CN102050946A - Ultraviolet positive photoresist containing nano silicon polyamide and film-forming resin thereof - Google Patents

Ultraviolet positive photoresist containing nano silicon polyamide and film-forming resin thereof Download PDF

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CN102050946A
CN102050946A CN 201010552630 CN201010552630A CN102050946A CN 102050946 A CN102050946 A CN 102050946A CN 201010552630 CN201010552630 CN 201010552630 CN 201010552630 A CN201010552630 A CN 201010552630A CN 102050946 A CN102050946 A CN 102050946A
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nano
silicon
formula
poss
general formula
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CN102050946B (en
Inventor
冉瑞成
沈吉
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Kunshan Xidi Optoelectronic Material Co ltd
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KUNSHAN SD PHOTOELECTRIC MATERIAL Co Ltd
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Abstract

The invention discloses an ultraviolet positive photoresist containing nano silicon polyamide and film-forming resin thereof. The film-forming resin is formed by polymerizing aroyl chloride, aromatic amine and a component unit containing nano silicon; the ultraviolet positive photoresist containing nano silicon polyamide is prepared from the film-forming resin, wherein the weight parts of the film-forming resin and a solvent are respectively 8-30 and 70-90. The photoresist prepared by the invention has favorable high-temperature resisting property, mechanical property, electricity property, blocking property and erosion resistance property.

Description

Contain nano-silicon polymeric amide ultraviolet positive photoresist and film-forming resin thereof
Technical field
What the present invention relates to use in the fields such as a kind of manufacturing that is applicable to semi-conductor discrete device and large-scale integrated circuit and encapsulation contains nano-silicon polymeric amide ultraviolet positive photoresist and film-forming resin thereof.
Background technology
In the preparation process of semi-conductor discrete device and large-scale integrated circuit, not only chip manufacturing process makes rapid progress, and encapsulation technology and packaged material also are the very important technology integral parts of a fast development.At present, advanced encapsulation technology develops into the encapsulation of silicon chip level by the single encapsulation respectively of one integrated circuit block, and be superimposed to form 3 D stereo combination package with better function etc. by the polylith chip, in encapsulation process applied packaged material also since the improvement of technology bring in constant renewal in.The heat resistant polyamide type uv-exposure positive light-sensitive material that the present invention relates to is not only the critical material of unicircuit and discrete device manufacturing process, also is necessary key function material in the packaging process.
Summary of the invention
The object of the invention provides a kind of being applied to and contains nano-silicon polymeric amide ultraviolet positive photoresist and this polymeric amide type of film-forming resin uv photosensitivity material thereof in semi-conductor discrete device and large-scale integrated circuit manufacturing and the advanced potting process.
For achieving the above object, first kind of technical scheme that the present invention adopts is: a kind of film-forming resin is mainly made by following two steps:
The first step: by fragrant acyl chlorides, contain nano-silicon component units and three kinds of comonomers of aromatic amine and carry out copolyreaction obtain containing nano-silicon polyamide prepolymer polymers in solvent, the mass percent of described three kinds of comonomers is as follows:
Fragrance acyl chlorides 20%～70%;
Contain nano-silicon component units 1%～10%;
Aromatic amine 20%～70%;
Described fragrant acyl chlorides be meet chemical general formula ( ) and chemical general formula ( ) compound at least a:
Figure 2010105526301100002DEST_PATH_IMAGE003
（
Figure 679096DEST_PATH_IMAGE001
）；
Figure 330658DEST_PATH_IMAGE004
（
Figure 251340DEST_PATH_IMAGE002
）；
In the formula, R 1, R 2Represent H or OH independently of one another; R 3For
Figure DEST_PATH_IMAGE005
,
Figure 542423DEST_PATH_IMAGE006
,
Figure DEST_PATH_IMAGE007
,
Figure 966583DEST_PATH_IMAGE008
,
Figure DEST_PATH_IMAGE009
,
Figure 929991DEST_PATH_IMAGE010
Or
Figure DEST_PATH_IMAGE011
Described contain the nano-silicon component units be meet chemical general formula (
Figure 72390DEST_PATH_IMAGE012
) at least a compound:
（
Figure 691197DEST_PATH_IMAGE012
）；
In the formula, at least one substituent R fGeneral molecular formula (
Figure 422393DEST_PATH_IMAGE014
) shown in, remaining substituent R fBe carbonatoms be 1～10 alkyl,
Figure DEST_PATH_IMAGE015
, ,
Figure DEST_PATH_IMAGE017
Or
Figure 920818DEST_PATH_IMAGE018
Figure DEST_PATH_IMAGE019
（
Figure 795846DEST_PATH_IMAGE014
）；
In the formula, R 4Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group;
Described aromatic amine be meet chemical general formula ( ), chemical general formula (
Figure DEST_PATH_IMAGE021
) and chemical general formula (
Figure 171912DEST_PATH_IMAGE022
) compound at least a:
（
Figure 288903DEST_PATH_IMAGE020
）；
Figure 891923DEST_PATH_IMAGE024
（
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）；
Figure DEST_PATH_IMAGE025
（
Figure 556046DEST_PATH_IMAGE022
）；
In the formula, R 5, R 6Representative independently of one another
Figure 81705DEST_PATH_IMAGE008
,
Figure 239148DEST_PATH_IMAGE009
, ,
Figure 118560DEST_PATH_IMAGE011
,
Figure 397094DEST_PATH_IMAGE007
,
Figure 89719DEST_PATH_IMAGE005
Or
Figure 504520DEST_PATH_IMAGE006
Second step: photosensitizers is coupled to the nano-silicon polyamide prepolymer polymers that contains that the first step makes obtains containing nano-silicon photosensitive polyamide film-forming resin, described photosensitizers for meet structural formula (
Figure 994538DEST_PATH_IMAGE026
) or structural formula (
Figure DEST_PATH_IMAGE027
) the diazo naphthoquinone acyl chlorides, described photosensitizers is with to contain the mass percent of nano-silicon polyamide prepolymer polymers as follows:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 307839DEST_PATH_IMAGE028
（
Figure 56352DEST_PATH_IMAGE026
）；
Figure DEST_PATH_IMAGE029
（
Figure 138709DEST_PATH_IMAGE027
）。
For achieving the above object, second kind of technical scheme that the present invention adopts is: a kind of adopt that above-mentioned film-forming resin makes contain nano-silicon polymeric amide ultraviolet positive photoresist, it is characterized in that: mainly form by the compound of following mass parts:
8～30 parts of film-forming resins;
70～90 parts of solvents;
Described solvent is selected from dimethylbenzene, methyl-phenoxide, propylene glycol monomethyl ether, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, ethyl lactate, gamma-butyrolactone, the N-Methyl pyrrolidone.
For achieving the above object, the third technical scheme that the present invention adopts is: a kind of film-forming resin is mainly made by following three steps:
The first step: carry out copolyreaction by fragrant acyl chlorides and two kinds of comonomers of aromatic amine in solvent and obtain the polyamide prepolymer polymers, the mass percent of described two kinds of comonomers is as follows:
Fragrance acyl chlorides 30%～70%;
Aromatic amine 30%～70%;
Described fragrant acyl chlorides be meet chemical general formula (
Figure 62278DEST_PATH_IMAGE030
) and chemical general formula (
Figure DEST_PATH_IMAGE031
) at least a in the compound:
Figure 862875DEST_PATH_IMAGE032
（
Figure 149500DEST_PATH_IMAGE030
）；
Figure DEST_PATH_IMAGE033
（
Figure 164992DEST_PATH_IMAGE031
）；
In the formula, R 7, R 8Represent H or OH independently of one another, R 9For
Figure 511659DEST_PATH_IMAGE005
,
Figure 468726DEST_PATH_IMAGE006
,
Figure 559042DEST_PATH_IMAGE007
,
Figure 553674DEST_PATH_IMAGE008
,
Figure 71243DEST_PATH_IMAGE009
,
Figure 846432DEST_PATH_IMAGE010
Or
Figure 225592DEST_PATH_IMAGE011
Described aromatic amine be meet chemical general formula (
Figure 323998DEST_PATH_IMAGE034
), chemical general formula (
Figure DEST_PATH_IMAGE035
) and chemical general formula (
Figure 635637DEST_PATH_IMAGE036
) compound at least a:
Figure 819494DEST_PATH_IMAGE023
（
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）；
Figure DEST_PATH_IMAGE037
（
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）；
（
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）；
In the formula, R 10, R 11Representative independently of one another
Figure 305881DEST_PATH_IMAGE008
,
Figure 191928DEST_PATH_IMAGE009
,
Figure 972933DEST_PATH_IMAGE010
,
Figure 131382DEST_PATH_IMAGE011
,
Figure 656036DEST_PATH_IMAGE006
,
Figure 849120DEST_PATH_IMAGE005
Or
Figure 860413DEST_PATH_IMAGE007
Second step: will contain polyamide prepolymer polymers that the nano-silicon component units and the first step make and carry out copolyreaction obtain containing nano-silicon polyamide prepolymer polymers in solvent, the described mass percent that contains nano-silicon component units and polyamide prepolymer polymers is as follows:
Polyamide prepolymer polymers 90%～99%;
Contain nano-silicon component units 1%～10%;
Described contain the nano-silicon component units be meet chemical general formula ( ) at least a compound:
（ ）；
In the formula, at least one substituent R hMeet chemical general formula (
Figure DEST_PATH_IMAGE041
), chemical general formula (
Figure 242613DEST_PATH_IMAGE042
), chemical general formula (
Figure DEST_PATH_IMAGE043
) or chemical general formula (
Figure 424808DEST_PATH_IMAGE044
) shown in, remaining substituent R fBe carbonatoms be 1～10 alkyl,
Figure 292270DEST_PATH_IMAGE015
,
Figure 158726DEST_PATH_IMAGE016
, Or
Figure 354532DEST_PATH_IMAGE018
Figure DEST_PATH_IMAGE045
（
Figure 787918DEST_PATH_IMAGE041
）；
In the formula, R 12Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 13Be , ,
Figure 274056DEST_PATH_IMAGE048
Or
Figure DEST_PATH_IMAGE049
The example that can enumerate: for example:
The different ethyl Si of eight epoxypropyl 8-POSS, eight epoxypropyl sec.-propyl Si 8-POSS, eight epoxypropyl isobutyl-Si 8-POSS, eight epoxypropyl isopentyl Si 8-POSS, eight epoxypropyl iso-octyl Si 8-POSS, eight epoxypropyl cyclopentyl Si 8-POSS, eight epoxypropyl cyclohexyl Si 8-POSS, eight epoxies, the third oxygen ethyl sec.-propyl Si 8-POSS, eight epoxypropoxy sec.-propyl Si 8-POSS, eight epoxies, the third oxygen ethyl isobutyl-Si 8-POSS, eight epoxypropoxy isobutyl-Si 8-POSS, eight epoxies, the third oxygen ethyl isopentyl Si 8-POSS, eight epoxypropoxy iso-octyl Si 8-POSS, eight oxirane ring amyl group ethyl Si 8-POSS, eight epoxy cyclohexyl ethyl Si 8-POSS, eight oxirane ring amyl group sec.-propyl Si 8-POSS, eight epoxy cyclohexyl sec.-propyl Si 8-POSS, eight oxirane ring amyl group isobutyl-Si 8-POSS, eight epoxy cyclohexyl isobutyl-Si 8-POSS, eight oxirane ring amyl group isopentyl Si 8-POSS, eight epoxy cyclohexyl isopentyl Si 8-POSS, eight oxirane ring amyl group iso-octyl Si 8-POSS, eight epoxy cyclohexyl iso-octyl Si 8-POSS, eight oxirane ring amyl group cyclopentyl Si 8-POSS, eight oxirane rings are basic ring amyl group Si 8-POSS, eight oxirane ring amyl group cyclohexyl Si 8-POSS, the basic cyclohexyl Si of eight oxirane rings 8-POSS, eight epoxy dicyclos [2,2,1] heptyl isobutyl-Si 8-POSS, eight epoxy dicyclos [2,2,1] heptyl cyclohexyl Si 8-POSS.
Figure 614032DEST_PATH_IMAGE050
（
Figure 456086DEST_PATH_IMAGE042
）；
In the formula, R 14Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 15Be OH,
Figure DEST_PATH_IMAGE051
,
Figure 536782DEST_PATH_IMAGE052
Or
Figure DEST_PATH_IMAGE053
Figure 226520DEST_PATH_IMAGE054
（ ）；
In the formula, R 16Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 17Be
Figure DEST_PATH_IMAGE055
,
Figure 253699DEST_PATH_IMAGE056
,
Figure DEST_PATH_IMAGE057
Or
Figure 138085DEST_PATH_IMAGE058
Chemical general formula (
Figure 869281DEST_PATH_IMAGE042
) and chemical general formula (
Figure 675694DEST_PATH_IMAGE043
) example that can enumerate for example:
Eight hydroxyethyl ethyl Si 8-POSS, eight hydroxyethyl sec.-propyl Si 8-POSS, eight hydroxyethyl isobutyl-Si 8-POSS, eight hydroxyethyl base isopentyl Si 8-POSS, eight hydroxyethyl base iso-octyl Si 8-POSS, eight hydroxyethyl basic ring amyl group Si 8-POSS, eight hydroxyethyl base cyclohexyl Si 8-POSS, eight hydroxypropyl ethyl Si 8-POSS, eight hydroxypropyl base sec.-propyl Si 8-POSS, eight hydroxypropyl isobutyl-Si 8-POSS, eight hydroxypropyl base isopentyl Si 8-POSS, eight hydroxypropyl iso-octyl Si 8-POSS, eight hydroxypropyl cyclopentyl Si 8-POSS, eight hydroxypropyl cyclohexyl Si 8-POSS, eight hydroxypropyl oxygen ethyl sec.-propyl Si 8-POSS, eight hydroxypropyl oxygen ethyl sec.-propyl Si 8-POSS, eight hydroxypropyl oxygen ethyl isobutyl-Si 8-POSS, eight hydroxypropyl oxygen ethyl cyclohexyl Si 8-POSS, eight hydroxypropyl oxygen propyl group cyclopentyl Si 8-POSS, eight hydroxypropyl oxygen propyl group iso-octyl Si 8-POSS, eight couples of hydroxy-cyclohexyl sec.-propyl Si 8-POSS, eight couples of hydroxy-cyclohexyl isobutyl-Si 8-POSS, eight couples of hydroxy-cyclohexyl cyclopentyl Si 8-POSS, eight couples of hydroxy-cyclohexyl cyclohexyl Si 8-POSS, eight adjacent dihydroxypropyl cyclohexyl Si 8-POSS, eight adjacent dihydroxypropyl isobutyl-Si 8-POSS, eight adjacent dihydroxypropyl cyclopentyl Si 8-POSS, eight adjacent dihydroxypropyl iso-octyl Si 8-POSS, eight adjacent dihydroxy cyclohexyl cyclohexyl Si 8-POSS, eight adjacent dihydroxy cyclohexyl isobutyl-Si 8-POSS, eight adjacent dihydroxy cyclopentyl iso-octyl Si 8-POSS, eight adjacent dihydroxy cyclopentyl isopentyl Si 8-POSS, eight adjacent dihydroxy dicyclo [2,2,1] heptyl isobutyl-Si 8-POSS, eight adjacent dihydroxy dicyclo [2,2,1] heptyl cyclohexyl Si 8-POSS.
Figure DEST_PATH_IMAGE059
（ ）；
In the formula, R 18Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 19Be NH 2Or
Figure 370297DEST_PATH_IMAGE060
The example that can enumerate is for example:
Eight aminoethyl ethyl Si 8-POSS, eight aminoethyl sec.-propyl Si 8-POSS, eight aminoethyl isobutyl-Si 8-POSS, eight aminoethyl base iso-octyl Si 8-POSS, eight aminoethyl base cyclohexyl Si 8-POSS, octa-aminopropyl ethyl Si 8-POSS, octa-aminopropyl base sec.-propyl Si 8-POSS, octa-aminopropyl isobutyl-Si 8-POSS, octa-aminopropyl base isopentyl Si 8-POSS, octa-aminopropyl iso-octyl Si 8-POSS, octa-aminopropyl cyclopentyl Si 8-POSS, eight N-methyl aminopropyl cyclohexyl Si 8-POSS, eight N-methyl aminopropyl isobutyl-Si 8-POSS, eight N-methyl aminopropyl iso-octyl Si 8-POSS, eight N-phenylamino propyl group isobutyl-Si 8-POSS, eight N-phenylamino propyl group cyclohexyl Si 8-POSS, eight couples of aminophenyl isobutyl-Si 8-POSS, eight couples of aminophenyl cyclohexyl Si 8-POSS, eight aminophenyl isobutyl-Si 8-POSS, eight aminophenyl cyclohexyl Si 8-POSS, eight ammonia second aminopropyl isobutyl-Si 8-POSS, eight ammonia second aminopropyl cyclohexyl Si 8-POSS.
The 3rd step: photosensitizers is coupled to the second nano-silicon polyamide prepolymer polymers that contains that make of step obtains containing nano-silicon photosensitive polyamide film-forming resin, described photosensitizers for meet structural formula (
Figure DEST_PATH_IMAGE061
) or structural formula (
Figure 769049DEST_PATH_IMAGE062
) the diazo naphthoquinone acyl chlorides, described photosensitizers is with to contain the mass percent of nano-silicon polyamide prepolymer polymers as follows:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 805750DEST_PATH_IMAGE028
（
Figure 860425DEST_PATH_IMAGE061
）；
Figure 463445DEST_PATH_IMAGE029
（
Figure 654386DEST_PATH_IMAGE062
）。
For achieving the above object, the 4th kind of technical scheme that the present invention adopts is: a kind of adopt that above-mentioned film-forming resin makes contain nano-silicon polymeric amide ultraviolet positive photoresist, it is characterized in that: mainly form by the compound of following mass parts:
8～30 parts of film-forming resins;
70～90 parts of solvents;
Described solvent is selected from dimethylbenzene, methyl-phenoxide, propylene glycol monomethyl ether, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, ethyl lactate, gamma-butyrolactone, the N-Methyl pyrrolidone.
Related content in the technique scheme is explained as follows:
1, in the such scheme, film-forming resin is a kind of polyamide prepolymer polymers that contains photosensitive functional group among the present invention, it comprises two functional moieties: a part contains polyhedron oligomeric silsesquioxanes (Polyhedral Oligomeric Silsesquioxanes for alkali soluble, POSS) polyamide prepolymer polymers, another part are the photosensitizerss that links to each other with this prepolymer chemical bond.POSS be have nano-scale the inorganic SHAPE of siloxanes the assorted multiatomic system of * MERGEFORMAT polyhedron kernel and the outer field cage shape of organism.The polymeric amide film-forming resin that contains POSS and photosensitive group is that alkalescence is insoluble, and it can be dissolved in alkaline-based developer through becoming after the ultraviolet photoetching.After overexposure and developing, also can pass through the hot setting operation, make polymeric amide (or polyamic acid) be converted into the polyimide type polymkeric substance.The polyimide type polymkeric substance has good thermotolerance, oxidation-resistance and anti-etching performance.In addition, because containing " inorganic-organic " with nano-scale assorted polyatom cage shape microstructure as one, polyhedron oligomeric silsesquioxanes (POSS) introduced prepolymer, not only can further improve the resistance toheat of photosensitive material, also can improve its rheological property, be modified into film properties.This application art to photosensitive material all is very important.
2, in the such scheme, POSS be have nano-scale the inorganic SHAPE of siloxanes the assorted multiatomic system of * MERGEFORMAT polyhedron kernel and the outer field cage shape of organism, its skeleton diameter of the Si8-POSS that contains eight Siliciumatoms commonly used is 1.5nm, if comprise organic skin, its diameter is about 2-4nm.The chemical general formula of Si8-POSS is Si 8O 12R (8-n)Rf n, n=8-0 wherein, chemical three-dimensional arrangement is as follows:
。
POSS will have tremendous influence to the physicals of polymkeric substance.In polyamide prepolymer polymers molecular chain, POSS can be connected among the molecular chain, and POSS also can the grafting mode hang over the molecular chain outside, and its connecting mode can be controlled by synthetic method.The ratio of POSS in the polyamide prepolymer polymers generally is about 1～10%(mass percent),
Figure 192814DEST_PATH_IMAGE064
。
3, in the such scheme, contain polyamide prepolymer polymers (containing nano-silicon polyamide prepolymer polymers) synthetic of nano-silicon polyhedron oligomeric silsesquioxanes (POSS):
The polyamide prepolymer polymers that contains nano-silicon polyhedron oligomeric silsesquioxanes (POSS) can be prepared by two approach: an approach is by aromatic amine, contains POSS aromatic amine and fragrant acyl chloride reaction and directly generates the desired polyamide prepolymer polymers that contains nano-silicon polyhedron oligomeric silsesquioxanes (POSS).Another approach is at first to generate the polyamide prepolymer polymers by aromatic amine and fragrant acyl chloride reaction, and then with contain epoxy group(ing), hydroxyl, the POSS reactive grafting of particular functional groups such as amido generates polymeric amide (or polyamic acid) prepolymer that contains POSS.This method generally prepares the polyamide prepolymer polymers that contains POSS (being that POSS is grafted on the chain of polyamide prepolymer polymers) of side hanging.Employ method fibrous root is according to raw material sources in the production, and factors such as product performance requirement and production technique and equipment determine.
4, in the such scheme, the coupling of photosensitizers:
Owing to contain on the nano-silicon polyamide prepolymer polymers molecular chain and contain many amidos, many functional groups such as hydroxyl, they can with photosensitizers DNQ-215 or DNQ-214 linked reaction, preparation contains the photosensitive polyamide film-forming resin (containing nano-silicon photosensitive polyamide film-forming resin) of POSS.Following showing:
Figure DEST_PATH_IMAGE065
5, in the such scheme, contain nano-silicon polymeric amide ultraviolet positive photoresist by containing nano-silicon photosensitive polyamide film-forming resin (calculating 8～30 parts) with solid weight, solvent (70-90 part) and a small amount of other additives (0.01～1 part) are formulated, then through 5 microns, the strainer of 1 micron and 0.2 micron filters.
6, in the such scheme, manyly contain, hydroxyl, amido, epoxy alkyl, aromatic amine Si8-POSS can buy, and also can synthesize, synthetic method is exemplified below, other is similar:
The nitration reaction of the first step: POSS:
In 500 ml flasks that agitator, thermometer and reflux exchanger be housed, add 150 milliliters of tetracol phenixin (CCl 4) and 10 gram isobutyl phenenyl Si8-POSS, make its dissolving.Stir and slowly add 50 milliliters of vitriol oils (98%) and 50 milliliters of nitric acid (27%) down.Slowly change in the acid solution mixture over to restir reaction 1 hour, then reaction mixture is slowly added in 500 milliliters of frozen water.Separate organic layer with separating funnel, water layer merges organic layer with 25 milliliters of carbon tetrachloride extraction, and with salt solution washing twice, neutralizes with 5% sodium carbonate solution, and distillation gets thick product after removing tetracol phenixin.Thick then product dissolves back deposition and purification in methyl alcohol in tetrahydrofuran (THF), get nitrated POSS after the drying, and yield is 90%.
Second step: the reduction of nitrated POSS:
In 500 ml flasks that agitator, thermometer and reflux exchanger be housed, add 150 milliliters of tetrahydrofuran (THF)s (THF), the nitrated POSS product of 9 grams, 6 times of equivalent zinc powders (Zn) begin to stir.Slowly add 7 times of equivalent concentrated hydrochloric acids (12M), reaction mixture becomes clear solution gradually, continues reaction 1 hour.Remove by filter insolubles, distillation removes and desolvates, and is dissolved in ether and precipitates in methyl alcohol carrying out purifying, gets the canescence powdery solid, yield 95%.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
In general film-forming resin prescription, introduced the Si8-POSS that contains nano-silicon of copolymerization with it, carry out copolymerization and be prepared into the new film-forming resin of a class, perhaps will have the new film-forming resin of Si8-POSS group introducing polymer molecule chain formation one class of nano-scale with the method for graft reaction.This new film-forming resin has increased the adhesive property between photoresist material and the silicon chip owing to contain the effect of the Si8-POSS group with nano-scale.The present invention makes contains the once even glue of nano-silicon polymeric amide ultraviolet positive photoresist and gets rid of the sheet thickness and can reach 0.5～5 micron, after preceding baking, and with UV-light (g, h, i-line) exposure, by developing liquid developing, the final high temperature baking-curing.The nano-silicon polymeric amide ultraviolet positive photoresist that contains that the present invention makes has good temperature resistance energy, mechanical property, electric property, adhesion property and anti-etching performance.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: a kind of film-forming resin
Contain nano-silicon photosensitive polyamide film-forming resin (photosensitivity contains POSS polyamide prepolymer polymers film-forming resin) preparation method:
The first step: contain the synthetic of nano-silicon polyamide prepolymer polymers
Figure DEST_PATH_IMAGE067
In 1000 ml flasks that agitator, thermometer, reflux exchanger and nitrogen gangway be housed, add 21.1 gram pyridines, 175 gram N-Methyl pyrrolidone (NMP), 51.2 restrain 3,3 '-diamino hexafluoro bisphenol-a (BPAF) and 4.5 gram diaminotoluene base ethyl POSS.Dissolving mixt and be cooled to-22 ℃ to-25 ℃ gradually under agitation with dry ice.Slowly add be pre-mixed by 12.6 gram m-phthaloyl chloride (IPC) and 120 milliliters of solution that anhydrous NMP is mixed with, and the maintenance reaction mixture temperature is in-18 ± 2 ℃ of scopes.Stop cooling then, allow reaction mixture delay curtain and be warming up to room temperature (25 ℃) and kept the reaction end 20 hours.With dropping funnel reaction mixture is slowly added under agitation 5 liters of pure water and to make its precipitation, filter and collect prepolymer, and washing three times in pure water.Get 65 gram prepolymers after the vacuum-drying.
The first step: the coupling of photosensitizers:
In the gold-tinted lighting environment, in 1000 ml flasks that agitator, thermometer, reflux exchanger and nitrogen gangway be housed, add 100 gram prepolymers, 450 gram tetrahydrofuran (THF)s (THF).At room temperature stirring dissolves prepolymer fully.Add 2.5 gram DNQ-215.Slow (10 minutes) add the mixed solution of 0.76 gram triethylamine (TEA) and 10 milliliters of THF then.Reaction mixture at room temperature continued stirring reaction 12 hours.Precipitated product in 8 liters of pure water under slowly adding is fully stirred with reaction mixture then filters, and washing then 40 ℃ of following vacuum-dryings, gets 95 gram photosensitivity and contains POSS polyamide prepolymer polymers film-forming resin.
Embodiment two: a kind of film-forming resin
The first step: contain the synthetic of nano-silicon polyamide prepolymer polymers
Figure 561403DEST_PATH_IMAGE068
In 1000 ml flasks that agitator, thermometer, reflux exchanger and nitrogen gangway be housed, add 21.1 gram pyridines, 175 gram N-Methyl pyrrolidone (NMP), 51.2 restrain 3,3 '-diamino hexafluoro bisphenol-a (BPAF) and 4.9 gram diaminotoluene base ethyl POSS.Dissolving mixt and be cooled to-22 ℃ to-25 ℃ gradually under agitation with dry ice.Slow curtain add be pre-mixed by 22.8 grams 4,4 ' to dimethyl chloride phenyl ether (ODC) and 150 milliliters of solution that anhydrous NMP is mixed with, and the maintenance reaction mixture temperature is in-18 ± 2 ℃ of scopes.Stop cooling then, allow reaction mixture delay curtain and be warming up to room temperature (25 ℃) and kept the reaction end 20 hours.With dropping funnel reaction mixture is slowly added under agitation 5 liters of pure water and to make its precipitation, filter and collect prepolymer, and washing three times in pure water.Get 72 gram prepolymers after the vacuum-drying.
Second step: the coupling of photosensitizers:
In the gold-tinted lighting environment, in 1000 ml flasks that agitator, thermometer, reflux exchanger and nitrogen gangway be housed, add 100 gram prepolymers, 450 gram tetrahydrofuran (THF)s (THF).At room temperature stirring dissolves prepolymer fully.Add 1.7 gram DNQ-215.Slow (10 minutes) add the mixed solution of 0.76 gram triethylamine (TEA) and 10 milliliters of THF then.Reaction mixture at room temperature continued stirring reaction 12 hours.Precipitated product in 8 liters of pure water under slowly adding is fully stirred with reaction mixture then filters, and washing then 40 ℃ of following vacuum-dryings, gets 95 gram photosensitivity and contains POSS polyamide prepolymer polymers film-forming resin.
Embodiment three: a kind of film-forming resin
The first step: contain the synthetic of nano-silicon polyamide prepolymer polymers
Method like the two-phase of applicating adn implementing example is reacted generation polyamide prepolymer polymers at low temperatures with fragrant acyl chlorides and aromatic amine.Then, this prepolymer can will obtain to contain the polyamide prepolymer polymers of POSS with the POSS reaction that contains the functional group (epoxypropyl) that is easy to react.This prepolymer carries out linked reaction with photosensitizers DNQ-214 again and gets final product to such an extent that have a polyamide prepolymer polymers that contains POSS of photosensitivity.
Embodiment four: a kind of film-forming resin
Figure 731484DEST_PATH_IMAGE070
The 30%(mass percent);
The 60%(mass percent);
Figure 399005DEST_PATH_IMAGE072
The 10%(mass percent).
The preparation method is with embodiment one.
Embodiment five: a kind of film-forming resin
Figure DEST_PATH_IMAGE073
The 71%(mass percent);
Figure 225010DEST_PATH_IMAGE074
The 25%(mass percent);
Eight epoxies, the third oxygen ethyl isopentyl Si 8-POSS 4%(mass percent).
The preparation method is with embodiment three
Embodiment six: a kind of film-forming resin
Figure DEST_PATH_IMAGE075
The 23%(mass percent);
The 72%(mass percent);
Octa-aminopropyl iso-octyl Si 8-POSS 5%(mass percent);
The preparation method is with embodiment three.
Embodiment seven: a kind of film-forming resin
Figure DEST_PATH_IMAGE077
The 45%(mass percent);
Figure 210731DEST_PATH_IMAGE078
The 48%(mass percent);
Eight oxirane ring amyl group iso-octyl Si 8-POSS 7%(mass percent);
The preparation method is with embodiment three.
Embodiment eight: a kind of film-forming resin
Figure DEST_PATH_IMAGE079
The 55%(mass percent);
The 35%(mass percent);
Eight hydroxyethyl base iso-octyl Si 8-POSS 10%(mass percent);
The preparation method is with embodiment three.
Embodiment nine～16: a kind of nano-silicon polymeric amide ultraviolet positive photoresist that contains
One, the preparation of photoresist material and photoetching test (operation all must be carried out under gold-tinted)
Join glue: according to different exposure requirements and thickness requirement, adjust the prescription of photoresist material, preparation as follows, by containing nano-silicon photosensitive polyamide film-forming resin (photosensitivity contains the polyamide prepolymer polymers film-forming resin of nano-silicon Si8-POSS) (5～30 parts), solvent (70～95 parts) and a small amount of other additives (0.01～1 part) are mixed with solution, stir more than 16 hours.Again successively by 5 microns, 1 micron, the filtration of 0.2 micron membranes.
Photoetching process comprises:
Even glue: 300 rev/mins of rotating speeds, 5 seconds; 1000 rev/mins, 50～60 seconds.
Preceding baking: 105-110 ℃, 1～3 minute.(can divide two sections bakings when glued membrane is thicker, temperature edges up, and temperature is decided by technology, generally is no more than 140 ℃).
Exposure: g-line, I-line or g-i-line mix, 10-30mW/cm 2, 10～100 seconds.
Develop: TMAH(2.3%)/60 second; Or the AZ400K/ pure water, 1:3,50-120 second, 23 ℃.
Back baking: hot plate, 120-150 ℃, 1-2 minute.
The removal of glue: with N-Methyl pyrrolidone (NMP) wash-out.
Two, the prescription of photoresist material is as shown in the table:
The film-forming resin that embodiment nine～16 adopt embodiment one～eight to make successively
? Film-forming resin Solvent Effect
Embodiment nine 8 N-BUTYL ACETATE 85 Well
Embodiment ten 20 Methyl-phenoxide 90 Well
Embodiment 11 15 Dihydroxypropane single-ether 85 Well
Embodiment 12 9 Ethyl lactate 75 Well
Embodiment 13 10 Gamma-butyrolactone 90 Well
Embodiment 14 13 1-Methoxy-2-propyl acetate 89 Well
Embodiment 15 15 Propylene glycol monomethyl ether 88 Well
Embodiment 16 21 N-Methyl pyrrolidone 90 Well
Annotate: 1, the unit of above-mentioned numeral is parts by weight.
2, the n-Butyl Amine 99 that also contains 0.1 weight part in the prescription.
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. film-forming resin is characterized in that: mainly made by following two steps:
The first step: by fragrant acyl chlorides, contain nano-silicon component units and three kinds of comonomers of aromatic amine and carry out copolyreaction obtain containing nano-silicon polyamide prepolymer polymers in solvent, the mass percent of described three kinds of comonomers is as follows:
Fragrance acyl chlorides 20%～70%;
Contain nano-silicon component units 1%～10%;
Aromatic amine 20%～70%;
Described fragrant acyl chlorides be meet chemical general formula (
Figure 34172DEST_PATH_IMAGE002
) and chemical general formula (
Figure 726185DEST_PATH_IMAGE004
) compound at least a:
Figure 148682DEST_PATH_IMAGE006
（
Figure 609751DEST_PATH_IMAGE002
）；
Figure 164229DEST_PATH_IMAGE008
（ ）；
In the formula, R 1, R 2Represent H or OH independently of one another; R 3For
Figure 307076DEST_PATH_IMAGE010
,
Figure 137498DEST_PATH_IMAGE012
,
Figure 95833DEST_PATH_IMAGE014
,
Figure 949389DEST_PATH_IMAGE016
,
Figure 965886DEST_PATH_IMAGE018
, Or
Figure 48560DEST_PATH_IMAGE022
Described contain the nano-silicon component units be meet chemical general formula ( ) at least a compound:
Figure 504873DEST_PATH_IMAGE026
（
Figure 795040DEST_PATH_IMAGE024
）；
In the formula, at least one substituent R fGeneral molecular formula (
Figure 924539DEST_PATH_IMAGE028
) shown in, remaining substituent R fBe carbonatoms be 1～10 alkyl,
Figure 300156DEST_PATH_IMAGE030
,
Figure 346872DEST_PATH_IMAGE032
,
Figure 6392DEST_PATH_IMAGE034
Or
Figure 57525DEST_PATH_IMAGE036
Figure DEST_PATH_IMAGE038
（
Figure DEST_PATH_IMAGE040
）；
In the formula, R 4Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group;
Described aromatic amine be meet chemical general formula (
Figure DEST_PATH_IMAGE042
), chemical general formula (
Figure DEST_PATH_IMAGE044
) and chemical general formula (
Figure DEST_PATH_IMAGE046
) compound at least a:
Figure DEST_PATH_IMAGE048
（
Figure 481291DEST_PATH_IMAGE042
）；
Figure DEST_PATH_IMAGE050
（
Figure 352205DEST_PATH_IMAGE044
）；
Figure DEST_PATH_IMAGE052
（
Figure 226752DEST_PATH_IMAGE046
）；
In the formula, R 5, R 6Representative independently of one another
Figure 448785DEST_PATH_IMAGE016
,
Figure 48263DEST_PATH_IMAGE018
,
Figure 13945DEST_PATH_IMAGE020
,
Figure 881013DEST_PATH_IMAGE022
,
Figure 133003DEST_PATH_IMAGE014
,
Figure 658925DEST_PATH_IMAGE010
Or
Figure 411986DEST_PATH_IMAGE012
Second step: photosensitizers is coupled to the nano-silicon polyamide prepolymer polymers that contains that the first step makes obtains containing nano-silicon photosensitive polyamide film-forming resin, described photosensitizers for meet structural formula (
Figure DEST_PATH_IMAGE054
) or structural formula ( ) the diazo naphthoquinone acyl chlorides, described photosensitizers is with to contain the mass percent of nano-silicon polyamide prepolymer polymers as follows:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure DEST_PATH_IMAGE058
（
Figure 399140DEST_PATH_IMAGE054
）；
Figure DEST_PATH_IMAGE060
（ ）。
2. a film-forming resin that adopts claim 1 makes contains nano-silicon polymeric amide ultraviolet positive photoresist, it is characterized in that: mainly be made up of the compound of following mass parts:
8～30 parts of film-forming resins;
70～90 parts of solvents;
Described solvent is selected from dimethylbenzene, methyl-phenoxide, propylene glycol monomethyl ether, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, ethyl lactate, gamma-butyrolactone, the N-Methyl pyrrolidone.
3. film-forming resin is characterized in that: mainly made by following three steps:
The first step: carry out copolyreaction by fragrant acyl chlorides and two kinds of comonomers of aromatic amine in solvent and obtain the polyamide prepolymer polymers, the mass percent of described two kinds of comonomers is as follows:
Fragrance acyl chlorides 30%～70%;
Aromatic amine 30%～70%;
Described fragrant acyl chlorides be meet chemical general formula (
Figure DEST_PATH_IMAGE062
) and chemical general formula (
Figure DEST_PATH_IMAGE064
) at least a in the compound:
（
Figure 333784DEST_PATH_IMAGE062
）；
（ ）；
In the formula, R 7, R 8Represent H or OH independently of one another, R 9For ,
Figure 139038DEST_PATH_IMAGE012
,
Figure 872508DEST_PATH_IMAGE014
,
Figure 983684DEST_PATH_IMAGE016
,
Figure 682780DEST_PATH_IMAGE018
,
Figure 588420DEST_PATH_IMAGE020
Or
Figure 871502DEST_PATH_IMAGE022
Described aromatic amine be meet chemical general formula (
Figure DEST_PATH_IMAGE070
), chemical general formula (
Figure DEST_PATH_IMAGE072
) and chemical general formula (
Figure DEST_PATH_IMAGE074
) compound at least a:
（
Figure 822195DEST_PATH_IMAGE070
）；
Figure DEST_PATH_IMAGE076
（
Figure 23370DEST_PATH_IMAGE072
）；
Figure DEST_PATH_IMAGE078
（
Figure 229967DEST_PATH_IMAGE074
）；
In the formula, R 10, R 11Representative independently of one another
Figure 666633DEST_PATH_IMAGE016
,
Figure 589590DEST_PATH_IMAGE018
,
Figure 587764DEST_PATH_IMAGE020
,
Figure 783122DEST_PATH_IMAGE022
,
Figure 774212DEST_PATH_IMAGE012
,
Figure 299478DEST_PATH_IMAGE010
Or
Figure 717821DEST_PATH_IMAGE014
Second step: will contain polyamide prepolymer polymers that the nano-silicon component units and the first step make and carry out copolyreaction obtain containing nano-silicon polyamide prepolymer polymers in solvent, the described mass percent that contains nano-silicon component units and polyamide prepolymer polymers is as follows:
Polyamide prepolymer polymers 90%～99%;
Contain nano-silicon component units 1%～10%;
Described contain the nano-silicon component units be meet chemical general formula (
Figure DEST_PATH_IMAGE080
) at least a compound:
Figure DEST_PATH_IMAGE082
（
Figure 823311DEST_PATH_IMAGE080
）；
In the formula, at least one substituent R hMeet chemical general formula (
Figure DEST_PATH_IMAGE084
), chemical general formula (
Figure DEST_PATH_IMAGE086
), chemical general formula (
Figure DEST_PATH_IMAGE088
) or chemical general formula (
Figure DEST_PATH_IMAGE090
) shown in, remaining substituent R fBe carbonatoms be 1～10 alkyl,
Figure 576283DEST_PATH_IMAGE030
, ,
Figure 548229DEST_PATH_IMAGE034
Or
Figure 531228DEST_PATH_IMAGE036
Figure DEST_PATH_IMAGE092
（
Figure 736557DEST_PATH_IMAGE084
）；
In the formula, R 12Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 13Be
Figure DEST_PATH_IMAGE094
,
Figure DEST_PATH_IMAGE096
,
Figure DEST_PATH_IMAGE098
Or
Figure DEST_PATH_IMAGE102
（
Figure 160716DEST_PATH_IMAGE086
）；
In the formula, R 14Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 15Be OH,
Figure DEST_PATH_IMAGE104
, Or
Figure DEST_PATH_IMAGE108
Figure DEST_PATH_IMAGE110
（
Figure 560343DEST_PATH_IMAGE088
）；
In the formula, R 16Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 17Be
Figure DEST_PATH_IMAGE112
,
Figure DEST_PATH_IMAGE114
,
Figure DEST_PATH_IMAGE116
Or
Figure DEST_PATH_IMAGE120
（
Figure 325911DEST_PATH_IMAGE090
）；
In the formula, R 18Representing carbonatoms is that the carbonatoms that contains 1～3 Siliciumatom on 1～10 aliphatic group or the molecular chain is 1～10 aliphatic group; R 19Be NH 2Or
Figure DEST_PATH_IMAGE122
The 3rd step: photosensitizers is coupled to the second nano-silicon polyamide prepolymer polymers that contains that make of step obtains containing nano-silicon photosensitive polyamide film-forming resin, described photosensitizers for meet structural formula (
Figure DEST_PATH_IMAGE124
) or structural formula (
Figure DEST_PATH_IMAGE126
) the diazo naphthoquinone acyl chlorides, described photosensitizers is with to contain the mass percent of nano-silicon polyamide prepolymer polymers as follows:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 397248DEST_PATH_IMAGE058
（
Figure 426646DEST_PATH_IMAGE124
）；
Figure 872540DEST_PATH_IMAGE060
（
Figure 564552DEST_PATH_IMAGE126
）。
4. a film-forming resin that adopts claim 3 makes contains nano-silicon polymeric amide ultraviolet positive photoresist, it is characterized in that: mainly be made up of the compound of following mass parts:
8～30 parts of film-forming resins;
70～90 parts of solvents;
Described solvent is selected from dimethylbenzene, methyl-phenoxide, propylene glycol monomethyl ether, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, ethyl lactate, gamma-butyrolactone, the N-Methyl pyrrolidone.
CN2010105526301A 2010-11-22 2010-11-22 Ultraviolet positive photoresist containing nano silicon polyamide and film-forming resin thereof Expired - Fee Related CN102050946B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448298A (en) * 2013-09-17 2015-03-25 达兴材料股份有限公司 Polymer, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display module

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Publication number Priority date Publication date Assignee Title
CN1535299A (en) * 2001-07-26 2004-10-06 日产化学工业株式会社 Polyamic acid resin composition
CN101750895A (en) * 2008-12-16 2010-06-23 华东理工大学 Silicon-containing (meth)acrylate light-cured stamping adhesive for ultraviolet nanometer-sized stamping and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1535299A (en) * 2001-07-26 2004-10-06 日产化学工业株式会社 Polyamic acid resin composition
CN101750895A (en) * 2008-12-16 2010-06-23 华东理工大学 Silicon-containing (meth)acrylate light-cured stamping adhesive for ultraviolet nanometer-sized stamping and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448298A (en) * 2013-09-17 2015-03-25 达兴材料股份有限公司 Polymer, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display module

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