CN103145624A - Molecular glass positive photoresist and patterning method thereof - Google Patents
Molecular glass positive photoresist and patterning method thereof Download PDFInfo
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- CN103145624A CN103145624A CN2012104969994A CN201210496999A CN103145624A CN 103145624 A CN103145624 A CN 103145624A CN 2012104969994 A CN2012104969994 A CN 2012104969994A CN 201210496999 A CN201210496999 A CN 201210496999A CN 103145624 A CN103145624 A CN 103145624A
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Abstract
The invention relates to a molecular glass positive photoresist composition for patterning realized by exposure and a method for forming a photoresist pattern. The positive photoresist composition comprises: (A) a functional group protected hexahydric nitrogenous heterocyclic derivative containing acid sensitive and functional group protected phenolic groups; (B) a photoacid generator (PAG); and (C) a solvent, wherein the functional group protected hexahydric nitrogenous heterocyclic derivative and the photoacid generator can dissolve in the solvent. When the molecular glass positive photoresist is exposed, the photoacid generator releases acids, which react with the acid sensitive functional groups to form the phenol groups. The hexahydric nitrogenous heterocyclic derivative containing phenol groups is accelerated to dissolve in a developer, thus forming a specific photoresist pattern. The molecular glass positive photoresist composition can be applied in the field of microelectronic technology.
Description
Technical field
The present invention relates to realize by exposure the positive photoresist that patterning uses, comprise and adopt extreme ultraviolet (EUV) light beam, KrF (248nm) or ArF (193nm) excimer laser, visible or near infrared laser, X-ray, electron beam, ionic fluid etc. as positive photoresist and the patterning method thereof of exposure light source, can be applied in microelectronics technology.
Background technology
Photoresist material is again photo-resist, is a class photosensitive material, utilizes its solvability difference of exposure front and back in developing solution, the fine structure that can obtain designing in advance.Utilizing photoresist material to carry out the processing of micro-nano structure, is to make a semiconducter device link as vital in super large-scale integration.Improving the Main Means of semiconducter device integrated level, be the characteristic dimension of dwindling photoetching agent pattern, and characteristic dimension is directly related with the wavelength of light source that photoetching is used.In photoetching technique, UV-light becomes the first-selection of exposure light source because wavelength is shorter, and turns to gradually more short wavelength's deep UV (ultraviolet light) (248nm and 193nm).Adopt at present ArF (193nm) excimer laser, realized the photoetching of 32nm lines, and photoengraving pattern is towards realizing the development of 22nm characteristic dimension.But information technology is constantly pursued speed and less volume faster, and this just requires further to reduce the characteristic dimension of photoengraving pattern.The research staff has research steering in the photoetching technique of short wavelength light source more and goes, and the EUV photoetching technique is arisen at the historic moment.Therefore EUV is the electromagnetic radiation of 13.4nm wavelength only, utilizes its extremely short wavelength to be expected to realize 22nm, the even processing of 15nm characteristic dimension pattern, and in international semiconductor Technology Roadmap in 2010, the EUV photoetching technique is confirmed as Next Generation Lithography.
Traditional photoresist material is comprised of photosensitive macromolecular material.Large and have a molecular dimension heterogeneity that polymolecularity causes due to the molecular weight of macromolecular material, and the contingent chain entanglement of macromolecular chain, detrimentally affect is caused to photoengraving pattern in the capital, and for example the resolving power of pattern is difficult to further improve, and the boundary characteristic of pattern is unintelligible etc.Molecular glass is as organic micromolecule compound, has amorphous state, definite molecular structure, the little and molecular dimension of homogeneous, and intermolecular do not have characteristics such as chain entanglement, therefore low-molecular-weight molecular glass had potential advantage as the photoresist material material.
Summary of the invention
The molecular weight that exists for the polymeric photoresist that proposes above is large and have the problem of polymolecularity, the purpose of this invention is to provide a kind of photoresist material based on the molecular glass compound.
According to an aspect of the present invention, provide a kind of hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group, this derivative has the structure of general formula I:
Wherein, X is carbon atom or nitrogen-atoms, is preferably carbon atom;
R
1, R
2, R
3, R
4Be selected from respectively hydrogen atom; C
1-C
6Alkyl; Unsubstituted or C
1-C
6Mono-substituted or the C of alkyl
1-C
6The polysubstituted phenyl of alkyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl or quinolyl; Or contain phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, the quinolyl of acid-sensitive sensitive group; And R
1, R
2, R
3, R
4In at least one is phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, the quinolyl that contains acid-sensitive sensitive group, described R
1, R
2, R
3, R
4Can be identical or different.Preferably, describedly contain the structure that acid-sensitive sensitive group has general formula I I:
Wherein, R
5Be CR
6R
7R
8, R wherein
6, R
7And R
8Be C independently
1-C
6Alkyl, C
1-C
6Alkoxyl group, phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, or quinolyl, and R
6, R
7And R
8Can be identical or different.
According to a further aspect in the invention, provide a kind of preparation method who contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group as above, the method comprises the steps:
Nitrogenous 6-membered heterocyclic compound and the reaction of methoxyl group aryl compound generate the methoxyl group aryl and replace nitrogenous 6-membered heterocyclic compound;
Described methoxyl group aryl replaces nitrogenous 6-membered heterocyclic compound demethylating and generates the nitrogenous 6-membered heterocyclic compound of hydroxyaryl replacement; And
With acid-sensitive sensitive group, the hydroxyl protection of the nitrogenous hexa-member heterocycle of hydroxyaryl replacement is obtained containing the hexa-atomic nitrogen-containing heterocycle compound of acid-sensitive sensitive group.
Preferably, the method comprises the steps:
Nitrogenous hexa-member heterocycle bromo-derivative and methoxyphenylboronic acid reaction with general formula III generate the nitrogenous 6-membered heterocyclic compound of methoxyl group aryl replacement;
Wherein, X is carbon atom or nitrogen-atoms, is preferably carbon atom; R
s1, R
s2, R
s3, R
s4Be selected from respectively hydrogen atom, bromine atoms, C
1-C
6Alkyl, or be respectively unsubstituted or C
1-C
6Mono-substituted or the C of alkyl
1-C
6The polysubstituted phenyl of alkyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, quinolyl, and R
s1, R
s2, R
s3, R
s4In at least one is bromine atoms, described R
s1, R
s2, R
s3, R
s4Can be identical or different;
Described methoxyl group aryl replaces nitrogenous hexa-member heterocycle and boron tribromide BBr
3The reaction demethylating generates hydroxyaryl and replaces nitrogenous 6-membered heterocyclic compound; And
With the tertbutyloxycarbonyl compound, the phenolic hydroxyl group protection of the nitrogenous hexa-member heterocycle of described hydroxyaryl replacement is obtained containing the hexa-atomic nitrogen-containing heterocycle compound of acid-sensitive sensitive group.
In accordance with a further aspect of the present invention, provide a kind of positive photoresist composition, comprising:
At least a hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group as above,
At least a photo-acid generator (PAG), and
Be used for dissolving the described hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group and the solvent of described photo-acid generator of containing.
Preferably, in positive photoresist composition of the present invention, the amount of this hexa-atomic nitogen-contained heterocycle derivant is 0.5wt% to 10wt%, and preferred 2wt% to 5wt% is with the total restatement of this photoetching compositions.
Positive photoresist composition of the present invention comprises at least a photo-acid generator, and when being exposed to exposure source, photo-acid generator produces the acid that is used for the acid-sensitive sensitive group of cracking.Usually, can be hard to bear the irradiation photo-acid generator that produces acid and have a better thermostability can be used in photoetching compositions of the present invention.These light acid producing agents include, but are not limited to following photo-acid generator: as trifluoromethanesulfonic acid triphenyl sulphur, and perfluor fourth sulfonic acid triphenyl sulphur, perfluor penta sulfonic acid triphenyl sulphur, perfluorooctane sulfonate triphenyl sulphur, six metaantimmonic acid triphenyl sulphur, hexafluoroarsenate triphenyl sulphur, phosphofluoric acid triphenyl sulphur, bromination triphenyl sulphur, chlorinated triphenyl〔Zeng Suji〕 base sulphur, iodate triphenyl sulphur, diphenyl antimony chloride base ethyl sulphur etc.; As trifluoromethanesulfonic acid diphenyl iodnium, perfluor fourth sulfonic acid diphenyl iodnium, perfluor penta sulfonic acid diphenyl iodnium, perfluorooctane sulfonate diphenyl iodnium, hexafluoro-antimonic acid diphenyl iodnium, hexafluoro-antimonic acid diphenyl iodnium, two (tert-butyl-phenyl) trifluoromethanesulfonic acid diphenyl iodnium; Two (p-toluenesulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyl diazomethane, two (cyclohexyl alkylsulfonyl) diazomethane.
In positive photoresist composition of the present invention, the amount of photo-acid generator is 0.01wt% to 1.5wt%, and preferred 0.1wt% to 0.5wt% is with the total restatement of this photoetching compositions.
Positive photoresist composition of the present invention also comprises solvent.Solvent described in the present invention will have solvability preferably to pyrimidine derivatives and photo-acid generator, and possesses suitable volatility so that the removal of solvent when front baking.Solvent of the present invention includes but not limited to following solvent: a kind of or mixture of 1-Methoxy-2-propyl acetate, cyclopentanone, pimelinketone, ethyl lactate, methyl glycol, N-BUTYL ACETATE, cellosolvo, two (ethylene glycol) diethyl ether, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, chlorobenzene etc.
The amount of the solvent of positive photoresist of the present invention accounts for the 88.5wt% to 99.49wt% of gross weight, and preferred 94.5wt% to 97.9wt% is with the total restatement of this photoetching compositions.
In accordance with a further aspect of the present invention, a kind of method that produces photoetching agent pattern in substrate is provided, comprise: coating contains above-mentioned positive photoresist composition formation photoresist film and baking removal solvent in substrate, and described positive photoresist contains hexa-atomic nitogen-contained heterocycle derivant, photo-acid generator and the solvent of acid labile group; Described positive photoresist film is exposed under light source exposes, the photoresist film after then exposing toasts, develops, thereby obtains photoetching agent pattern.
Preferably, form the step of toasting after photoresist film and comprise with 30-180 ℃, the described photoresist film of temperature baking of preferred 50-120 ℃.
Preferably, the baking procedure before described development step is that described photoresist film is heated to 30-180 ℃, preferred 50-120 ℃.
Preferably, the exposure source of step of exposure is selected from EUV, KrF, ArF, the visible and/or light sources such as near-infrared laser, electron beam, ionic fluid or X-ray.
Preferably, the developing solution of development step is the aqueous solution of the compounds such as Tetramethylammonium hydroxide, trimethylammonium-2-hydroxyethylammoniumhydroxide hydroxide, sodium hydroxide or potassium hydroxide, preferred 0.26mol/L tetramethylammonium hydroxide aqueous solution.
In positive photoresist composition disclosed by the invention, comprise the hexa-atomic nitogen-contained heterocycle derivant of protective group, it contains phenolic group and the photo-acid generator (Photoacid generator, PAG) of the protective group of acid-sensitive sense.When this resist exposure, photo-acid generator discharges acid, and the acid that discharges and the functional group reactions of acid-sensitive sense form phenolic group.These contain hexa-atomic nitogen-contained heterocycle derivant accelerate dissolution in developing solution of phenolic group, thereby form specific photoetching agent pattern.This molecular glass positive photoresist composition can be applied in microelectronics technology.According to the present invention, provide a kind of positive photoresist based on low-molecular-weight molecule glass.With hexa-atomic nitogen-contained heterocycle derivant as body material, by introducing the aromatic yl group of acid labile, not only can utilize the lightsensitivity of the principle raising photoresist material of chemistry amplification, and due to the high carbon of benzene ring structure/hydrogen than giving photoresist material good anti-etching performance, can satisfy the strict demand of existing microelectronic processing technology.
Description of drawings
Fig. 1 illustrates the preparation flow that contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group according to of the present invention.
Fig. 2 represents the organic compound M in embodiment 1
1Chemical structural formula.
Fig. 3 represents the organic compound M in embodiment 2
2Chemical structural formula.
Fig. 4 represents photoresist material P in embodiment 3
1Photoetching agent pattern after exposure imaging.
Fig. 5 represents photoresist material P in embodiment 4
2Photoetching agent pattern after exposure imaging.
Embodiment
Below in conjunction with some specific exampless, the present invention program is described further, its objective is person skilled in the art scholar can be understood content of the present invention and implement.These examples are only some explanations, can not be interpreted as a kind of restriction of the present invention.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Fig. 1 illustrates the preparation flow that contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group according to of the present invention.As shown in Figure 1, the preparation that contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group mainly is divided into three large steps.
Step 301: nitrogenous 6-membered heterocyclic compound and the reaction of methoxyl group aryl compound generate the methoxyl group aryl and replace nitrogenous 6-membered heterocyclic compound.
For example, the reaction of nitrogenous hexa-member heterocycle bromo-derivative and methoxyphenylboronic acid generates the nitrogenous 6-membered heterocyclic compound of methoxyl group aryl replacement.
Those skilled in the art as required, the nitrogenous hexa-member heterocycle bromo-derivative that can select to have general formula III is realized according to the various hexa-atomic nitogen-contained heterocycle derivants that contain acid-sensitive sensitive group of the present invention.
Wherein, X is carbon atom or nitrogen-atoms, is preferably carbon atom; R
s1, R
s2, R
s3, R
s4Be selected from respectively hydrogen atom, bromine atoms, C
1-C
6Alkyl, or C
1-C
6The alkyl list replaces or polysubstituted phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, or quinolyl, and R
s1, R
s2, R
s3, R
s4In at least one is bromine atoms, described R
s1, R
s2, R
s3, R
s4Can be identical or different.
Step 302: the methoxyl group aryl replaces nitrogenous 6-membered heterocyclic compound demethylating and generates the nitrogenous 6-membered heterocyclic compound of hydroxyaryl replacement.
For example, the methoxyl group aryl replaces nitrogenous hexa-member heterocycle and boron tribromide BBr
3The reaction demethylating generates hydroxyaryl and replaces nitrogenous 6-membered heterocyclic compound.
Step 303: with acid-sensitive sensitive group, the phenolic hydroxyl group protection of the nitrogenous hexa-member heterocycle of hydroxyaryl replacement is obtained containing the hexa-atomic nitrogen-containing heterocycle compound of acid-sensitive sensitive group.
For example, with acid-sensitive sensitive group tertbutyloxycarbonyl, the hydroxyl protection of the nitrogenous hexa-member heterocycle of hydroxyaryl replacement is obtained containing the hexa-atomic nitrogen-containing heterocycle compound of acid-sensitive sensitive group.
Embodiment 1
Add 50mL Isosorbide-5-Nitrae-dioxane in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, drum rare gas element such as nitrogen flooding oxygen half an hour under the condition that stirs.Subsequently, add 1g2 under the condition of drum nitrogen, 4-two bromo pyrimi piperidine 1g and catalyzer tetrakis triphenylphosphine palladium 200mg mix rear continuation drum nitrogen 10 minutes.Subsequently, add 2-methoxyphenylboronic acid 1.5g and the saturated wet chemical 2.5M of nitrogen in there-necked flask, 10mL, post-heating reaction system to be mixed is to reflux state, stopped reaction after the reaction certain hour.Reaction times is for example 1-48 hour, is preferably 1-10 hour.Concentrated, column chromatography for separation obtains intermediate product 2,4-two-(2-p-methoxy-phenyl)-pyrimidine.
Add 2,4-two (2-p-methoxy-phenyl)-pyrimidine 1g and methylene dichloride 40mL in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, cooling reaction system to temperature is-5 ℃, then slowly adds boron tribromide BBr
30.8mL the temperature with reaction system after fully mixing slowly rises to room temperature, reaction certain hour, then stopped reaction.Reaction times can be selected 1-48 hour usually, implements in preferred 10-15 hour.Reaction system is slowly poured into obtained suspension liquid in potassium bicarbonate aqueous solution, suction filtration obtains brown solid intermediate product 2,4-two (2-hydroxy phenyl)-pyrimidine.
Add N-Methyl pyrrolidone 50mL in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, 2,4-two (2-hydroxy phenyl)-pyrimidine 1g, two dimethyl dicarbonate butyl ester 2.5g and DMAP 0.5g, stirring reaction certain hour under room temperature.Reaction times can be selected 10-60 hour, preferred 20-30 hour.Reaction system is poured into water, uses ethyl acetate extraction three times, obtain pressed powder 2 after concentrate drying, 4-two [2-(tert.-butoxy carbonyl oxygen base) phenyl]-pyrimidine.Utilize 1H NMR and 13C NMR to carry out structural characterization to the compound that obtains, result is as follows:
1H NMR (400MHz, CDCl3, δ) 9.32 (d, J=1.3Hz, 1H), (7.98 d, J=1.3Hz, 1H), 7.87 (dd, J1=7.6Hz, J2=1.6Hz, 2H), 7.52 (dt, J1=7.6Hz, J2=1.6Hz, 2H), 7.19 (t, J=7.6Hz, 2H), 7.29 (dd, J1=8.2Hz, J2=1.0Hz, 2H), 1.44 (s, 18H).
13C NMR (100MHz, CDCl3) δ 163.18,158.60,151.37,148.94,131.38,130.69,130.55,126.52,123.47,119.50,83.69,27.51, show to have obtained the molecular glass compound M with definite structure and homogeneous molecular weight as shown in Figure 2
1
Embodiment 2
Add the 50mL tetrahydrofuran (THF) in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, drum rare gas element such as nitrogen flooding oxygen half an hour under the condition that stirs.Subsequently, add three bromo pyrimi piperidine 1g and catalyzer tetrakis triphenylphosphine palladium 120mg under the condition of drum nitrogen, mix rear continuation drum nitrogen 10 minutes.Subsequently, add 2-methoxyphenylboronic acid 1.5g and wet chemical 2.5M in there-necked flask, 6mL, post-heating reaction system to be mixed is to reflux state, and after the reaction certain hour, the system color transfers black purple, stopped reaction to from yellow.Reaction times can be selected 1-48 hour, is preferably 1-10 hour.Concentrated, column chromatography for separation obtains intermediate product 2,4,6-three-(2-p-methoxy-phenyl)-pyrimidine.
Add 50mL methylene dichloride and 2 in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, 4,6-three (2-anisole)-pyrimidine 1g, cooling reaction system to temperature is-5 ℃, then slowly add boron tribromide 1mL, temperature with reaction system after fully mixing slowly rises to room temperature, reaction certain hour, then stopped reaction.Reaction times can be selected 1-48 hour usually, implements in preferred 10-15 hour.Reaction system is slowly poured into obtained suspension liquid in sodium bicarbonate aqueous solution, suction filtration obtains orange red solid intermediate product 2,4,6-three-(2-hydroxy phenyl)-pyrimidine.
Add N-Methyl pyrrolidone 60mL in the 250mL there-necked flask that is fixed on magnetic stirring apparatus, 2,4,6-three (2-hydroxy phenyl)-pyrimidine (1g), two dimethyl dicarbonate butyl ester (2.4g) and DMAP 0.5g, stirring reaction certain hour under room temperature.Reaction times can be selected 10-60 hour, preferred 20-30 hour.Reaction system is poured into water, uses ethyl acetate extraction three times, obtain white solid powder 2,4 after concentrate drying, 6-three [2-(tert.-butoxy carbonyl oxygen base) phenyl]-pyrimidine.Utilize
1H NMR and
13C NMR carries out structural characterization to the compound that obtains, and result is as follows:
1H NMR (400MHz, CDCl
3, δ) 9.24 (s, 1H), 7.33 (m, 2H), 7.21 (m, 6H), 6.98 (m, 4H), 1.53 (s, 18H), 1.40 (s, 9H).
13C NMR (100MHz, CDCl
3, δ) 163.71,156.36,151.89,150.96,148.65,148.06,132.42,130.93,130.67,130.04,129.51,128.30,127.97,125.39,125.11,123.08,121.64,83.45,82.97,27.62,27.46,27.13, show to have prepared the small molecules organic compound M with definite structure and homogeneous molecular weight as shown in Figure 3
2
Embodiment 3
Dissolve 2,4 in 0.1g embodiment 1 in the 2g chlorobenzene, 6-three [2-(tert.-butoxy carbonyl oxygen base) phenyl]-pyrimidine and 0.005g photo-acid generator trifluoromethanesulfonic acid triphenyl sulphur, system stirs with magneton under the lucifuge condition and obtains photoresist solution half an hour.With this photoresist solution with the membrane filtration in 0.22 μ m aperture 3 times to remove impurity, obtain positive photoresist composition P
1Drip appropriate positive photoresist composition P2 in substrate, obtain photoresist film with the rotating speed spin coating in 500 rev/min of 5 second and 4000 rev/min of 30 second.The gained photoresist film was toasted 2 minutes on the hot plate of 100 ℃, obtain transparent photoresist film.Utilize the femtosecond laser of 780nm that this photoresist film is exposed, the photoresist film after exposure is rear the baking 30 seconds under 80 ℃.At last, use Tetramethylammonium hydroxide (TMAH) aqueous solution of 0.26mol/L to develop 30 seconds, washed with de-ionized water is also dry, obtains photoetching offset plate figure as shown in Figure 4.
Embodiment 4
Dissolve 2,4 in 0.1g embodiment 1 in the 2g chlorobenzene, 6-three [2-(tert.-butoxy carbonyl oxygen base) phenyl]-pyrimidine and 0.01g photo-acid generator trifluoromethanesulfonic acid triphenyl sulphur, system stirs with magneton under the lucifuge condition and obtains photoresist solution half an hour.With this photoresist solution with the membrane filtration in 0.22 μ m aperture 3 times to remove impurity, obtain positive photoresist composition P
2Drip appropriate positive photoresist composition P in substrate, obtain photoresist film with the rotating speed spin coating in 500 rev/min of 5 second and 4000 rev/min of 30 second.The gained photoresist film was toasted 2 minutes on the hot plate of 100 ℃, obtain transparent photoresist film.Utilize the femtosecond laser of 780nm that this photoresist film is exposed, the photoresist film after exposure is rear the baking 30 seconds under 80 ℃.At last, use Tetramethylammonium hydroxide (TMAH) aqueous solution of 0.26mol/L to develop 30 seconds, washed with de-ionized water is also dry, obtains photoetching offset plate figure as shown in Figure 5.
The above is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (12)
1. a hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group, is characterized in that, this derivative has the structure of general formula I:
Wherein, X is carbon atom or nitrogen-atoms, is preferably carbon atom;
R
1, R
2, R
3, R
4Be selected from respectively hydrogen atom; C
1-C
6Alkyl; Unsubstituted or C
1-C
6Mono-substituted or the C of alkyl
1-C
6The polysubstituted phenyl of alkyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl or quinolyl; Or contain phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, the quinolyl of acid-sensitive sensitive group; And R
1, R
2, R
3, R
4In at least one is phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, the quinolyl that contains acid-sensitive sensitive group, described R
1, R
2, R
3, R
4Can be identical or different.
2. the hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group as claimed in claim 1, is characterized in that, describedly contains the structure that acid-sensitive sensitive group has general formula I I:
Wherein, R
5Be CR
6R
7R
8, R wherein
6, R
7And R
8Be C independently
1-C
6Alkyl, C
1-C
6Alkoxyl group, phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, or quinolyl, and R
6, R
7And R
8Can be identical or different.
3. a preparation method who contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group as claimed in claim 1, is characterized in that, comprises the steps:
Nitrogenous 6-membered heterocyclic compound and the reaction of methoxyl group aryl compound generate the methoxyl group aryl and replace nitrogenous 6-membered heterocyclic compound;
Described methoxyl group aryl replaces nitrogenous 6-membered heterocyclic compound demethylating and generates the nitrogenous 6-membered heterocyclic compound of hydroxyaryl replacement; And
With acid-sensitive sensitive group, the phenolic hydroxyl group protection of the nitrogenous hexa-member heterocycle of hydroxyaryl replacement is obtained containing the hexa-atomic nitrogen-containing heterocycle compound of acid-sensitive sensitive group.
4. a preparation method who contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group as claimed in claim 3, is characterized in that, comprises the steps:
Nitrogenous hexa-member heterocycle bromo-derivative and methoxyphenylboronic acid reaction with general formula III generate the nitrogenous 6-membered heterocyclic compound of methoxyl group aryl replacement;
Wherein, X is carbon atom or nitrogen-atoms, is preferably carbon atom; R
s1, R
s2, R
s3, R
s4Be selected from respectively hydrogen atom, bromine atoms, C
1-C
6Alkyl, unsubstituted or C
1-C
6The alkyl list replaces or C
1-C
6The polysubstituted phenyl of alkyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, quinolyl, and R
s1, R
s2, R
s3, R
s4In at least one is bromine atoms, described R
s1, R
s2, R
s3, R
s4Can be identical or different.
Described methoxyl group aryl replaces nitrogenous hexa-member heterocycle and boron tribromide BBr
3The reaction demethylating generates hydroxyaryl and replaces nitrogenous 6-membered heterocyclic compound; And
With the tertbutyloxycarbonyl compound, the phenolic hydroxyl group protection of the nitrogenous hexa-member heterocycle of described hydroxyaryl replacement is obtained containing the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group.
5. positive photoresist composition comprises:
At least a hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group as claimed in claim 1,
At least a photo-acid generator (PAG), and
Be used for dissolving the described hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group and the solvent of described photo-acid generator of containing.
6. positive photoresist composition as claimed in claim 5, wherein said acid-sensitive sensitive group is the described structure of general formula I I:
Wherein, R
5Be CR
6R
7R
8, R wherein
6, R
7And R
8Be C independently
1-C
6Alkyl, C
1-C
6Alkoxyl group, phenyl, thienyl, thiazolyl, furyl, pyridyl, pyrimidyl, pyrryl, naphthyl, or quinolyl, and R
6, R
7And R
8Can be identical or different.
7. positive photoresist composition as claimed in claim 5, wherein said hexa-atomic nitogen-contained heterocycle derivant can be a kind of hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group, can be also the mixture of the different hexa-atomic nitogen-contained heterocycle derivant that contains acid-sensitive sensitive group.
8. positive photoresist composition as claimed in claim 5, the wherein said amount that contains the hexa-atomic nitogen-contained heterocycle derivant of acid-sensitive sensitive group is: 0.5wt% to 10wt%, preferred 2wt% to 5wt%, the amount of described photo-acid generator (PAG) is 0.01wt% to 1.5wt%, preferred 0.1wt% to 0.5wt%, the amount of described solvent is 88.5wt% to 99.49wt%, and preferred 94.5wt% to 97.9wt% is with the total restatement of this photoetching compositions.
9. produce the method for photoetching agent pattern in substrate, it comprises following steps:
Positive photoresist composition claimed in claim 4 is applied to forms photoresist film in substrate;
Make described photoresist film exposure;
Toast the described photoresist film that has exposed;
Develop in developing solution, obtain the photoetching agent pattern structure.
10. method as described in claim 9, wherein
The step of described formation photoresist film further comprises with 30-180 ℃, the described photoresist film of temperature baking of preferred 50-120 ℃;
Preferably, before described development step, described photoresist film is heated to 30-180 ℃, preferred 50-120 ℃.
11. method as described in claim 9, the exposure source of wherein said step of exposure are selected from EUV, KrF, ArF, the visible and/or light sources such as near-infrared laser, electron beam, ionic fluid or X-ray.
12. method as described in claim 9, the developing solution of wherein said development step is the aqueous solution of the compounds such as Tetramethylammonium hydroxide, trimethylammonium-2-hydroxyethylammoniumhydroxide hydroxide, sodium hydroxide or potassium hydroxide, preferred 0.26mol/L tetramethylammonium hydroxide aqueous solution.
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| CN106444281A (en) * | 2016-09-22 | 2017-02-22 | 京东方科技集团股份有限公司 | Photoresist and etching method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA787931A (en) * | 1968-06-18 | Brunetti Heimo | Process for the production of o-hydroxyphenyl-s-triazines | |
| US3896125A (en) * | 1963-01-24 | 1975-07-22 | Ciba Geigy Ag | O-hydroxyphenyl-s-triazines |
| US4358393A (en) * | 1979-05-15 | 1982-11-09 | Veb Werk Fur Fernsehelektronik Im Veb Kombinat Mikroelektronik | Nematic liquid crystals of 5-cyano-2-[4-acyloxyphenyl]-pyrimidines and mixtures containing the same |
-
2012
- 2012-11-28 CN CN201210496999.4A patent/CN103145624B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA787931A (en) * | 1968-06-18 | Brunetti Heimo | Process for the production of o-hydroxyphenyl-s-triazines | |
| US3896125A (en) * | 1963-01-24 | 1975-07-22 | Ciba Geigy Ag | O-hydroxyphenyl-s-triazines |
| US4358393A (en) * | 1979-05-15 | 1982-11-09 | Veb Werk Fur Fernsehelektronik Im Veb Kombinat Mikroelektronik | Nematic liquid crystals of 5-cyano-2-[4-acyloxyphenyl]-pyrimidines and mixtures containing the same |
Non-Patent Citations (2)
| Title |
|---|
| 山峰孝等: "光学曝光用光刻胶的种类及其特性", 《微电子学》, no. 02, 25 April 1980 (1980-04-25) * |
| 王江洪等: "5-(2-硫甲基-4-甲基-5-嘧啶基)-2,4戊二炔-l-醇α-甲基丙烯酸酯(PDMA)/PMMA的全光通道波导", 《功能高分子学报》, vol. 11, no. 03, 30 September 1998 (1998-09-30) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106444281A (en) * | 2016-09-22 | 2017-02-22 | 京东方科技集团股份有限公司 | Photoresist and etching method |
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