CN1818782A - Dark ultraviolet negative photoresist and filming resin - Google Patents
Dark ultraviolet negative photoresist and filming resin Download PDFInfo
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- CN1818782A CN1818782A CN 200610038787 CN200610038787A CN1818782A CN 1818782 A CN1818782 A CN 1818782A CN 200610038787 CN200610038787 CN 200610038787 CN 200610038787 A CN200610038787 A CN 200610038787A CN 1818782 A CN1818782 A CN 1818782A
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Abstract
A deep ultraviolet positive photo resist and its film forming resin is prepared as forming a new film forming resin by leading acrylic ester coupler containing silicon into normal film forming preparation using PHS as base, co polymerizing said acrylic ester coupler containing silicon with materials in said preparation to obtain a new type of film forming resin; then preparing deep ultraviolet positive photo resist by obtained new type of film forming resin, photo acid, solvent and additives.
Description
Technical field
The present invention relates to a kind of multipolymer film-forming resin that contains silicone couplet (also claiming " film forming agent ") and utilize this film-forming resin formulated to be used for KrF laser (248nm) be deep ultraviolet (DUV) the positivity chemical amplification type photoetching compositions of exposure light source.
Background technology
Photoresist is the key function material that carries out photoetching process in the large scale integrated circuit industry.Wherein film-forming resin is again the important component part of photoresist, and its chemistry and physical property directly influence the result of use of photoresist in large scale integrated circuit industry.
According to the difference of photoresist process, photoresist is divided into positive photoresist and negative photoresist two big classes again.So-called positive photoresist is meant that in photoetching process on the photoresist film, the part of graph exposure is developed the liquid flush away at last, stays unexposed part and forms figure.
What begin to grow up the eighties in last century be that the film-forming resin of principal ingredient and photoresist thereof be widely used in making in the large scale integrated circuit with KrF laser (248nm) with polycarboxylated styrene (PHS) is the photoetching process of deep ultraviolet (DUV) the wave band exposure of exposure light source, and its resolution can reach the 0.25-018 mu m range.Thereafter, through constantly improving, resolution improves constantly, and manufacturability is perfect day by day.But develop rapidly along with large scale integrated circuit industry, the variation of integrated circuit (IC) products and kind, the updating of photoetching process is to the key function material that uses in the photo-etching technological process, particularly the requirement of photoresist is also higher, and kind and performance are also wanted variation, specialized.So far still in constantly improving, develop and improving.
Summary of the invention
The invention provides the positivity chemical amplification type photoresist of deep ultraviolet (DUV) the wave band exposure of a kind of multipolymer film-forming resin that contains silicone couplet and application thereof, its objective is the adhesiveness that will effectively improve existing film forming agent and photoresist and base material silicon chip based on polycarboxylated styrene (PHS), reduce the thickness loss of unexposed area, increase the dissolubility of exposure region in alkaline-based developer, thereby increase the contrast of exposure region and non-exposed area, to obtain better figure.
For achieving the above object, the technical scheme that the present invention contains the multipolymer film-forming resin employing of silicone couplet is: a kind of multipolymer film-forming resin that contains silicone couplet, by comonomer under the condition that radical initiator exists, by carrying out copolymerization and corresponding aftertreatment is prepared from solvent, comonomer comprises:
(1), hydroxyl styrene monomer 40%-90% weight;
Its chemical general formula:
In the formula: R=H, acetyl group or propiono; X=1-2.
For example:
Para hydroxybenzene second is rare;
To acetoxy-styrene;
Between hydroxy benzenes second rare;
Between acetoxy-styrene;
3,4-dihydroxy benzenes ethene;
3,4-diacetoxy styrene;
3,5-dihydroxy benzenes ethene;
3,5-diacetoxy styrene.
(2), acrylate containing silicone class coupling agent 0.5%-20% weight;
Its chemical general formula:
In the formula: n=1-8; R
1=H, CH
3Or CF
3R
2=C
1-C
20Alkyl; R
3=C
1-C
20Alkyl; R
4=OH, C
1-C
20Alkyl or C
1-C
20Alkoxy.
For example:
Methacrylic acid propyl trialkoxy silane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid propyl trialkoxy silane ester (wherein alkoxy contains 1-20 carbon atom);
Methacrylic acid propyl group dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid propyl group dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom);
Methacrylic acid ethyl trialkoxy silane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid ethyl trialkoxy silane ester (wherein alkoxy contains 1-20 carbon atom);
Methacrylic acid ethyl dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid ethyl dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom);
Methacrylic acid methyl trialkoxy silane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid methyl trialkoxysilane ester (wherein alkoxy contains 1-20 carbon atom);
Methacrylic acid methyl dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom);
Acrylic acid methyl dialkoxy silicane ester (wherein alkoxy contains 1-20 carbon atom).
(3), contain acid-sensitive group monomer 5%-60% weight;
Its chemical general formula:
In the formula: R
5=H, CH
3Or CF
3
For example:
Tert-butyl acrylate;
The metering system tert-butyl acrylate;
The acrylic acid tert-pentyl ester;
The methacrylic acid tert-pentyl ester;
Acrylic acid 1-methyl ring pentyl ester;
Methacrylic acid 1-methyl ring pentyl ester;
Acrylic acid 1-methyl cyclohexane ester;
Methacrylic acid 1-methyl cyclohexane ester;
Acrylic acid 1-ethyl ring pentyl ester;
Methacrylic acid 1-ethyl ring pentyl ester;
Acrylic acid 1-ethyl cyclohexyl;
Methacrylic acid 1-ethyl cyclohexyl;
Acrylic acid 2-methyl adamantane alcohol ester;
Methacrylic acid 2-methyl adamantane alcohol ester;
Acrylic acid 2-ethyl diamantane alcohol ester;
Methacrylic acid 2-ethyl diamantane alcohol ester;
Acrylic acid 2-butyrolactone base ester;
Methacrylic acid 2-butyrolactone base ester;
Acrylic acid 2-caprolactone base ester;
Methacrylic acid 2-caprolactone base ester.
Perhaps its chemical general formula:
In the formula:
Or
Rx=CH
3Or C
2H
5
For example:
To tert-butoxy styrene;
To uncle's amyl phenyl ether ethene;
To tert-butyl group carbonic ester styrene;
To the different ethoxybenzene ethene of 1-ethoxy.
The molecular weight of described multipolymer film-forming resin is 4000-100000, and molecular weight distribution is 1.4-2.8.
Related content in the technique scheme is explained as follows:
1, described comonomer also comprises styrene monomer or acrylic ester monomer 1～40%,
Its chemical general formula:
Perhaps
In the formula:
Ry=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
Rz=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
8=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
9=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group.
Styrene monomer is for example:
Styrene;
To t-butyl styrene;
To tert-amyl benzene ethene;
To ethoxybenzene ethene;
3, the 5-dimethoxy styrene;
3,5-diethoxy styrene;
To phenoxy group styrene;
To 2-hydroxy ethoxy styrene.
Acrylic ester monomer is for example:
Isobornyl methacrylate;
Isobornyl acrylate;
The methacrylic acid benzyl ester;
The acrylic acid benzyl ester;
Methacrylic acid biphenyl ester;
Biphenyl acrylate;
The methacrylic acid cholesterol ester;
The acrylic acid cholesterol ester;
Methacrylic acid diamantane alcohol ester;
Acrylic acid diamantane alcohol ester.
2, about polyreaction
(1), above-mentionedly have copolymerization to carry out separately or in their potpourri at all kinds of solvents, these solvents are selected from methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran, toluene, benzene, dimethylbenzene, methylene chloride, chloroform, methenyl choloride, ethylene dichloride, trichloroethanes etc.
(2), these copolymerizations can carry out in the presence of various radical initiators, comprise that azo two isobutyls are fine, azo initiator such as two different heptan of azo are fine, and the radical initiator of various superoxide, as tert-butyl hydroperoxide pivalate, tert-butyl hydroperoxide, benzoic acid hydrogen peroxide, benzoyl peroxides etc., initiator amount are the 0.3%-15% of total monomer weight.
(3), the adding of radical initiator can be adopted dual mode: first kind is after each comonomer is dissolved in solvent, is heated to polymerization temperature earlier, adds initiating agent then and carries out polyreaction.Second kind is after each comonomer is dissolved in solvent, adds earlier initiating agent, and then is warmed to polymerization temperature and carries out polyreaction.Described initiating agent can disposablely add in this dual mode, also can gradation add.The temperature of polyreaction is controlled at 40～150 ° of scopes according to the solvent that uses is different with initiating agent.Polymerization reaction time is also according to be controlled at 4～28 hour different with initiating agent of solvent of using.
3. the aftertreatment of polyreaction:
(1), purification process
After polyreaction was finished, unreacted residual monomer and part organic impurities thereof can be removed after extracting with heptane, hexane, cyclohexane, pentane, sherwood oil, ether equal solvent.
(2), separating solids multipolymer
Multipolymer can be in organic or inorganic solvents such as the potpourri of potpourri, isopropyl alcohol and the water thereof of potpourri, ethanol and the water thereof of pure water, methyl alcohol, first alcohol and water, heptane, hexane, cyclohexane, pentane, sherwood oil, ether precipitate and separate, the yield of vacuum drying rear copolymer is 60%-90%.
(3), the reaction of polymkeric substance
Some multipolymer also can be obtained through suitable chemical reaction by the specific polymkeric substance of forming except can directly being formed by their corresponding monomer copolymerization.Can obtain via polyreaction by monomer para hydroxybenzene ethene as poly(4-hydroxystyrene), also can remove deacetylate and obtain poly(4-hydroxystyrene) through hydrolysis reaction acetoxy-styrene by poly-.Hydrolysis reaction can carry out in the presence of acidic catalyst, also can carry out in the presence of base catalyst.As sulfuric acid, hydrochloric acid, ammonium hydroxide, NaOH, potassium hydroxide, lithium hydroxide, sodium methoxide, caustic alcohols etc. can be as the catalyzer of hydrolysis reaction.
And for example, gather, outside can obtaining by the direct polymerization of monomer whose, also can and obtain by poly(4-hydroxystyrene) and di-tert-butyl dicarbonate (DBDC) reaction to tert-butyl group carbonic ester styrene.Reality is used the sort of method, should decide according to technological requirement and pricing.
For achieving the above object, the technical scheme that photoresist of the present invention adopts is: a kind of deep ultraviolet positivity chemical amplification type photoresist, mainly mixed by following component and content thereof and form:
10～30 parts of weight of film-forming resin;
Photic sour 0.5～5 part of weight;
70～90 parts of weight of solvent;
0.01～0.5 part of weight of organic base;
Wherein:
Described film-forming resin adopts above-mentioned constructed scheme, is not repeated in this description here.
Described photic acid is selected from one of following material:
(1), sulfosalt
Its chemical general formula:
Perhaps
R
10=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
11=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
12=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
13=H, C
1-C
20Alkyl or C
1-C
20Alkoxy.
As triphenyl sulfosalt, three p-methylphenyl sulfosalts, the three pairs of tert-butyl-phenyl sulfosalts, three (3,5 3,5-dimethylphenyl) sulfosalt, three (3,5 di-tert-butyl-phenyl) sulfosalt etc.Coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthalene sulfonic acids etc.
(2), diaryl group iodized salt
Its chemical general formula:
-SO
3(CF
2)
mCF
3?m＝0-12
R
14=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
15=H, C
1-C
20Alkyl or C
1-C
20Alkoxy.
As diphenyl iodnium, di-p-tolyl salt compounded of iodine, two pairs of tert-butyl-phenyl salt compounded of iodine etc.Coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthalene sulfonic acids etc.
(3), acid imide sulphonic acid ester
Its chemical general formula:
Perhaps
Perhaps
As phenyl acid imide benzene sulfonate, phenyl acid imide tosylate, phenyl acid imide napsylate, naphthalimide benzene sulfonate, naphthalimide trifluoromethane sulfonic acid ester etc.
Described solvent is selected from one of following material:
1-Methoxy-2-propyl acetate, ethyl lactate, methyl isobutyl ketone;
Described organic base is selected from one of following material:
Tripropyl amine (TPA), tri-n-butylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxy monoethanolamine, trimethoxy methoxy ethyl amine, Tetramethylammonium hydroxide.
Other adjuvants can also have a small amount of component such as 0.01～0.3 part of weight of levelling agent, resistance solvent, dyestuff.
Design of the present invention and characteristics: in general film-forming resin prescription, introduced the siliceous esters of acrylic acid coupling agent of copolymerization with it, carried out copolymerization and be prepared into the new film-forming resin of a class based on poly(4-hydroxystyrene).This new film-forming resin is because the effect of acrylate containing silicone class coupling agent unit has increased the adhesive property between photoresist and the silicon chip.Simultaneously, also improved the performance of anti-dry etching.Furtherly, because the siliceous existence of esters of acrylic acid coupling agent unit in film-forming resin, photoresist glued membrane on its silicon chip is in photoetching process, in the non-exposed area, Si-OR group in the coupling agent will reduce the dissolubility of glued membrane in developer solution, exposure region is under the strong acid effect that photic acid forms, the Si-OR group is decomposed to form Si-OH and increases the dissolubility of glued membrane in alkaline-based developer in the coupling agent, and so just increased exposure region and non-exposed area contrast, and form litho pattern more clearly.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
Between hydroxy styrenes 98.5 gram;
Styrene 32.9 grams;
Metering system tert-butyl acrylate 30.5 grams;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 7.0 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, hydroxy styrenes 98.5 grams between adding, styrene 32.9 grams, metering system tert-butyl acrylate 30.5 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 7.0 grams, tetrahydrofuran 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 9.5 grams in 100 gram tetrahydrofurans, continue the reaction backflow after 6-24 hour, be cooled to room temperature then.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 85% after the vacuum drying.
Embodiment two:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 132 grams;
Methacrylic acid isoborneol fat 18 grams;
To tert-butoxy styrene 40 grams;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 132 grams, methacrylic acid isoborneol fat 18 grams, to tert-butoxy styrene 40 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams, tetrahydrofuran 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 12 grams in 100 gram tetrahydrofurans, continue the reaction backflow after 8-28 hour, add 80 gram A-15 (Rohm﹠amp; Haas, Amberlyst 15) ion exchange resin and 200 gram tetrahydrofurans, back flow reaction 8 hours, and steam about 100 milliliters and steam thing, be cooled to room temperature then.Remove by filter ion exchange resin.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 81% after the vacuum drying.
Embodiment three:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 125 grams;
To t-butyl styrene 32 grams;
Acrylic acid 1-methyl ring pentyl ester 36 grams;
Methacrylic acid ethyl trimethoxy silane ester 7 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 125 grams, to t-butyl styrene 32 grams, acrylic acid 1-methyl ring pentyl ester 36 grams, methacrylic acid ethyl trimethoxy silane ester 7 grams, tetrahydrofuran 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 11 grams in 100 gram tetrahydrofurans, continue the reaction backflow after 8-18 hour, add 3.0 caustic alcohols, add 200 gram tetrahydrofurans after 15 minutes, back flow reaction 8 hours, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 86% after the vacuum drying.
Embodiment four:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
Para hydroxybenzene ethene 120 grams;
Methacrylic acid 2-ethyl diamantane ester 64 grams;
Methacrylic acid propyl group dimethoxy-ethyl silicon ester 14 grams.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature controller, heating jacket and nitrogen inlet, add para hydroxybenzene ethene 120 grams, methacrylic acid 2-ethyl diamantane ester 64 grams, methacrylic acid propyl group dimethoxy-ethyl silicon ester 14 grams, tetrahydrofuran 500 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 9.8 grams in 100 gram tetrahydrofurans, continue the reaction backflow after 4-18 hour, be cooled to room temperature then.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 85% after the vacuum drying.
Embodiment five:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 126 grams;
Styrene 27 grams;
Acrylic acid 1-methyl ring pentyl ester 36 grams;
Methacrylic acid methyl trimethoxy silane ester 9 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 126 grams, styrene 27 grams, acrylic acid 1-methyl ring pentyl ester 36 grams, methacrylic acid methyl trimethoxy silane ester 9 grams, tetrahydrofuran 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 13 grams in 100 gram THF, continue the reaction backflow after 8-24 hour, add 20 gram styrene-titanium tetrachloride compound (PS-TiCl
4) and 200 gram tetrahydrofurans, back flow reaction 4-8 hour, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Cross the Lu and remove compound (PS-TiCl
4) resin.Polymer solution precipitates in pure water, gets polymer solids, yield 78% after the vacuum drying.
Embodiment six:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 120 grams;
Acrylic acid isoborneol fat 18 grams;
To tert-amyl benzene ethene 40 grams;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 120 grams, acrylic acid isoborneol fat 18 grams, to tert-amyl benzene ethene 40 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams, tetrahydrofuran 200 grams, methyl alcohol 200 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of tert-butyl hydroperoxide pivalate (26 gram) in 100 gram methyl alcohol, continue the reaction backflow after 8-28 hour, add 80 gram A-15 (Rohm﹠amp; Haas, Amberlyst15) ion exchange resin and 200 gram methyl alcohol, back flow reaction 8 hours, and steam about 100 milliliters and steam thing, be cooled to room temperature then.Remove by filter ion exchange resin.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 81% after the vacuum drying.
Embodiment seven:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 120 grams;
To ethyl styrene 32 grams;
Acrylic acid 1-ethyl cyclohexyl 45 grams;
Methacrylic acid ethyl trimethoxy silane ester 7 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 120 grams, to ethyl styrene 32 grams, acrylic acid 1-ethyl cyclohexyl 45 grams, methacrylic acid ethyl trimethoxy silane ester 7 grams, methyl alcohol 300 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of tert-butyl hydroperoxide pivalate 29 grams in 100 gram methyl alcohol, continue the reaction backflow after 8-18 hour, add 3.2 gram caustic alcohols, add 200 gram methyl alcohol after 15 minutes, back flow reaction 8 hours, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 82% after the vacuum drying.
Embodiment eight:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
Para hydroxybenzene ethene 120 grams;
Methacrylic acid diamantane ester 24 grams;
Methacrylic acid propyl group dimethoxy-ethyl silicon ester 9 grams;
Di-tert-butyl dicarbonate (DBDC) 66 grams.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature controller, heating jacket and nitrogen inlet, add para hydroxybenzene ethene 120 grams, methacrylic acid diamantane ester 24 grams, methacrylic acid propyl group dimethoxy-ethyl silicon ester 9 grams, tetrahydrofuran 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 9.8 grams in 100 gram tetrahydrofurans, continue the reaction backflow after 4-18 hour, be cooled to room temperature then.Add 6 gram N, the N dimethylamine yl pyridines slowly drips the solution of 66 gram di-tert-butyl dicarbonates (DBDC) in 300 milliliters of THF then, and reaction constantly generates bubble (carbon dioxide), and the control rate of addition prevents that a large amount of foams from producing.Temperature of reaction should be controlled at below 40 ℃.After DBDC solution adds, continue to stir reflection 6 hours.Extract three times with 200 milliliters of heptane then, polymer solution precipitates in pure water, vacuum drying at every turn.
1329% phenolic hydroxyl group is protected by tert-butyl group carbonate group in this polymkeric substance of C NMR analytical proof.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 76% after the vacuum drying.
Embodiment nine:
A kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from:
To acetoxy-styrene 120 grams;
Styrene 22 grams;
Acrylic acid 2-butyrolactone base ester 68 grams;
Methacrylic acid propyl trimethoxy silicane ester 7 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature controller, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 120 grams, styrene 22 grams, acrylic acid 2-butyrolactone base ester 68 grams, methacrylic acid propyl trimethoxy silicane ester 7 grams, methyl alcohol 300 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of tert-butyl hydroperoxide pivalate 30 grams in 100 gram methyl alcohol, continue the reaction backflow after 8-18 hour, add 3.0 gram sodium methoxides, add 200 gram methyl alcohol after 15 minutes, back flow reaction 8 hours, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Extract three times with heptane, polymer solution precipitates in pure water, gets polymer solids, yield 84% after the vacuum drying.
Embodiment ten:
The compound method of a kind of deep ultraviolet (248nm) photoresist: in clean 250 new ml polypropylene plastic bottles, the multipolymer that adds preparation among the 17.0 gram embodiment one, 0.21 gram triphenyl trifluoromethyl sulfosalt, 100 gram electronic grade propylene glycol monomethyl ether acetate (PGMEA) solvents, and 0.2 the gram n-butylamine, 0.12 the gram surfactant.This potpourri is fixed on the mechnical oscillator, at room temperature shakes 10-24 hour, and it is fully dissolved.Filtrator with 0.5 micron pore size filters one time, and the filtrator with 0.1 micron pore size filters one time then.
Lithography experiments method and result: the photoresist of above-mentioned preparation is 6 "-8 " on the silicon chip with 2000-6000 rev/min speed rotation film forming, in 90 seconds of baking on 120 ℃ of hot plates, use ASMAL 248nm step-by-step exposure machine (NA=0.63) to go up exposure then.Exposure intensity 10-50mJ/cm
2Toasted for 90 seconds on 110 ℃ of hot plates the exposure back, developed for 60 seconds oven dry back electron microscopy lithographic results at last again in 2.38%TMAH developer solution (23 ℃).The result proves that this photoresist resolution can reach 0.25-0.18 μ m, and has good photoetching process operation allowed band.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (4)
1, a kind of multipolymer film-forming resin that contains silicone couplet, under the condition that radical initiator exists, by carrying out copolymerization and corresponding aftertreatment is prepared from solvent, it is characterized in that: comonomer comprises by comonomer:
(1), hydroxyl styrene monomer 40%-90% weight;
Its chemical general formula:
In the formula: R=H, acetyl group or propiono; X=1-2;
(2), acrylate containing silicone class coupling agent 0.5%-20% weight;
Its chemical general formula:
In the formula: n=1-8; R
1=H, CH
3Or CF
3R
2=C
1-C
20Alkyl; R
3=C
1-C
20Alkyl; R
4=OH, C
1-C
20Alkyl or C
1-C
20Alkoxy;
(3), contain acid-sensitive group monomer 5%-60% weight;
Its chemical general formula:
Perhaps
In the formula: R
5=H, CH
3Or CF
3
Or
Rx=CH
3Or C
2H
5
The molecular weight of described multipolymer film-forming resin is 4000-100000, and molecular weight distribution is 1.4-2.8.
2, film-forming resin according to claim 1 is characterized in that: described comonomer also comprises styrene monomer or acrylic ester monomer 1～40%,
Its chemical general formula:
Perhaps
In the formula:
Ry=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
Rz=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
8=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
9=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group.
3, a kind of deep ultraviolet positivity chemical amplification type photoresist is characterized in that: mainly mixed by following component and content thereof and form:
10～30 parts of weight of film-forming resin;
Photic sour 0.5～5 part of weight;
70～90 parts of weight of solvent;
0.01～0.5 part of weight of organic base;
Wherein:
Described film-forming resin, under the condition that radical initiator exists, by carrying out copolymerization and corresponding aftertreatment is prepared from solvent, comonomer comprises by comonomer:
(1), hydroxyl styrene monomer 40%-90% weight;
Its chemical general formula:
In the formula: R=H, acetyl group or propiono; X=1-2;
(2), acrylate containing silicone class coupling agent 0.5%-20% weight;
Its chemical general formula:
In the formula: n=1-8; R
1=H, CH
3Or CF
3R
2=C
1-C
20Alkyl; R
3=C
1-C
20Alkyl; R
4=OH, C
1-C
20Alkyl or C
1-C
20Alkoxy;
(3), contain acid-sensitive group monomer 5%-60% weight;
Its chemical general formula:
Perhaps
In the formula: R
5=H, CH
3Or CF
3
Rx=CH
3Or C
2H
5
The molecular weight of described multipolymer film-forming resin is 4000-100000, and molecular weight distribution is 1.4-2.8; Described photic acid is selected from one of following material:
(1), sulfosalt
Its chemical general formula:
Perhaps
R
10=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
11=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
12=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
13=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
(2), diaryl group iodized salt
Its chemical general formula:
-SO
3(CF
2)
mCF
3 m＝0-12
R
14=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
R
15=H, C
1-C
20Alkyl or C
1-C
20Alkoxy;
(3), acid imide sulphonic acid ester
Its chemical general formula:
Perhaps
Perhaps
Described solvent is selected from one of following material:
1-Methoxy-2-propyl acetate, ethyl lactate, methyl isobutyl ketone;
Described organic base is selected from one of following material:
Tripropyl amine (TPA), tri-n-butylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxy monoethanolamine, trimethoxy methoxy ethyl amine, Tetramethylammonium hydroxide.
4, photoresist according to claim 3 is characterized in that: the comonomer in the described film-forming resin also comprises styrene monomer or acrylic ester monomer 1～40%,
Its chemical general formula:
In the formula:
Ry=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
Rz=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
8=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group;
R
9=H, C
1-C
20Alkyl, C
1-C
20Alkoxy, C
1-C
20Aryl or C
1-C
20Aryloxy group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610038787 CN1818782A (en) | 2006-03-13 | 2006-03-13 | Dark ultraviolet negative photoresist and filming resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610038787 CN1818782A (en) | 2006-03-13 | 2006-03-13 | Dark ultraviolet negative photoresist and filming resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1818782A true CN1818782A (en) | 2006-08-16 |
Family
ID=36918840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610038787 Pending CN1818782A (en) | 2006-03-13 | 2006-03-13 | Dark ultraviolet negative photoresist and filming resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1818782A (en) |
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| CN101974119A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Nano silicon containing deep ultraviolet positive photoresist and forming resin thereof |
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| CN101974121A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof |
| CN101974201A (en) * | 2010-09-30 | 2011-02-16 | 昆山西迪光电材料有限公司 | Ultraviolet thick-film photoresist and film-forming resin thereof |
| CN101974120A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Nano-crystalline silicon containing deep ultraviolet negative amplification type photoresist and film forming resin thereof |
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| CN103387636A (en) * | 2013-07-05 | 2013-11-13 | 昆山西迪光电材料有限公司 | Sesquiterpene-containing film-forming resin and positive 248 nm photoresist thereof |
| CN104387524A (en) * | 2014-11-25 | 2015-03-04 | 昆山西迪光电材料有限公司 | Sesquiterpene lactone-containing film-forming resin and negative 248nm photoresist thereof |
| CN104448114A (en) * | 2014-11-25 | 2015-03-25 | 昆山西迪光电材料有限公司 | Sesquiterpenes-containing film-forming resin and positive dry-method exposure 193nm photoresist prepared from same |
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| CN101974120B (en) * | 2010-09-28 | 2012-12-26 | 昆山西迪光电材料有限公司 | Nano-crystalline silicon containing deep ultraviolet negative amplification type photoresist and film forming resin thereof |
| CN101974121A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof |
| CN101974119A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Nano silicon containing deep ultraviolet positive photoresist and forming resin thereof |
| CN101974119B (en) * | 2010-09-28 | 2012-10-03 | 昆山西迪光电材料有限公司 | Nano silicon containing deep ultraviolet positive photoresist and forming resin thereof |
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| CN101974201A (en) * | 2010-09-30 | 2011-02-16 | 昆山西迪光电材料有限公司 | Ultraviolet thick-film photoresist and film-forming resin thereof |
| CN101974201B (en) * | 2010-09-30 | 2012-10-31 | 昆山西迪光电材料有限公司 | Ultraviolet thick-film photoresist and film-forming resin thereof |
| CN101974202A (en) * | 2010-09-30 | 2011-02-16 | 昆山西迪光电材料有限公司 | Silicon-contained I-ray ultraviolet positive photoresist and film-forming resin thereof |
| CN102050908A (en) * | 2010-11-22 | 2011-05-11 | 昆山西迪光电材料有限公司 | Chemical amplitude-increasing type silicon-containing I-line ultraviolet negative photoresist and forming resin thereof |
| CN103387636A (en) * | 2013-07-05 | 2013-11-13 | 昆山西迪光电材料有限公司 | Sesquiterpene-containing film-forming resin and positive 248 nm photoresist thereof |
| CN103387636B (en) * | 2013-07-05 | 2015-08-12 | 昆山西迪光电材料有限公司 | Containing film-forming resin and the positivity 248nm photoresist material thereof of sesquiterpene |
| CN104387524A (en) * | 2014-11-25 | 2015-03-04 | 昆山西迪光电材料有限公司 | Sesquiterpene lactone-containing film-forming resin and negative 248nm photoresist thereof |
| CN104448114A (en) * | 2014-11-25 | 2015-03-25 | 昆山西迪光电材料有限公司 | Sesquiterpenes-containing film-forming resin and positive dry-method exposure 193nm photoresist prepared from same |
| CN104387524B (en) * | 2014-11-25 | 2017-06-16 | 昆山西迪光电材料有限公司 | Film-forming resin containing sesquiterpene lactone and its negativity 248nm photoresists |
| CN112558409A (en) * | 2019-09-25 | 2021-03-26 | 常州强力先端电子材料有限公司 | Sulfonyl imide photoacid generator capable of generating acid at I line |
| CN112558409B (en) * | 2019-09-25 | 2022-05-20 | 常州强力先端电子材料有限公司 | Sulfonylimide photoacid generators capable of highly generating acid on line I |
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