) and polymkeric substance (F
12) resin film.Then, measure static contact angle, roll angle, the receding angle of this resin film respectively to water.
Except using composition (9) replacement composition (8), similarly measure.The result gathers and is shown in table 6.
[table 6]
| Form the material of resin film | Static contact angle | Roll angle | Receding angle |
| Composition (8) | 103 | 15 | 93 |
| Composition (9) | 97 | 18 | 84 |
[routine 9-2] developing powder evaluation Example
Spin coating composition (8) carries out heat treated on quartz crystal unit, forms to contain polymkeric substance (B on quartz crystal unit
1) and polymkeric substance (F
12) resin film.Use that little balancing method measures impregnated in this quartz crystal unit in the tetramethylammonium hydroxide aqueous solution time the film of this resin film reduce speed more than 200nm/s.
The formation example of [routine 9-3] corrosion-resisting pattern
Be formed with (Sumitomo Chemical Company Ltd (Sumitomo Chemical society) system of spin coating photonasty resist composition on the silicon substrate of antireflection film, trade name PAR715), carry out heat treated, obtain being formed with the substrate of the resist film that forms by described photonasty resist composition.Then,, carry out heat treated, form by polymkeric substance (B on described resist film surface at described resist film surface spin coating composition (8)
1) and polymkeric substance (F
12) the resist-protecting membrane layer that forms.
Then, use, carry out the immersion exposure test (immersion liquid: ultrapure water, developer solution: tetramethylammonium hydroxide aqueous solution) of the 90nmL/S of silicon substrate with the two beam interference exposure devices of ArF laser (wavelength 193nm) as light source.Consequently, can confirm that the resist film on silicon substrate is formed with good pattern by the SEM image.
By above result also as can be known, if use resist-protecting membrane for immersion lithography polymkeric substance of the present invention, then can form alkali solubility and water repellency well, the dynamic good resist-protecting membrane of water repellency particularly.Therefore, in immersion lithography process, the water capacity is changed places and the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.
The Production Example (its 3) of [example 10] resist-protecting membrane for immersion lithography composition
The Production Example of [routine 10-1] composition (10)
Make compound (f
3) and compound (b
1) copolymerization, obtain comprising the unit (F of 8 moles of % with respect to all repetitives
3) and the unit (B of 92 moles of %
1) the polymkeric substance (F of Mw14000
13).Make polymkeric substance (F
13) be dissolved in 4-methyl-2-amylalcohol, obtain containing the polymkeric substance (F of 6.17 quality %
13) solution.With this solution (0.972g) with contain the polymkeric substance (B of 4.2 quality %
1) solution (1.428g) mix, obtain with respect to polymkeric substance (B
1) gross mass comprise the polymkeric substance (F of 100 quality %
13) composition (10).Composition (10) is transparent and uniform solution.
The Production Example of [routine 10-2] composition (11)
Make compound (f
3) and compound (b
1) copolymerization, obtain comprising the unit (F of 10 moles of % with respect to all repetitives
3) and the unit (B of 90 moles of %
1) the polymkeric substance (F of Mw14000
14).Make polymkeric substance (F
14) be dissolved in 4-methyl-2-amylalcohol, obtain containing the polymkeric substance (F of 3.8 quality %
14) solution.With this solution (1.129g) with contain the polymkeric substance (B of 5.8 quality %
1) solution (1.728g) mix, obtain with respect to polymkeric substance (B
1) gross mass comprise the polymkeric substance (F of 43 quality %
14) composition (11).Composition (11) is transparent and uniform solution.
The evaluation Example (its 3) of [example 11] resist-protecting membrane for immersion lithography composition
[routine 11-1] water repellency evaluation Example
Composition (10) is spin-coated on the silicon substrate that the surface is formed with antireflection film, carries out heat treated (100 ℃, 60 seconds), on silicon substrate, form and contain polymkeric substance (B
1) and polymkeric substance (F
13) resin film.Then, measure static contact angle, roll angle, the receding angle of this resin film respectively to water.
Except using composition (11) replacement composition (10), similarly measure.The result gathers and is shown in table 7.
[table 7]
| Form the material of resin film | Static contact angle | Roll angle | Receding angle |
| Composition (10) | 91 | 20 | 74 |
| Composition (11) | 93 | 20 | 79 |
[routine 11-2] developing powder evaluation Example
Operate equally with routine 7-1, coating composition on silicon substrate (10), formation contains polymkeric substance (F on silicon substrate
13) and polymkeric substance (B
1) resin film.This silicon substrate be impregnated in the aqueous solution of the tetramethylammonium hydroxide that contains 2.38 quality %, use the little balancing method of quartz crystal unit, measure the dissolution velocity (unit: nm/s) (following note make developing powder) of resin film for this aqueous solution.In addition, use composition (11) to replace composition (10), similarly measure developing powder.The result gathers and is shown in table 8.
[table 8]
| Form the material of resin film | Developing powder |
| Composition (10) | 280 |
| Composition (11) | 330 |
The formation example of [routine 11-3] corrosion-resisting pattern
Be formed with (Sumitomo Chemical Company Ltd (Sumitomo Chemical society) system of spin coating photonasty resist composition on the silicon substrate of antireflection film, trade name PAR715), carry out heat treated, obtain being formed with the substrate of the resist film that forms by described photonasty resist composition.Then,, carry out heat treated, form by polymkeric substance (B on described resist film surface at described resist film surface spin coating composition (10)
1) and polymkeric substance (F
13) the resist-protecting membrane layer that forms.
Then, use, carry out the immersion exposure test (immersion liquid: ultrapure water, developer solution: tetramethylammonium hydroxide aqueous solution) of the 90nmL/S of silicon substrate with the two beam interference exposure devices of ArF laser (wavelength 193nm) as light source.Consequently, can confirm that the resist film on silicon substrate is formed with good pattern by the SEM image.
By above result also as can be known, if use resist-protecting membrane for immersion lithography polymkeric substance of the present invention, then can form alkali solubility and water repellency well, the dynamic good resist-protecting membrane of water repellency particularly.Therefore, in immersion lithography process, the water capacity is changed places and the projecting lens servo-actuated of high-speed mobile on resist-protecting membrane.
The possibility of utilizing on the industry
If employing the present invention; then can provide the resist-protecting membrane characteristic (suppress the photonasty resist that the intrusion of water causes swelling, suppress the stripping of photonasty resist composition in the liquid medium etc.) and dynamically water repellency is good especially, the difficult resist-protecting membrane for immersion lithography material that is slided well by water intrusion. The resist-protecting membrane for immersion lithography material of the application of the invention can be realized and can implement with the stable high speed of the immersion lithography process of the pattern image of high-resolution transfer mask.
In addition, quote the announcement of all the elements of Japanese patent application 2006-144121 number of filing an application on May 24th, Japanese patent application 2006-116735 number 1 of filing an application on April 20th, 2006 and Japanese patent application 2006-207392 number instructions, claims and the summary of filing an application on July 31st, 2006 here as instructions of the present invention.
Claims (21)
1. alkali-soluble resist-protecting membrane for immersion lithography material is characterized in that, comprises polymkeric substance (F), and described polymkeric substance (F) comprises the repetitive (F that the polymerization by the polymerizable compound (fm) with fluorine-containing bridged ring structure forms
U).
2. resist-protecting membrane for immersion lithography material as claimed in claim 1 is characterized in that, polymerizable compound (fm) is the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
Fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
3. the resist-protecting membrane for immersion lithography polymkeric substance is characterized in that, it is to comprise repetitive (F
U) and repetitive (B
U) polymkeric substance (FB), described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form described repetitive (B
U) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and form.
4. resist-protecting membrane for immersion lithography polymkeric substance as claimed in claim 3 is characterized in that, polymerizable compound (f
m) be the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
Fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
5. as claim 3 or 4 described resist-protecting membrane for immersion lithography polymkeric substance, it is characterized in that polymerizable compound (b
m) be to have (CF with formula-C
3) (OH)-, formula-C (CF
3)
2(OH) or the polymerizable compound of the group represented of formula-C (O) OH.
6. as each the described resist-protecting membrane for immersion lithography polymkeric substance in the claim 3～5, it is characterized in that polymerizable compound (b
m) be the compound (b) that is selected from the compound of following formula (b1), following formula (b2), following formula (b3) and following formula (b4) expression;
CF
2＝CF—Q
B1-CH＝CH
2(b1)
CH
2＝CR
B2-C(O)O-Q
B2(-C(CF
3)
2OH)
b(b2)
CH
2＝CH—Q
B3(-C(CF
3)
2OH)
b(b3)
Mark in the formula is represented following implication,
QB1: with formula-CF
2C (CF
3) (OH) (CH
2)
m-expression group, with formula-CH
2CH ((CH
2)
nC (CF
3)
2(OH)) (CH
2)
m-expression group or with formula-CH
2CH (C (O) OH) (CH
2)
mThe group of-expression,
M and n: independently be respectively 0,1 or 2,
R
B2: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
Q
B2And Q
B2: independent respectively is (b+1) valency alkyl of carbon number 1～20,
B:1 or 2,
Q
B4: the divalent alkyl of singly-bound or carbon number 1～10;
Q
B2, Q
B3Or Q
B4In carbon atom can be combined with fluorine atom.
7. as each the described resist-protecting membrane for immersion lithography polymkeric substance in the claim 3～6, it is characterized in that polymkeric substance (FB) is the repetitive (F that comprises 1～70 mole of % with respect to all repetitives
U), the above repetitive (B of 10 moles of %
U) polymkeric substance.
8. as each the described resist-protecting membrane for immersion lithography polymkeric substance in the claim 3～7, it is characterized in that polymkeric substance (FB) is the repetitive (F that comprises 3～15 moles of % with respect to all repetitives
U), the repetitive (B of 85～97 moles of %
U) polymkeric substance.
9. resist-protecting membrane for immersion lithography forms composition, it is characterized in that, comprises each described resist-protecting membrane for immersion lithography polymkeric substance and organic solvent in the claim 3～8.
10. the formation method of corrosion-resisting pattern, it is the formation method that adopts the corrosion-resisting pattern of immersion lithography process, it is characterized in that, carries out following operation successively, forming corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate, the operation of formation photonasty resist film on substrate; The described resist-protecting membrane for immersion lithography of claim 9 is formed composition coat the photonasty resist film, on the photonasty resist film, form the operation of resist-protecting membrane layer; The liquid immersion lithography operation; And developing procedure.
11. alkali-soluble resist-protecting membrane for immersion lithography composition is characterized in that, comprises polymkeric substance (F) and polymkeric substance (B), described polymkeric substance (F) comprises by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and the repetitive (F that forms
U), described polymkeric substance (B) comprises by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and the repetitive (B that forms
U).
12. resist-protecting membrane for immersion lithography composition as claimed in claim 11 is characterized in that, polymerizable compound (f
m) be the compound (f) that is selected from the compound of following formula (f1), following formula (f2), following formula (f3) and following formula (f4) expression;
Mark in the formula is represented following implication,
R
F: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
X
F: fluorine atom, hydroxyl or methylol;
Fluorine atom in the compound (f) can be replaced by the perfluoro alkoxy of the perfluoroalkyl of carbon number 1～6 or carbon number 1～6.
13., it is characterized in that polymerizable compound (b as claim 11 or 12 described resist-protecting membrane for immersion lithography compositions
m) be to have (CF with formula-C
3) (OH)-, formula-C (CF
3)
2(OH) or the polymerizable compound of the group represented of formula-C (O) OH.
14. each the described resist-protecting membrane for immersion lithography composition as in the claim 11～13 is characterized in that polymerizable compound (b
m) be the compound (b) that is selected from the compound of following formula (b1), following formula (b2), following formula (b3) and following formula (b4) expression;
CF
2＝CF—Q
B1-CH＝CH
2 (b1)
CH
2＝CR
B2-C(O)O-Q
B2(-C(CF
3)
2OH)
b (b2)
CH
2＝CH-Q
B3(-C(CF
3)
2OH)
b (b3)
Mark in the formula is represented following implication,
QB1: with formula-CF
2C (CF
3) (OH) (CH
2)
m-expression group, with formula-CH
2CH ((CH
2)
nC (CF
3)
2(OH)) (CH
2)
m-expression group or with formula-CH
2CH (C (O) OH) (CH
2)
mThe group of-expression,
M and n: independently be respectively 0,1 or 2,
R
B2: the alkyl of hydrogen atom, fluorine atom, carbon number 1～3 or the fluoro-alkyl of carbon number 1～3,
Q
B2And Q
B3: independent respectively is (b+1) valency alkyl of carbon number 1～20,
B:1 or 2,
Q
B4: the divalent alkyl of singly-bound or carbon number 1～10;
Q
B2, Q
B3Or Q
B4In carbon atom can be combined with fluorine atom.
15. each the described resist-protecting membrane for immersion lithography composition as in the claim 11～14 is characterized in that polymkeric substance (F) is only by repetitive (F
U) polymkeric substance that forms, described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form.
16. each the described resist-protecting membrane for immersion lithography composition as in the claim 11～14 is characterized in that polymkeric substance (F) is to comprise repetitive (F
U) and repetitive (B
U) polymkeric substance, comprise the repetitive (F of 1～25 mole of % with respect to all repetitives
U), the repetitive (B of 75～99 moles of %
U), described repetitive (F
U) by having the polymerizable compound (f of fluorine-containing bridged ring structure
m) polymerization and form described repetitive (B
U) by having the polymerizable compound (b of hydroxyl, carboxyl, sulfonic group, sulfoamido, amino or phosphate
m) polymerization and form.
17. each the described resist-protecting membrane for immersion lithography composition as in the claim 11～16 is characterized in that, with respect to polymkeric substance (B), comprises the polymkeric substance (F) of 0.1～30 quality %.
18. each the described resist-protecting membrane for immersion lithography composition as in the claim 11～16 is characterized in that, with respect to polymkeric substance (B), comprises more than 30 quality % and is less than the polymkeric substance (F) that equals 200 quality %.
19. resist-protecting membrane for immersion lithography forms composition, it is characterized in that, comprises each described resist-protecting membrane for immersion lithography composition and organic solvent in the claim 11～18.
20. the formation method of corrosion-resisting pattern, it is the formation method that adopts the corrosion-resisting pattern of immersion lithography process, it is characterized in that, carries out following operation successively, forming corrosion-resisting pattern on the substrate: coating photonasty anticorrosive additive material on substrate, the operation of formation photonasty resist film on substrate; The described resist-protecting membrane for immersion lithography of claim 19 is formed composition coat the photonasty resist film, on the photonasty resist film, form the operation of resist-protecting membrane layer; The liquid immersion lithography operation; And developing procedure.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP116735/2006 | 2006-04-20 | ||
| JP2006116735 | 2006-04-20 | ||
| JP144121/2006 | 2006-05-24 | ||
| JP207392/2006 | 2006-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101421673A true CN101421673A (en) | 2009-04-29 |
Family
ID=40631492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800132668A Pending CN101421673A (en) | 2006-04-20 | 2007-03-30 | The resist-protecting membrane for immersion lithography material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101421673A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003666A (en) * | 2021-10-22 | 2023-04-25 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
| CN116003665A (en) * | 2021-10-22 | 2023-04-25 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
-
2007
- 2007-03-30 CN CNA2007800132668A patent/CN101421673A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003666A (en) * | 2021-10-22 | 2023-04-25 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
| CN116003665A (en) * | 2021-10-22 | 2023-04-25 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
| CN116003665B (en) * | 2021-10-22 | 2024-03-29 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
| CN116003666B (en) * | 2021-10-22 | 2024-04-26 | 上海芯刻微材料技术有限责任公司 | Polymer and preparation method of 193nm photoetching top coating film containing same |
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