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CN102050946B - 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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Publication number
CN102050946B
CN102050946B CN2010105526301A CN201010552630A CN102050946B CN 102050946 B CN102050946 B CN 102050946B CN 2010105526301 A CN2010105526301 A CN 2010105526301A CN 201010552630 A CN201010552630 A CN 201010552630A CN 102050946 B CN102050946 B CN 102050946B
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formula
nano
silicon
poss
film
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CN102050946A (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 ME, 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 polyamide based uv photosensitivity of film-forming resin 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 in solvent, carry out copolyreaction and obtain containing nano-silicon polyamide prepolymer polymers, the mass percent of said three kinds of comonomers is following:
Fragrance acyl chlorides 20%～70%;
Contain nano-silicon component units 1%～10%;
Aromatic amine 20%～70%;
Said fragrant acyl chlorides is to meet chemical general formula; (
Figure DEST_PATH_IMAGE001
) and chemical general formula; At least a in the compound of (
Figure 47127DEST_PATH_IMAGE002
):
Figure DEST_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 929991DEST_PATH_IMAGE010
Or
The said nano-silicon component units that contains is at least a compound that meets chemical general formula ( ):
Figure DEST_PATH_IMAGE013
（
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 556702DEST_PATH_IMAGE016
,
Figure DEST_PATH_IMAGE017
Or
Figure 920818DEST_PATH_IMAGE018
Figure DEST_PATH_IMAGE019
（ ）；
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;
The aromatic amine is in line with the general chemical formula (
Figure 132280DEST_PATH_IMAGE020
), chemical formula (
Figure DEST_PATH_IMAGE021
) and the chemical formula (
Figure 171912DEST_PATH_IMAGE022
) in the compound of at least one of:
Figure DEST_PATH_IMAGE023
（
Figure 288903DEST_PATH_IMAGE020
）；
Figure 891923DEST_PATH_IMAGE024
（
Figure 79934DEST_PATH_IMAGE021
）；
Figure DEST_PATH_IMAGE025
（ ）；
In the formula, R 5, R 6Representative independently of one another
Figure 81705DEST_PATH_IMAGE008
,
Figure 239148DEST_PATH_IMAGE009
,
Figure 799443DEST_PATH_IMAGE010
, ,
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; Said photosensitizers is for meeting the diazo naphthoquinone acyl chlorides of structural formula (
Figure 994538DEST_PATH_IMAGE026
) or structural formula (
Figure DEST_PATH_IMAGE027
), and said photosensitizers is following with the mass percent that contains nano-silicon polyamide prepolymer polymers:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 307839DEST_PATH_IMAGE028
（ ）；
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;
Said solvent is selected from YLENE, 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: in solvent, carry out copolyreaction by fragrant acyl chlorides and two kinds of comonomers of aromatic amine and obtain the polyamide prepolymer polymers, the mass percent of said two kinds of comonomers is following:
Fragrance acyl chlorides 30%～70%;
Aromatic amine 30%～70%;
Said fragrant acyl chlorides is to meet chemical general formula; (
Figure 62278DEST_PATH_IMAGE030
) and chemical general formula; At least a in (
Figure DEST_PATH_IMAGE031
) compound:
Figure 862875DEST_PATH_IMAGE032
（
Figure 149500DEST_PATH_IMAGE030
）；
（
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 559042DEST_PATH_IMAGE007
,
Figure 553674DEST_PATH_IMAGE008
,
Figure 71243DEST_PATH_IMAGE009
,
Figure 846432DEST_PATH_IMAGE010
Or
Figure 225592DEST_PATH_IMAGE011
The aromatic amine is in line with the general chemical formula (
Figure 323998DEST_PATH_IMAGE034
), chemical formula (
Figure DEST_PATH_IMAGE035
) and the chemical formula (
Figure 635637DEST_PATH_IMAGE036
) in the compound of at least one of:
Figure 819494DEST_PATH_IMAGE023
（
Figure 2345DEST_PATH_IMAGE034
）；
Figure DEST_PATH_IMAGE037
（
Figure 33886DEST_PATH_IMAGE035
）；
Figure 893257DEST_PATH_IMAGE038
（
Figure 335651DEST_PATH_IMAGE036
）；
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
Second step: will contain polyamide prepolymer polymers that the nano-silicon component units and the first step make and in solvent, carry out copolyreaction and obtain containing nano-silicon polyamide prepolymer polymers, the said mass percent that contains nano-silicon component units and polyamide prepolymer polymers is following:
Polyamide prepolymer polymers 90%～99%;
Contain nano-silicon component units 1%～10%;
The said nano-silicon component units that contains is at least a compound that meets chemical general formula ( ):
Figure 53629DEST_PATH_IMAGE040
（
Figure 381973DEST_PATH_IMAGE039
）；
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
,
Figure 60822DEST_PATH_IMAGE017
Or
Figure 354532DEST_PATH_IMAGE018
（
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 441753DEST_PATH_IMAGE046
,
Figure DEST_PATH_IMAGE047
,
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
（ ）；
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
, Or
（
Figure 111299DEST_PATH_IMAGE043
）；
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 Chemical general formula (
Figure 869281DEST_PATH_IMAGE042
) and chemical general formula ( ) 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
（
Figure 305389DEST_PATH_IMAGE044
）；
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; Said photosensitizers is for meeting the diazo naphthoquinone acyl chlorides of structural formula (
Figure DEST_PATH_IMAGE061
) or structural formula ( ), and said photosensitizers is following with the mass percent that contains nano-silicon polyamide prepolymer polymers:
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;
Said solvent is selected from YLENE, 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 following:
Figure DEST_PATH_IMAGE063
。
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 compound method.The ratio of POSS in the polyamide prepolymer polymers generally is about 1～10% (mass percent),
。
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.Show as follows:
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, compound method is exemplified below, other is similar:
Figure 528593DEST_PATH_IMAGE066
The nitration reaction of the first step: POSS:
In 500 ml flasks that whisking appliance, TM 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, with the neutralization of 5% sodium carbonate solution, distillation gets thick product after removing tetracol phenixin.Thick then product dissolves back deposition and purification in methyl alcohol in THF, get nitrated POSS after the drying, and yield is 90%.
Second step: the reduction of nitrated POSS:
In 500 ml flasks that whisking appliance, TM and reflux exchanger be housed, add 150 milliliters of THFs (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 in methyl alcohol, precipitates carrying out purifying, gets the pearl powdery solid, yield 95%.
Because the technique scheme utilization, the present invention compared with prior art has 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 one type of new film-forming resin, perhaps will have one type of new film-forming resin of Si8-POSS group introducing polymer molecule chain formation 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, make public with UV-light (g, h, i-line), and 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 ability, 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 whisking appliance, TM, 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 chlorides (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, let reaction mixture delay curtain and be warming up to room temperature (25 ℃) and kept the reaction end 20 hours.With tap funnel reaction mixture is slowly added in 5 liters of pure water under agitation and to make its deposition, 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 whisking appliance, TM, reflux exchanger and nitrogen gangway be housed, add 100 gram prepolymers, 450 gram THFs (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 whisking appliance, TM, 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, let reaction mixture delay curtain and be warming up to room temperature (25 ℃) and kept the reaction end 20 hours.With tap funnel reaction mixture is slowly added in 5 liters of pure water under agitation and to make its deposition, 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 whisking appliance, TM, reflux exchanger and nitrogen gangway be housed, add 100 gram prepolymers, 450 gram THFs (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
Figure DEST_PATH_IMAGE069
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 be with the polyamide prepolymer polymers that obtains to contain 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
30% (mass percent);
Figure DEST_PATH_IMAGE071
60% (mass percent);
Figure 399005DEST_PATH_IMAGE072
10% (mass percent).
The preparation method is with embodiment one.
Embodiment five: a kind of film-forming resin
Figure DEST_PATH_IMAGE073
71% (mass percent);
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
23% (mass percent);
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
45% (mass percent);
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
55% (mass percent);
Figure 838765DEST_PATH_IMAGE076
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; The prescription of adjustment 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 through 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 let 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 in solvent, carry out copolyreaction and obtain containing nano-silicon polyamide prepolymer polymers, the mass percent of said three kinds of comonomers is following:
Fragrance acyl chlorides 20%～70%;
Contain nano-silicon component units 1%～10%;
Aromatic amine 20%～70%;
Said fragrant acyl chlorides is to meet at least a in the compound of chemical general formula (I) and chemical general formula (II):
（I）；
Figure 952277DEST_PATH_IMAGE004
（II）；
In the formula, R 1, R 2Represent H or OH independently of one another; R 3For ,
Figure 675010DEST_PATH_IMAGE006
, , ,
Figure 720393DEST_PATH_IMAGE009
, Or
Figure 800530DEST_PATH_IMAGE011
The said nano-silicon component units that contains is at least a compound that meets chemical general formula (III):
Figure 262047DEST_PATH_IMAGE013
（III）；
In the formula, at least one substituent R fShown in the general molecular formula (IV), remaining substituent R fBe carbonatoms be 1～10 alkyl,
Figure 150478DEST_PATH_IMAGE015
,
Figure 258111DEST_PATH_IMAGE016
,
Figure 279419DEST_PATH_IMAGE017
Or
Figure 890529DEST_PATH_IMAGE018
（
Figure 936949DEST_PATH_IMAGE020
）；
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;
The aromatic amine is in line with the general chemical formula (
Figure 198166DEST_PATH_IMAGE021
), chemical formula (
Figure 663783DEST_PATH_IMAGE022
) and the chemical formula (
Figure 985043DEST_PATH_IMAGE023
) at least one of the compounds:
Figure 365471DEST_PATH_IMAGE024
（
Figure 164799DEST_PATH_IMAGE021
）；
Figure 750502DEST_PATH_IMAGE025
（
Figure 741198DEST_PATH_IMAGE022
）；
Figure 779561DEST_PATH_IMAGE026
（ ）；
In the formula, R 5, R 6Representative independently of one another
Figure 714467DEST_PATH_IMAGE008
,
Figure 111951DEST_PATH_IMAGE009
,
Figure 903189DEST_PATH_IMAGE010
,
Figure 560434DEST_PATH_IMAGE011
,
Figure 120728DEST_PATH_IMAGE007
,
Figure 689113DEST_PATH_IMAGE005
Or
Figure 531429DEST_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; Said photosensitizers is for meeting the diazo naphthoquinone acyl chlorides of structural formula (
Figure 476251DEST_PATH_IMAGE027
) or structural formula (
Figure 953369DEST_PATH_IMAGE028
), and said photosensitizers is following with the mass percent that contains nano-silicon polyamide prepolymer polymers:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 456769DEST_PATH_IMAGE029
（
Figure 957021DEST_PATH_IMAGE027
）；
（ ）。
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;
Said solvent is selected from YLENE, 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: in solvent, carry out copolyreaction by fragrant acyl chlorides and two kinds of comonomers of aromatic amine and obtain the polyamide prepolymer polymers, the mass percent of said two kinds of comonomers is following:
Fragrance acyl chlorides 30%～70%;
Aromatic amine 30%～70%;
The aromatic chloride is consistent with the general chemical formula (
Figure 448810DEST_PATH_IMAGE031
) and the chemical formula (
Figure 436358DEST_PATH_IMAGE032
) at least one of the compounds:
Figure 722982DEST_PATH_IMAGE033
（
Figure 616770DEST_PATH_IMAGE031
）；
（ ）；
In the formula, R 7, R 8Represent H or OH independently of one another, R 9For , ,
Figure 650585DEST_PATH_IMAGE007
,
Figure 111260DEST_PATH_IMAGE008
,
Figure 802004DEST_PATH_IMAGE009
, Or
Figure 152662DEST_PATH_IMAGE011
The aromatic amine is in line with the general chemical formula (
Figure 602098DEST_PATH_IMAGE035
), chemical formula (
Figure 768637DEST_PATH_IMAGE036
) and the chemical formula (
Figure 479805DEST_PATH_IMAGE037
) at least one of the compounds:
（
Figure 10329DEST_PATH_IMAGE035
）；
（ ）；
Figure 850875DEST_PATH_IMAGE039
（
Figure 9323DEST_PATH_IMAGE037
）；
In the formula, R 10, R 11Representative independently of one another
Figure 517665DEST_PATH_IMAGE008
,
Figure 209284DEST_PATH_IMAGE009
,
Figure 410458DEST_PATH_IMAGE010
,
Figure 56203DEST_PATH_IMAGE011
, ,
Figure 917291DEST_PATH_IMAGE005
Or
Figure 289367DEST_PATH_IMAGE007
Second step: will contain polyamide prepolymer polymers that the nano-silicon component units and the first step make and in solvent, carry out copolyreaction and obtain containing nano-silicon polyamide prepolymer polymers, the said mass percent that contains nano-silicon component units and polyamide prepolymer polymers is following:
Polyamide prepolymer polymers 90%～99%;
Contain nano-silicon component units 1%～10%;
The said nano-silicon component units that contains is at least a compound that meets chemical general formula (
Figure 422408DEST_PATH_IMAGE040
):
Figure 104843DEST_PATH_IMAGE041
（
Figure 6940DEST_PATH_IMAGE040
）；
In the formula, at least one substituent R hMeet chemical general formula (
Figure 487600DEST_PATH_IMAGE042
), chemical general formula (
Figure 904675DEST_PATH_IMAGE043
), chemical general formula (
Figure 325554DEST_PATH_IMAGE044
) or chemical general formula (
Figure 19840DEST_PATH_IMAGE045
) shown in, remaining substituent R hBe carbonatoms be 1～10 alkyl, ,
Figure 903669DEST_PATH_IMAGE016
,
Figure 298878DEST_PATH_IMAGE017
Or
Figure 408523DEST_PATH_IMAGE018
（ ）；
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 883870DEST_PATH_IMAGE047
,
Figure 116530DEST_PATH_IMAGE048
,
Figure 437790DEST_PATH_IMAGE049
Or
Figure 988857DEST_PATH_IMAGE050
Figure 53765DEST_PATH_IMAGE051
（
Figure 217897DEST_PATH_IMAGE043
）；
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 444479DEST_PATH_IMAGE052
,
Figure 312203DEST_PATH_IMAGE053
Or
Figure 355432DEST_PATH_IMAGE055
（
Figure 579346DEST_PATH_IMAGE044
）；
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 105006DEST_PATH_IMAGE056
,
Figure 574033DEST_PATH_IMAGE057
,
Figure 635792DEST_PATH_IMAGE058
Or
Figure 204177DEST_PATH_IMAGE059
Figure 482711DEST_PATH_IMAGE060
（
Figure 427534DEST_PATH_IMAGE045
）；
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 346729DEST_PATH_IMAGE061
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; Said photosensitizers is for meeting the diazo naphthoquinone acyl chlorides of structural formula ( ) or structural formula ( ), and said photosensitizers is following with the mass percent that contains nano-silicon polyamide prepolymer polymers:
Photosensitizers 0.5%～15%;
Contain nano-silicon polyamide prepolymer polymers 85%～99.5%;
Figure 334780DEST_PATH_IMAGE029
（
Figure 167869DEST_PATH_IMAGE062
）；
（ ）。
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;
Said solvent is selected from YLENE, 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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