WO2020015665A1 - Semiconductor device and solar cell - Google Patents

Semiconductor device and solar cell Download PDF

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Publication number
WO2020015665A1
WO2020015665A1 PCT/CN2019/096270 CN2019096270W WO2020015665A1 WO 2020015665 A1 WO2020015665 A1 WO 2020015665A1 CN 2019096270 W CN2019096270 W CN 2019096270W WO 2020015665 A1 WO2020015665 A1 WO 2020015665A1
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semiconductor device
polyimide
formula
mol
weight
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PCT/CN2019/096270
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French (fr)
Chinese (zh)
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徐芳荣
李平
池田武史
弓場智之
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东丽先端材料研究开发（中国）有限公司
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Priority to CN201980004450.9A priority Critical patent/CN111344859A/en
Publication of WO2020015665A1 publication Critical patent/WO2020015665A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a semiconductor device and a solar cell, and in particular to a special-composition insulating material used in the device.
  • the design of the smallest electrode spacing of IBC back contact batteries reaches about 20 microns, which has high requirements for insulation, stability, and coating properties.
  • the present invention adopts a material with excellent performance and good balance in terms of cost.
  • the present invention provides a semiconductor device including an insulating material; the insulating material is a thermosetting resin composition.
  • thermosetting resin composition contains soluble polyimide, epoxy-modified polybutadiene, and an organic solvent, with respect to 100 parts by weight of the soluble polyacrylic acid.
  • the epoxy-modified polybutadiene is 20 to 200 parts by weight.
  • soluble polyimide means that more than 5 grams of the target polyimide can be dissolved per 100 grams of solvent in the corresponding solvent.
  • the soluble polyimide is a soluble polyimide having a phenolic hydroxyl group of 0.55mol / kg to 1.0mol / kg. Imide.
  • the soluble polyimide is polymerized from at least three of the dianhydride represented by Formula 1 and the diamine represented by Formula 2 to Formula 4;
  • a mol is represented by A mole
  • B mol is represented by Diamine represented by Formula 2
  • C mole is represented by Diamine represented by Formula 3
  • B / (B + C + D) 0.2 to 0.5
  • the end of the soluble polyimide is at least blocked by an amine derivative or a carboxylic anhydride;
  • Y in Formula 2 is selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond;
  • a in formula 3 is an integer from 0 to 5; when Z is 2 or more, they may be the same or different, and are selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond;
  • M is independent When there are two or more substituents, they may be the same or different, and are each selected from one of an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group, an alkoxy group, or a hydrogen atom;
  • R in Formula 4 is In the case of two or
  • the blocking agent is preferably aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-amino among amine derivatives.
  • phthalic anhydride maleic anhydride, phthalic anhydride is preferred among carboxylic anhydrides
  • thermosetting resin composition further contains at least one or more of an inorganic powder or a colorant.
  • the molar amount of the terminal blocking agent is 5 to 15% of the total molar amount of the diamine.
  • the inorganic powder contains one or more of spherical silica a or talc b; the content of the inorganic powder is 20% by weight in the total solid content
  • the content of the inorganic powder is 50% by weight or less, more preferably 25% by weight or more and 0% by weight or less in the total solid content; and the weight content of the spherical silica a in the inorganic powder is 60 to 100%.
  • the average particle diameter of the spherical silica a is 1 ⁇ m or less; and the average particle diameter of the talc b is 3 ⁇ m or less.
  • the spherical silica a is composed of spherical silica having an average particle diameter of 0.4 to 0.8 micrometers with a weight content of 80 to 95%, and an average of 5 to 20% by weight. Spherical silica with a particle size of 10-20 nm.
  • thermosetting resin composition used in the present invention.
  • the insulating material can be cured at 110 to 400 ° C.
  • the insulating material can be cured at 220-350 ° C.
  • the weight average molecular weight of the soluble polyimide is preferably 10,000 to 32,000.
  • the present invention also provides a solar cell using the above-mentioned insulating material.
  • the invention also provides an IBC back-contact solar cell, and the electrode insulating part of the IBC back-contact solar cell uses the above-mentioned insulating material.
  • the above-mentioned insulation material is selected.
  • the above-mentioned insulating material may be used only in a portion where the electrodes are insulated.
  • the selected insulating material can be fully printed or patterned.
  • the composition of the selected insulating material can be fine-tuned so that it can be coated by screen printing or inkjet printing.
  • the size of the device can be reduced, the amount of material used can be reduced, and the purpose of reducing costs can be achieved.
  • the use of selected insulating materials at the electrodes can reduce the efficiency reduction caused by leakage and improve the stability and service life of the device.
  • FIG. 1 is a plan view of a semiconductor substrate on which p-type semiconductors and n-type semiconductors are fabricated on the same surface, and the plan view point is directly above the p-type semiconductor and the n-type semiconductor.
  • FIG. 2 is a cross-sectional view of the semiconductor substrate shown in FIG. 1 cut transversely from a longitudinal middle portion.
  • FIG. 3 is a cross-sectional view of the device after processing, and the cutting position is the same as that of FIG. 2.
  • FIG. 4 is a top view of the device after processing, and the top point is directly above the electrode surface.
  • Fig. 5 is a plan view of a semiconductor device obtained by performing a series of post-processing after a p-type semiconductor and an n-type semiconductor are fabricated on the same surface, and the plan view point is directly above the p-type semiconductor and the n-type semiconductor.
  • FIG. 6 is a cross-sectional view of the bus electrode along 6a in FIG. 5.
  • FIG. 7 is a cross-sectional view of the bus electrode along 7a in FIG. 5.
  • 1 is an electronic semiconductor.
  • 5 is a main body of a semiconductor substrate.
  • 6a is a bus electrode.
  • the particle diameter of the spherical silica is a test value using a laser diffraction particle size distribution meter.
  • the purity of the bis-anhydride monomer used in the production example may be 97% or more, and preferably 98.5% or more.
  • Dibasic anhydride can be exemplified but not limited to the following: 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride) (BSAA), 4,4'-oxybis-ortho Phthalic anhydride (ODPA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • diamine examples include, but are not limited to, the following: 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (BAHF), bis (3-amino-4-hydroxyphenyl) sulfone (ABPS) , 1,3-bis (3-aminophenoxy) benzene (APB-N), 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (SiDA) .
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane
  • ABPS bis (3-amino-4-hydroxyphenyl) sulfone
  • APIB-N 1,3-bis (3-aminophenoxy) benzene
  • SiDA 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane
  • the end-capping agent may be a general reagent grade purity of 95% or more, and preferably 98% or more.
  • the capping agent is an amine derivative, aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid are preferred.
  • the solvent may be a commonly used industrial grade, preferably an electronic grade.
  • the solvent include, but are not limited to, the following solvents: N-methylpyrrolidone, dimethylacetamide, 1,4-butyrolactone, ⁇ -terpineol, diethylene glycol dimethyl ether, and diethylene glycol monomethyl ether .
  • the epoxy-modified polybutadiene resin has the following optional uses, and the performance can meet the requirements of the present invention: PB4700 (Daicel Corporation.), PB3600 (Daicel Corporation.), NC6000 (Japanese Chemicals), EP-49- 25 (ADEKA), BF1000 (Asahi Chemical Industry Co., Ltd.), R45-EPT (Nagaze Industry Co., Ltd.).
  • the spherical silica gel can be selected from the following products, and the performance can meet the requirements of the present invention: SO-E1 (ADMATECHS Co., Ltd.), SO-E2 (ADMATECHS Co., Ltd.), SO-E3 (ADMATECHS Co.,. Ltd.), SO-E5 (ADMATECHS Co., Ltd.), # 300 (NIPPON AEROSIL CO., LTD).
  • Talc powder can be selected from the following products, and the performance can meet the requirements of the present invention: particle size 1 ⁇ m (Takehara Chemical Industry Co., Ltd.), particle size 2.5 ⁇ m (Takehara Chemical Industry Co., Ltd.), particle size 4 ⁇ m (Takehara Chemical Industry Co., Ltd. ).
  • Titanium dioxide may be selected from A-120 (Sakai Chemical Industry Co., Ltd.).
  • Examples of the inorganic particle dispersant include, but are not limited to, FLOWLENDOPA-100 (Kyodo Chemical Co., Ltd.), FLOWLENDOPA-35 (Kyodo Chemical Co., Ltd.), and FLOWLENG-700 (Kyodo Chemical Co., Ltd.).
  • an electronic semiconductor 1 is fabricated on the surface of a substrate.
  • the n-type impurities used may include Group V elements, such as phosphorus (P) or arsenic (As).
  • the processing method may use POCl 3 thermal diffusion and phosphorus slurry thermal diffusion. Or an ion implantation method using phosphane.
  • the p-type impurity used may include a group III element, such as boron (B), aluminum (Al), or gallium (Ga).
  • the processing method may use BBr 3 or BCl 3 thermal diffusion, boron
  • the slurry is thermally diffused, or ion implantation is used.
  • the semiconductor substrate may be a hole type semiconductor or an electronic type semiconductor.
  • 5 is an electronic semiconductor substrate.
  • the passivation insulating layer 4 in FIG. 3 is formed of at least one of silicon oxide (SiO x ), silicon nitride (SiN x ), or aluminum oxide (Al 2 O x ).
  • the processing method may use plasma enhanced chemical vapor deposition ( PECVD) method.
  • it may be formed as a single silicon oxide (SiO x ) layer, a single silicon nitride (SiN x ) layer or a single silicon oxynitride (SiO x N y ) layer, or include silicon oxide (SiO x ), silicon nitride ( SiN x ), and a composite layer of silicon oxynitride (SiO x N y ).
  • the processing method can be by using chemical deposition (CVD), sputtering or spin coating.
  • the electrodes 6 and 7 and the bus electrodes 6a and 7a in FIG. 4 may include silver (Ag), gold (Au), copper (Cu), aluminum (Al), or an alloy thereof. All the electrodes 6 converge on the bus electrode 6a, and all the electrodes 7 converge on the bus electrode 7a.
  • the electrode uses a printing method to print a conductive paste at the corresponding position, and the required electrode is obtained after pre-baking and high temperature sintering.
  • a passivation insulating layer 4 made of silicon oxide (SiO x), silicon nitride (SiN x) or aluminum oxide (Al 2 O x) in at least one of forming a plasma processing method can be used to enhance Chemical vapor deposition (PECVD) method.
  • the electrodes 6 and 7 and the bus electrodes 6a and 7a may include silver (Ag), gold (Au), copper (Cu), aluminum (Al), or an alloy thereof. All the electrodes 6 converge on the bus electrode 6a, and all the electrodes 7 converge on the bus electrode 7a.
  • the electrode uses a printing method to print a conductive paste at the corresponding position, and the required electrode is obtained after pre-baking and high temperature sintering.
  • the antireflection layer 8 is made of silicon oxide (SiO x ), silicon nitride (SiN x ), silicon oxynitride (SiO x N y ), titanium oxide (TiO x ), zinc oxide (ZnO), or sulfide. At least one of zinc (ZnS) is formed.
  • the semiconductor device is an IBC back-contact solar cell.
  • Examples of the method for preparing the polyimide composition used in the present invention are as follows, but the monomer, composition, and reaction conditions are not limited thereto.
  • polyimide resin 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.5 Moles of 1,4-diaminobenzene and 0.3 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, a terminal blocking agent of 0.01 mol of phthalic anhydride was added to perform a blocking reaction for 15 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 50 grams of titanium dioxide A-120 as an inorganic filler and stir thoroughly to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mol 4,4'-oxybisphthalic anhydride, 0.24 mol 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.32 Moles of 1,4-diaminobenzene and 0.44 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, a terminal blocking agent of 0.01 mol of phthalic anhydride was added to perform a blocking reaction for 15 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 30 grams of titanium dioxide A-120 as an inorganic filler and stir well to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1.1 moles of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 moles of 3,3' -Diamino-4,4'-dihydroxybiphenyl, 0.2 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 1,3-bis (3-aminopropyl) -1,1, 3,3-tetramethyldisiloxane was added to N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours, and then a capping agent of 0.01 mole of aniline was added for capping reaction for 15 minutes to obtain polyimide.
  • Polyamic acid the precursor of amines. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 50 g of inorganic filler talc powder b with an average particle diameter of 4 ⁇ m was added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole 4,4' -Diamino-2,2'-dihydroxybiphenyl, 0.5 mole 4,4'-diaminodiphenylmethane and 0.2 mole 3-bis (3-aminopropyl) -1,1,3,3-tetra Methyldisiloxane was added to N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours, and then a capping agent of 0.01 mole of phthalic anhydride was added for capping reaction for 15 minutes to obtain a polyimide Precursor of polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 15 grams of inorganic filler with a mean particle diameter of 1 micrometer spherical silica a and 60 grams of talc powder with an average particle diameter of 4 micrometers b were added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 0.9 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 900 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C.
  • polyamic acid precursor polyamic acid was obtained.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of polyimide solid was dissolved in 200 g of N-methylpyrrolidone, and then 80 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then 108 g of inorganic filler having a mean particle diameter of 0.4 micron silica a and 72 g of talc powder b having an average particle diameter of 2.5 ⁇ m were added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.45 moles of 1,3-bis (3-aminophenoxy) benzene and 0.25 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 900 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C. for 2 hours under a nitrogen stream, a blocking agent of 0.11 mole of phthalic anhydride was added to perform the blocking reaction. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to form a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 170 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 160 g of inorganic filler silica a (silica a: consisting of 144 g of silica with an average particle size of 0.5 ⁇ m, 16 g of silica with an average particle size of 18 nm) 40 g of average particle size It is talcum powder b of 2.5 micrometers, and it is fully mixed to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1.1 moles of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 0.2 moles of bis (3-amino-4-hydroxyphenyl) sulfone, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 750 g of N In methylpyrrolidone, polymerization was performed at 70 to 80 ° C.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of polyimide solid was dissolved in 220 g of N-methylpyrrolidone, and then 200 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 90 g of silica a, an inorganic filler (silica a: consisting of 85.5 g of silica with an average particle size of 0.7 ⁇ m, and 4.5 g of silica with an average particle size of 20 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of bis (3-amino-4-hydroxyphenyl) sulfone, 0.5 mole of 4,4 '-Diaminodiphenylmethane and 0.3 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 700 g of N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, an end-capping agent, 0.1 mol of aniline was added, and the end-capping reaction was performed for 17 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of a polyimide solid was dissolved in 170 g of N-methylpyrrolidone, and then 140 g of an epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 100 g of silica a, an inorganic filler (silica a: consisting of 90 g of silica having an average particle diameter of 0.6 ⁇ m and 10 g of silica having an average particle diameter of 14 nm) was added, and the mixture was thoroughly stirred to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours.
  • an end-capping agent 0.1 mole of aniline, was added for end-capping reaction for 17 minutes to obtain polyimide.
  • Polyamic acid the precursor of amines.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of polyimide solid was dissolved in a mixed solvent of 200 g of N-methylpyrrolidone and 160 g of ⁇ -terpineol, and then 140 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 grams of inorganic filler silica a (silica a: consisting of 90 grams of silica with an average particle size of 0.8 microns, 10 grams of silica with an average particle size of 10 nanometers) and 10 grams of average particle size. The talc powder b having a diameter of 1 micron was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1.2 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C.
  • polyamic acid precursor polyamic acid was obtained.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 450 grams of 1,4-butyrolactone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 70 grams of inorganic filler silica a (silica a: consisting of 63 grams of silica with an average particle size of 0.4 microns, 7 grams of silica with an average particle size of 12 nm) and 30 grams of average particle size.
  • the talc powder b having a diameter of 4 micrometers was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.25 mole of bis (3- Amino-4-hydroxyphenyl) sulfone, 0.4 moles of 3,3'-diaminodiphenylsulfone, and 0.35 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisilazyl Alkane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of polyimide solid was dissolved in a mixed solvent of 60 g of N-methylpyrrolidone and 100 g of 1,4-butyrolactone, and then 100 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. . Then add 100 g of silica a, an inorganic filler (silica a: consisting of 85 g of silica with an average particle size of 0.5 ⁇ m, 15 g of silica with an average particle size of 12 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4'-oxybisphthalic anhydride, 1 mole of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoro Propane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.18 mol of aniline was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 170 grams of N-methylpyrrolidone to form the polyimide composition required for the present invention.
  • polyimide resin 1 mole of 4,4'-oxybisphthalic anhydride, 1 mole of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoro Propane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.18 mol of aniline was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 220 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.6 mol of 1,3-bis (3-aminophenoxy) benzene was added to 800 g of N-methylpyrrolidone, and 70 to 80 under nitrogen flow. After polymerizing at 2 ° C for 2 hours, an end-capping agent, 0.11 mol of phthalic anhydride, was added for an end-capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 300 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.2 mol of 2-aminobenzenesulfonic acid was added as a capping agent to perform a capping reaction for 20 minutes. To obtain polyamic acid precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of diethylamine was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polymer.
  • Polyamic acid the precursor of imide.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of aniline as a capping agent was added for capping reaction for 20 minutes to obtain polyimide.
  • Polyamic acid the precursor of amines.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of aniline as a capping agent was added for capping reaction for 20 minutes to obtain polyimide.
  • Polyamic acid the precursor of amines.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved to form the polyimide composition required by the present invention.
  • polyimide resin 1 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C.
  • polyamic acid precursor polyamic acid was obtained.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of a polyimide solid was dissolved in 190 g of N-methylpyrrolidone, and then 70 g of an epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 g of silica a, an inorganic filler (silica a: consisting of 85 g of silica with an average particle size of 0.6 ⁇ m, 15 g of silica with an average particle size of 14 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.2 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.09 mole of phthalic anhydride was added as a capping agent to perform a capping reaction. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 g of polyimide solid was dissolved in 130 g of N-methylpyrrolidone, and then 90 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 100 g of silica a, an inorganic filler (silica a: consisting of 70 g of silica having an average particle size of 0.2 ⁇ m and 30 g of silica having an average particle size of 15 nm) was added, and the mixture was thoroughly stirred to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C for 2 hours under a nitrogen stream, a capping agent of 0.01 mole of 2-aminobenzenesulfonic acid was added for capping. The reaction was performed for 20 minutes to obtain polyamic acid precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 165 grams of N-methylpyrrolidone, and then 90 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 g of inorganic filler silica a (silica a: consisting of 70 g of silica with an average particle size of 1 micron and 30 g of silica with an average particle size of 18 nm) and stir thoroughly well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.5 Moles of 1,4-diaminobenzene and 0.3 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen
  • an end-capping agent was added to 0.1 mol of phthalic anhydride to perform an end-capping reaction for 15 minutes to obtain a polyimide precursor polyamic acid.
  • the obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 110 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 50 grams of inorganic filler titanium dioxide A-120 and 15 grams of inorganic particle dispersant FLOWLENDOPA-100 and stir well to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • polyimide resin 1 mole of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 0.2 mole of bis (3-amino-4-hydroxyphenyl) sulfone, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 750 g of N -In methylpyrrolidone, polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.5 mol of aniline, a capping agent, was added for capping reaction for 17 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
  • the obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used.
  • methods using solids 100 grams of polyimide solid was dissolved in 180 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 90 grams of inorganic filler silica a (silica a: consisting of 85.5 grams of silica with an average particle size of 0.7 microns, 4.5 grams of silica with an average particle size of 20 nm), 9 grams of inorganic particles
  • the dispersant FLOWLENDOPA-100 is fully stirred to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BCl 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, mask B on one side of the mask is removed by one-sided cleaning, and then mask C is formed on the hole semiconductor formed by diffusion; POCl 3 diffusion is performed to form an electronic semiconductor;
  • Remove the barrier layer A and the mask C form an antireflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print the polyimide (PI) insulating material of Preparation Example 1, and the line width of the printed pattern is 150 Micron, adjacent line and line spacing of 30 microns, thickness of 10 microns, dried and then cured at 390 ° C for 4 minutes; printed on the surface of the cavity type semiconductor and electronic type semiconductor by screen printing electrode material, and then sintered to complete the IBC Production of back
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove barrier layer A and mask C; form anti-reflection layer on the side where barrier layer A is removed, and passivation layer on the other side; print polyimide (PI) insulation material of Preparation Example 2 with a line width of 155 Micron, adjacent line and line spacing of 20 microns, thickness of 10 microns, and then cured at 120 ° C for 20 minutes after drying; use screen printing to print electrode materials on the surface of hole-type semiconductors and electronic semiconductors, and then sinter to complete IBC Production of back contact batteries.
  • PI polyimide
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then, the fine grid of the electrode is sintered; then, the polyimide (PI) insulation material of Preparation Example 3 is printed, and the printed pattern is shown in FIG. 5 as the 3 insulation material, and it is directly cured at 260 ° C for 10 minutes; The bus electrodes 6a and 7a are printed as shown in FIG. 5, and the production of the IBC back-contact battery is completed after sintering.
  • PI polyimide
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin TCA-7020C (Taichang Resin (Foshan) Co., Ltd.) insulation material.
  • the printed pattern is shown as 3 insulation material in Figure 5, and it is directly cured at 200 ° C for 15 minutes. ; Then, the bus electrodes 6a and 7a shown in FIG. 5 are printed at corresponding positions, and the production of the IBC back contact battery is completed after sintering.
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin HK-100 / W (Guangdong Sanqiu Guanggu Material Co., Ltd.) insulation material, and print the pattern as shown in 3 insulation material in Figure 5, and directly go to 200 ° C Cure for 15 minutes; then, bus electrodes 6a and 7a as shown in FIG. 5 are printed at corresponding positions, and the IBC back-contact battery is completed after sintering. Note: Before using the above HK-100 / W, the
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin LR-7568 (Japan Mitsubishi Chemical) insulation material, and print the pattern as shown in 3 insulation material in Figure 5, and directly cure at 200 ° C for 15 minutes; The bus electrodes 6a and 7a are printed as shown in FIG. 5, and the production of the IBC back-contact battery is completed after sintering.
  • the composition used in Comparative Example 1 was selected from UV-curable aromatic polyurethane acrylate UV-3722 (Dongguan Inshang Chemical Technology Co., Ltd.). This composition does not contain the epoxy resin and silica a of the present invention. And talcum powder b.
  • a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BCl 3 diffusion was performed to make a mask B on the silicon wafer.
  • a local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove barrier layer A and mask C; form anti-reflection layer on the side where barrier layer A is removed, and passivation layer on the other side; print UV-3722 insulation material as a contrast material, the line width of the printed pattern is 150 microns, and The line-to-line spacing is 30 micrometers and the thickness is 10 micrometers, and then UV curing is performed for 15 minutes. Screen printing is used to print electrode materials on the surface of hole-type semiconductors and electronic semiconductors, and then sintering is completed to make the IBC back-contact battery
  • Table 1 shows the performance immediately after the battery is manufactured
  • Table 2 shows the performance of the battery sheet in Table 1 after being heated at 300 ° C for 240 minutes.
  • the battery prepared by the insulating material used in the present invention has superior performance to the battery sheet prepared by using other insulating materials in Comparative Example 1. Moreover, in experiments testing high temperature resistance, its stability is also better than that of comparative materials. Because the use temperature of solar cells is relatively high, and the life of the general battery is about 25 years. In order to ensure the service life, an insulating material with excellent insulation and stability must be used. The PI insulation material selected by the present invention can undoubtedly provide better protection.

Abstract

Provided is a semiconductor device including an insulating material (3). The insulating material (3) is a thermosetting resin composition. The thermosetting resin composition can be used to improve device performance by reducing current leakage. The excellent stability of the material can also extend the service life of the device. The material can be cured at both a high and low temperature, and is particularly suited for a device manufactured under low temperature conditions.

Description

一种半导体器件及太阳能电池Semiconductor device and solar cell 技术领域Technical field
本发明涉及一种半导体器件及太阳能电池，具体涉及一种在所述器件中使用的特殊组成的绝缘材料。The invention relates to a semiconductor device and a solar cell, and in particular to a special-composition insulating material used in the device.
背景技术Background technique
在以往的半导体或者太阳能电池的制造中，特别是导电电极或者导线之间距离非常近的情况下，需要在电极之间或者导线之间引入具有高绝缘性的绝缘材料。现有技术中虽然有使用绝缘材料，但是仍然存在一些不足。比如使用的丙烯酸树脂，其耐高温性能不足，导致半导体器件的后期加工操作余地很小。也有使用聚酰胺、聚酰亚胺，但是所使用材料价格昂贵、绝缘性能的稳定性不足、热稳定性不足，需要较高的固化温度以及多阶段固化带来的工艺复杂化而导致成本升高。In the manufacture of conventional semiconductors or solar cells, particularly when the distance between conductive electrodes or wires is very close, it is necessary to introduce an insulating material having high insulation between the electrodes or between the wires. Although insulation materials are used in the prior art, there are still some shortcomings. For example, the acrylic resin used has insufficient high-temperature resistance, resulting in little room for post-processing operations of semiconductor devices. There are also polyamides and polyimides, but the materials used are expensive, the insulation performance is not stable enough, the thermal stability is insufficient, the higher curing temperature is required and the process complexity caused by multi-stage curing leads to higher costs .
特别是在一些特殊应用场合，比如IBC背接触电池的电极间距最小的设计方案达到了20微米左右，对绝缘性、稳定性、涂布性都有很高的要求。Especially in some special applications, for example, the design of the smallest electrode spacing of IBC back contact batteries reaches about 20 microns, which has high requirements for insulation, stability, and coating properties.
发明内容Summary of the invention
为了解决现有半导体器件制造中，对高绝缘性能、高热稳定性、可一次性固化材料的需求，本发明采用了一种各项性能优异、在成本方面也能达到良好均衡的材料。In order to solve the demand for high insulation performance, high thermal stability, and one-time curable materials in the manufacture of existing semiconductor devices, the present invention adopts a material with excellent performance and good balance in terms of cost.
本发明提供了一种半导体器件，所述半导体器件中包含绝缘材料；所述绝缘材料为热固性树脂组合物。The present invention provides a semiconductor device including an insulating material; the insulating material is a thermosetting resin composition.
为了具有良好的绝缘性和热固化工艺适配，优选所述热固性树脂组合物包含可溶性聚酰亚胺、环氧改性聚丁二烯以及有机溶剂，相对于100重量份的所述可溶性聚酰亚胺而言，所述环氧改性聚丁二烯为20～200重量份。In order to have good insulation and thermal curing process adaptation, it is preferred that the thermosetting resin composition contains soluble polyimide, epoxy-modified polybutadiene, and an organic solvent, with respect to 100 parts by weight of the soluble polyacrylic acid. In terms of imines, the epoxy-modified polybutadiene is 20 to 200 parts by weight.
在本文中使用时，“可溶性聚酰亚胺”表示在相应的溶剂中每100克溶剂可溶解5克以上的目标聚酰亚胺。As used herein, "soluble polyimide" means that more than 5 grams of the target polyimide can be dissolved per 100 grams of solvent in the corresponding solvent.
为了提高聚酰亚胺可溶性的同时又不降低热稳定性、并降低成膜后的曲翘，进一步优选所述可溶性聚酰亚胺为具有0.55mol/kg～1.0mol/kg苯酚羟基的可溶性聚酰亚胺。In order to improve the solubility of polyimide without reducing thermal stability and reducing warpage after film formation, it is further preferred that the soluble polyimide is a soluble polyimide having a phenolic hydroxyl group of 0.55mol / kg to 1.0mol / kg. Imide.
为了达到成本和性能的均衡，所述可溶性聚酰亚胺由式1所示的二酸酐和式2至式4所示的二胺中的至少三种聚合而成；其中将式1所示的二酸酐作为A摩尔、式2所示的二胺作为B摩尔、式3所示的二胺作为C摩尔、式4所示的二胺作为D摩尔时，满足A/(B+C+D)＝0.85～1.2、B/(B+C+D)＝0.2～0.5，并且所述可溶性聚酰亚胺的末端至少由胺衍生物或者羧酸酐进行封端；To achieve a cost and performance balance, the soluble polyimide is polymerized from at least three of the dianhydride represented by Formula 1 and the diamine represented by Formula 2 to Formula 4; When A mol is represented by A mole, B mol is represented by Diamine represented by Formula 2, C mole is represented by Diamine represented by Formula 3, and D mole represented by Diamine represented by Formula 4, satisfies A / (B + C + D). = 0.85 to 1.2, B / (B + C + D) = 0.2 to 0.5, and the end of the soluble polyimide is at least blocked by an amine derivative or a carboxylic anhydride;
Figure PCTCN2019096270-appb-000001
Figure PCTCN2019096270-appb-000001
Figure PCTCN2019096270-appb-000002
Figure PCTCN2019096270-appb-000002
其中，式2中的Y为选自-CO-、-SO2-、-O-、-S-、-CH 2-、-NHCO-、-C(CH 3) 2-、-C(CF 3) 2-、-COO-或单键中的一种；式3中的a为0～5的整数；Z为2个以上的情况下可以相同或不同，分别选自-CO-、-SO2-、-O-、-S-、-CH 2-、-NHCO-、-C(CH 3) 2-、-C(CF 3) 2-、-COO-或单键中的一种；M为独立的取代基，为2个以上的情况下可以相同或不同，分别选自碳原子数1～3的烷基、氟化烷基、烷氧基或者氢原子中的一种；式4中的R为2个以上的情况下可以相同或不同，分别选自碳原子数1～3的烷基或含有一个苯环的芳基中的任意一个；l以及m各自独立地为1～6的整数；n为1～10的整数。为了可以达到良好的封端效果，并能得到性能稳定的聚合物，封端剂在胺衍生物中优选苯胺、2-氨基苯甲酸、3-氨基苯甲酸、4-氨基苯甲酸、4-氨基水杨酸、5-氨基水杨酸、6-氨基水杨酸、2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸、2-氨基苯酚、3-氨基苯酚、4-氨基苯酚、2-氨基苯硫酚、3-氨基苯硫酚或4-氨基苯硫酚中的一种或多种；在羧酸酐中优选邻苯二甲酸酐、马来酸酐、邻苯二甲酸酐、环己烷二羧酸酐、5-降冰片烯-2,3-二羧酸酐、1,2-二羧基萘酐或3-羟基邻苯二甲酸酐中的一种或多种。 Wherein Y in Formula 2 is selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond; a in formula 3 is an integer from 0 to 5; when Z is 2 or more, they may be the same or different, and are selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond; M is independent When there are two or more substituents, they may be the same or different, and are each selected from one of an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group, an alkoxy group, or a hydrogen atom; R in Formula 4 is In the case of two or more, they may be the same or different, and are respectively selected from any one of an alkyl group having 1 to 3 carbon atoms or an aryl group containing a benzene ring; l and m are each independently an integer of 1 to 6; n It is an integer from 1 to 10. In order to achieve a good blocking effect and obtain a stable polymer, the blocking agent is preferably aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-amino among amine derivatives. Salicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4 One or more of -aminophenol, 2-aminothiophenol, 3-aminothiophenol, or 4-aminothiophenol; phthalic anhydride, maleic anhydride, phthalic anhydride is preferred among carboxylic anhydrides One or more of formic anhydride, cyclohexanedicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2-dicarboxynaphthalic anhydride, or 3-hydroxyphthalic anhydride.
为了可以达到更低固化温度，所选绝缘材料中含有的环氧改性聚丁二烯为式5所示：In order to achieve a lower curing temperature, the epoxy-modified polybutadiene contained in the selected insulating material is shown in Formula 5:
Figure PCTCN2019096270-appb-000003
Figure PCTCN2019096270-appb-000003
其中，式5中的x为5～20的整数；y为2～8的整数；z为3～12的整 数。为了提高耐热性以及可调节涂布性能，优选所述热固性树脂组合物还包含无机粉末、或者染色剂中的至少一种或多种。Here, x in Formula 5 is an integer of 5 to 20; y is an integer of 2 to 8; and z is an integer of 3 to 12. In order to improve heat resistance and adjust coating performance, it is preferable that the thermosetting resin composition further contains at least one or more of an inorganic powder or a colorant.
为了控制合适的分子量以及提高材料稳定性，相对所述二胺而言，所述封端剂的摩尔量为二胺总摩尔量的5～15％。In order to control a suitable molecular weight and improve material stability, relative to the diamine, the molar amount of the terminal blocking agent is 5 to 15% of the total molar amount of the diamine.
为了进一步提高耐热性和调整涂布特性，优选所述无机粉末含有球状二氧化硅a，或滑石粉b的一种或多种；所述无机粉末的含量在全部固体成分中为20重量％以上50重量％以下、进一步优选所述无机粉末的含量在全部固体成分中为25重量％以上0重量％以下；并且，无机粉末中，球状二氧化硅a的重量含量为60～100％。In order to further improve heat resistance and adjust coating characteristics, it is preferred that the inorganic powder contains one or more of spherical silica a or talc b; the content of the inorganic powder is 20% by weight in the total solid content The content of the inorganic powder is 50% by weight or less, more preferably 25% by weight or more and 0% by weight or less in the total solid content; and the weight content of the spherical silica a in the inorganic powder is 60 to 100%.
为了提高均匀性和存放稳定性，所述球状二氧化硅a的平均粒径为1微米以下；滑石粉b的平均粒径为3微米以下。In order to improve uniformity and storage stability, the average particle diameter of the spherical silica a is 1 μm or less; and the average particle diameter of the talc b is 3 μm or less.
为了进一步提升均匀性和保存稳定性，所述球状二氧化硅a由重量含量为80～95％的平均粒径为0.4～0.8微米的球状二氧化硅、和重量含量为5～20％的平均粒径为10～20纳米的球状二氧化硅组成。In order to further improve uniformity and storage stability, the spherical silica a is composed of spherical silica having an average particle diameter of 0.4 to 0.8 micrometers with a weight content of 80 to 95%, and an average of 5 to 20% by weight. Spherical silica with a particle size of 10-20 nm.
为了更高限度地提高组成物的保存稳定性，在本发明所使用的热固性树脂组合物中引入了无机粒子分散剂。In order to improve the storage stability of the composition to a higher extent, an inorganic particle dispersant is introduced into the thermosetting resin composition used in the present invention.
为了适用各种工艺，拓宽可进行操作的条件范围，优选所述绝缘材料可以在110～400℃进行固化。In order to apply various processes and widen the range of operating conditions, it is preferable that the insulating material can be cured at 110 to 400 ° C.
为了提高生产效率，更进一步优选所述绝缘材料可以在220～350℃进行固化。In order to improve production efficiency, it is further preferred that the insulating material can be cured at 220-350 ° C.
为了良好的机械性能和耐热性能，优选所述可溶性聚酰亚胺的重均分子量为10000～32000。For good mechanical properties and heat resistance, the weight average molecular weight of the soluble polyimide is preferably 10,000 to 32,000.
本发明还提供了一种太阳能电池，所述太阳能电池使用了上述的绝缘材 料。The present invention also provides a solar cell using the above-mentioned insulating material.
本发明还提供了一种IBC背接触太阳能电池，所述IBC背接触太阳能电池的电极绝缘部分使用了上述的绝缘材料。The invention also provides an IBC back-contact solar cell, and the electrode insulating part of the IBC back-contact solar cell uses the above-mentioned insulating material.
因为IBC背接触电池电极间的间距更接近，所以为了满足绝缘性能的要求，得到高性能的IBC背接触太阳能电池，选择上述绝缘材料。Because the distance between the IBC back-contact battery electrodes is closer, in order to meet the requirements of insulation performance, to obtain a high-performance IBC back-contact solar cell, the above-mentioned insulation material is selected.
为了降低成本，可仅在电极绝缘的部分使用上述绝缘材料。In order to reduce the cost, the above-mentioned insulating material may be used only in a portion where the electrodes are insulated.
为了适用各种设计方案，所选绝缘材料可以全面印刷或图案化印刷。In order to apply a variety of design solutions, the selected insulating material can be fully printed or patterned.
为了适用各种应用要求，可通过对所选绝缘材料的组成的微调，从而能够使用丝网印刷、或者喷墨印刷进行涂布。In order to meet various application requirements, the composition of the selected insulating material can be fine-tuned so that it can be coated by screen printing or inkjet printing.
本发明的有益效果在于：The beneficial effects of the present invention are:
由于选择了比现用绝缘材料性能好的材料，所以可以减小器件的尺寸，减少材料使用量，达到降低成本的目的。特别对于IBC背接触太阳能电池，在电极处使用所选绝缘材料，可以减少漏电导致的效率降低，提升器件稳定性和使用寿命。Since a material with better performance than the current insulating material is selected, the size of the device can be reduced, the amount of material used can be reduced, and the purpose of reducing costs can be achieved. Especially for IBC back-contact solar cells, the use of selected insulating materials at the electrodes can reduce the efficiency reduction caused by leakage and improve the stability and service life of the device.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为在同一面上制作了p型半导体和n型半导体的半导体基板的俯视图，俯视点为p型半导体和n型半导体这一面的正上方。FIG. 1 is a plan view of a semiconductor substrate on which p-type semiconductors and n-type semiconductors are fabricated on the same surface, and the plan view point is directly above the p-type semiconductor and the n-type semiconductor.
图2为图1所示半导体基板从纵向中间部位横向切割的断面图。FIG. 2 is a cross-sectional view of the semiconductor substrate shown in FIG. 1 cut transversely from a longitudinal middle portion.
图3为加工完成后的器件断面图，切割位置与图2相同。FIG. 3 is a cross-sectional view of the device after processing, and the cutting position is the same as that of FIG. 2.
图4为加工完成后的器件的俯视图，俯视点为电极面的正上方。FIG. 4 is a top view of the device after processing, and the top point is directly above the electrode surface.
图5为在同一面上制作了p型半导体和n型半导体后，进行一系列后加工所得到的半导体器件的俯视图，俯视点为p型半导体和n型半导体这一面 的正上方。Fig. 5 is a plan view of a semiconductor device obtained by performing a series of post-processing after a p-type semiconductor and an n-type semiconductor are fabricated on the same surface, and the plan view point is directly above the p-type semiconductor and the n-type semiconductor.
图6为沿着图5中6a汇流电极的横向切割断面图。FIG. 6 is a cross-sectional view of the bus electrode along 6a in FIG. 5.
图7为沿着图5中7a汇流电极的横向切割断面图。FIG. 7 is a cross-sectional view of the bus electrode along 7a in FIG. 5. FIG.
其中，among them,
1为电子型半导体。1 is an electronic semiconductor.
2为空穴型半导体。2 is a hole-type semiconductor.
3为绝缘材料。3 is an insulating material.
4为钝化绝缘层。4 is a passivation insulating layer.
5为半导体基板的本体。5 is a main body of a semiconductor substrate.
6为电极。6 is an electrode.
6a为汇流电极。6a is a bus electrode.
7为电极。7 is an electrode.
7a为汇流电极。7a is a bus electrode.
8为减反射层。8 is an antireflection layer.
球状二氧化硅的粒径说明：Explanation of the particle size of spherical silica:
球状二氧化硅的粒径为采用激光衍射式粒度分布计的测试值。The particle diameter of the spherical silica is a test value using a laser diffraction particle size distribution meter.
具体实施方式detailed description
现在开始参照附图更详尽地描述本发明。The invention will now be described in more detail with reference to the drawings.
制备例中所使用的双二酸酐单体纯度97％以上即可、优选98.5％以上。双二酸酐可以列举但不限于以下物质：4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)(BSAA)、4,4'-氧双邻苯二甲酸酐(ODPA)、3,3',4,4'-联苯四羧酸二酐(BPDA)。二胺可以列举但不限于以下物质：2,2-双(3-氨基-4-羟基苯基)- 六氟丙烷(BAHF)、双(3-氨基-4-羟苯基)砜(ABPS)、1,3-双(3-氨基苯氧基)苯(APB-N)、3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷(SiDA)。The purity of the bis-anhydride monomer used in the production example may be 97% or more, and preferably 98.5% or more. Dibasic anhydride can be exemplified but not limited to the following: 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride) (BSAA), 4,4'-oxybis-ortho Phthalic anhydride (ODPA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA). Examples of the diamine include, but are not limited to, the following: 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (BAHF), bis (3-amino-4-hydroxyphenyl) sulfone (ABPS) , 1,3-bis (3-aminophenoxy) benzene (APB-N), 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (SiDA) .
封端剂为普通试剂级纯度95％以上即可、优选98％以上。封端剂为胺衍生物时，优选苯胺、2-氨基苯甲酸、3-氨基苯甲酸、4-氨基苯甲酸、4-氨基水杨酸、5-氨基水杨酸、6-氨基水杨酸、2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸、2-氨基苯酚、3-氨基苯酚、4-氨基苯酚、2-氨基苯硫酚、3-氨基苯硫酚或4-氨基苯硫酚中的一种或多种；在羧酸酐中优选邻苯二甲酸酐、马来酸酐、邻苯二甲酸酐、环己烷二羧酸酐、5-降冰片烯-2,3-二羧酸酐、1,2-二羧基萘酐或3-羟基邻苯二甲酸酐中的一种或多种。The end-capping agent may be a general reagent grade purity of 95% or more, and preferably 98% or more. When the capping agent is an amine derivative, aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid are preferred. , 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol Or one or more of 4-aminothiophenol; phthalic anhydride, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, 5-norbornene-2 is preferred among carboxylic anhydrides One or more of 1,3-dicarboxylic anhydride, 1,2-dicarboxynaphthalic anhydride or 3-hydroxyphthalic anhydride.
溶剂为常用的工业级即可、优选电子级的溶剂。溶剂可列举但不限于以下溶剂：N-甲基吡咯烷酮、二甲基乙酰胺、1,4-丁内酯、α-松油醇、二乙二醇二甲醚、二乙二醇单甲醚。The solvent may be a commonly used industrial grade, preferably an electronic grade. Examples of the solvent include, but are not limited to, the following solvents: N-methylpyrrolidone, dimethylacetamide, 1,4-butyrolactone, α-terpineol, diethylene glycol dimethyl ether, and diethylene glycol monomethyl ether .
环氧改性聚丁二烯树脂有如下可选择使用，并且性能都能达到本发明的要求：PB4700(Daicel Corporation.)、PB3600(Daicel Corporation.)、NC6000(日本化药)、EP-49-25(ADEKA/艾迪科)、BF1000(旭电化工株式会社)、R45-EPT(长濑产业株式会社)。The epoxy-modified polybutadiene resin has the following optional uses, and the performance can meet the requirements of the present invention: PB4700 (Daicel Corporation.), PB3600 (Daicel Corporation.), NC6000 (Japanese Chemicals), EP-49- 25 (ADEKA), BF1000 (Asahi Chemical Industry Co., Ltd.), R45-EPT (Nagaze Industry Co., Ltd.).
球状硅胶可选自如下产品，并且性能都能达到本发明的要求：SO-E1(ADMATECHS Co.,Ltd.)、SO-E2(ADMATECHS Co.,Ltd.)、SO-E3(ADMATECHS Co.,Ltd.)、SO-E5(ADMATECHS Co.,Ltd.)、#300(NIPPON AEROSIL CO.,LTD)。The spherical silica gel can be selected from the following products, and the performance can meet the requirements of the present invention: SO-E1 (ADMATECHS Co., Ltd.), SO-E2 (ADMATECHS Co., Ltd.), SO-E3 (ADMATECHS Co.,. Ltd.), SO-E5 (ADMATECHS Co., Ltd.), # 300 (NIPPON AEROSIL CO., LTD).
滑石粉可选自如下产品，并且性能都能达到本发明的要求：粒径1μm(竹原化学工业株式会社)、粒径2.5μm(竹原化学工业株式会社)、粒径4μm(竹原化学工业株式会社)。Talc powder can be selected from the following products, and the performance can meet the requirements of the present invention: particle size 1 μm (Takehara Chemical Industry Co., Ltd.), particle size 2.5 μm (Takehara Chemical Industry Co., Ltd.), particle size 4 μm (Takehara Chemical Industry Co., Ltd. ).
二氧化钛可以选自A-120(堺化学工业株式会社)。Titanium dioxide may be selected from A-120 (Sakai Chemical Industry Co., Ltd.).
无机粒子分散剂可列举但不限于FLOWLENDOPA-100(共栄社化学株式会社)、FLOWLENDOPA-35(共栄社化学株式会社)、FLOWLENG-700(共栄社化学株式会社)。Examples of the inorganic particle dispersant include, but are not limited to, FLOWLENDOPA-100 (Kyodo Chemical Co., Ltd.), FLOWLENDOPA-35 (Kyodo Chemical Co., Ltd.), and FLOWLENG-700 (Kyodo Chemical Co., Ltd.).
在附图中示出了本发明的示例性实施例。然而，本发明可以以许多其它不同的形式来实施。所以本发明不仅限于在下文中此提出的实施例。下文实施例用于对本发明进行清楚的阐释，并能够支持本发明的保护范围。Exemplary embodiments of the invention are shown in the drawings. However, the invention can be implemented in many other different forms. Therefore, the present invention is not limited to the embodiments set forth herein below. The following embodiments are used to clearly explain the present invention, and can support the protection scope of the present invention.
在附图中，为了方便说明，有时会人为缩放图示的尺寸。但是附图中在相邻各部件或者相邻各层之间，如果没有图示则表明各层之间没有其它层。In the drawings, for convenience of description, the size of the illustration may be artificially scaled. However, in the drawings, there are no other layers between adjacent components or between adjacent layers if there is no illustration.
图1中，在基板表面制作电子型半导体1，所使用的n型杂质可以包括V族元素，例如磷(P)、或者砷(As)，加工方式可以使用POCl 3热扩散、磷浆热扩散、或者使用磷烷的离子注入方法。空穴型半导体2制作中，所使用的p型杂质可以包括III族元素，例如硼(B)、铝(Al)、或者镓(Ga)，加工方式可以使用BBr 3或者BCl 3热扩散、硼浆热扩散、或者使用离子注入。 In FIG. 1, an electronic semiconductor 1 is fabricated on the surface of a substrate. The n-type impurities used may include Group V elements, such as phosphorus (P) or arsenic (As). The processing method may use POCl 3 thermal diffusion and phosphorus slurry thermal diffusion. Or an ion implantation method using phosphane. In the fabrication of the hole-type semiconductor 2, the p-type impurity used may include a group III element, such as boron (B), aluminum (Al), or gallium (Ga). The processing method may use BBr 3 or BCl 3 thermal diffusion, boron The slurry is thermally diffused, or ion implantation is used.
半导体基板可以为空穴型半导体、也可以为电子型半导体。附图中5为电子型半导体基板。The semiconductor substrate may be a hole type semiconductor or an electronic type semiconductor. In the drawing, 5 is an electronic semiconductor substrate.
图3中的钝化绝缘层4由氧化硅(SiO x)、氮化硅(SiN x)或氧化铝(Al 2O x)中至少一种形成，加工方法可以使用等离子体增强化学气相沉积(PECVD)方法。 The passivation insulating layer 4 in FIG. 3 is formed of at least one of silicon oxide (SiO x ), silicon nitride (SiN x ), or aluminum oxide (Al 2 O x ). The processing method may use plasma enhanced chemical vapor deposition ( PECVD) method.
图3中，减反射层8由氧化硅(SiO x)、氮化硅(SiN x)、氮氧化硅(SiO xN y)、氧化钛(TiO x)、氧化锌(ZnO)或硫化锌(ZnS)中至少一种形成。例如，可以为形成为单个氧化硅(SiO x)层、单个氮化硅(SiN x)层或单个氮氧化硅(SiO xN y)层、或者包含氧化硅(SiO x)、氮化硅(SiN x)、氮氧化硅(SiO xN y) 的复合层。加工方法为，可以通过利用化学沉积(CVD)、溅射或旋涂。 In FIG 3, Save 8 of silicon oxide (SiO x), silicon nitride (SiN x), silicon oxynitride (SiO x N y), titanium oxide (TiO x), zinc oxide (ZnO) or zinc sulfide reflective layer ( At least one of ZnS) is formed. For example, it may be formed as a single silicon oxide (SiO x ) layer, a single silicon nitride (SiN x ) layer or a single silicon oxynitride (SiO x N y ) layer, or include silicon oxide (SiO x ), silicon nitride ( SiN x ), and a composite layer of silicon oxynitride (SiO x N y ). The processing method can be by using chemical deposition (CVD), sputtering or spin coating.
图4中的电极6和7、汇流电极6a和7a，可以包含银(Ag)、金(Au)、铜(Cu)、铝(Al)或者它们的合金。所有的电极6汇流于汇流电极6a，所有的电极7汇流于汇流电极7a。电极使用印刷的方法在相应的位置上印刷导电浆料，经过预烘干、高温烧结得到所需的电极。The electrodes 6 and 7 and the bus electrodes 6a and 7a in FIG. 4 may include silver (Ag), gold (Au), copper (Cu), aluminum (Al), or an alloy thereof. All the electrodes 6 converge on the bus electrode 6a, and all the electrodes 7 converge on the bus electrode 7a. The electrode uses a printing method to print a conductive paste at the corresponding position, and the required electrode is obtained after pre-baking and high temperature sintering.
图5、6、7中，钝化绝缘层4由氧化硅(SiO x)、氮化硅(SiN x)或氧化铝(Al 2O x)中至少一种形成，加工方法可以使用等离子体增强化学气相沉积(PECVD)方法。电极6和7、汇流电极6a和7a，可以包含银(Ag)、金(Au)、铜(Cu)、铝(Al)或者它们的合金。所有的电极6汇流于汇流电极6a，所有的电极7汇流于汇流电极7a。电极使用印刷的方法在相应的位置上印刷导电浆料，经过预烘干、高温烧结得到所需的电极。 In FIG. 6, 7, a passivation insulating layer 4 made of silicon oxide (SiO x), silicon nitride (SiN x) or aluminum oxide (Al 2 O x) in at least one of forming a plasma processing method can be used to enhance Chemical vapor deposition (PECVD) method. The electrodes 6 and 7 and the bus electrodes 6a and 7a may include silver (Ag), gold (Au), copper (Cu), aluminum (Al), or an alloy thereof. All the electrodes 6 converge on the bus electrode 6a, and all the electrodes 7 converge on the bus electrode 7a. The electrode uses a printing method to print a conductive paste at the corresponding position, and the required electrode is obtained after pre-baking and high temperature sintering.
图6、7中，减反射层8由氧化硅(SiO x)、氮化硅(SiN x)、氮氧化硅(SiO xN y)、氧化钛(TiO x)、氧化锌(ZnO)或硫化锌(ZnS)中至少一种形成。例如，可以为形成为单个氧化硅(SiO x)层、单个氮化硅(SiN x)层或单个氮氧化硅(SiO xN y)层、或者包含氧化硅(SiO x)、氮化硅(SiN x)、氮氧化硅(SiO xN y)的复合层。加工方法为，可以通过利用化学沉积(CVD)、溅射或旋涂。现将本发明的其中一种半导体器件的实施例作详细说明，但是本发明不限于此。该半导体器件为IBC背接触太阳能电池。本发明所选用的聚酰亚胺组合物制作方法举例如下，但是其单体、组成、反应条件等不限于此。 In FIGS. 6 and 7, the antireflection layer 8 is made of silicon oxide (SiO x ), silicon nitride (SiN x ), silicon oxynitride (SiO x N y ), titanium oxide (TiO x ), zinc oxide (ZnO), or sulfide. At least one of zinc (ZnS) is formed. For example, it may be formed as a single silicon oxide (SiO x ) layer, a single silicon nitride (SiN x ) layer or a single silicon oxynitride (SiO x N y ) layer, or include silicon oxide (SiO x ), silicon nitride ( SiN x ), a composite layer of silicon oxynitride (SiO x N y ). The processing method can be by using chemical deposition (CVD), sputtering or spin coating. An embodiment of one of the semiconductor devices of the present invention will now be described in detail, but the present invention is not limited thereto. The semiconductor device is an IBC back-contact solar cell. Examples of the method for preparing the polyimide composition used in the present invention are as follows, but the monomer, composition, and reaction conditions are not limited thereto.
制备例1：Preparation Example 1:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、0.2摩尔3,3'-二氨基-4,4'-二羟基联苯、0.5摩尔1,4-二氨基苯和0.3摩尔1,3-二(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到N-甲基吡咯烷酮中，在氮气流 下70～80℃聚合2小时后，添加封端剂0.01摩尔邻苯二甲酸酐进行封端反应15分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.5 Moles of 1,4-diaminobenzene and 0.3 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, a terminal blocking agent of 0.01 mol of phthalic anhydride was added to perform a blocking reaction for 15 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于600克N-甲基吡咯烷酮，然后加入50克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料50克二氧化钛A-120，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 50 grams of titanium dioxide A-120 as an inorganic filler and stir thoroughly to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例2：Preparation Example 2:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、0.24摩尔3,3'-二氨基-4,4'-二羟基联苯、0.32摩尔1,4-二氨基苯和0.44摩尔1,3-二(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.01摩尔邻苯二甲酸酐进行封端反应15分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mol 4,4'-oxybisphthalic anhydride, 0.24 mol 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.32 Moles of 1,4-diaminobenzene and 0.44 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, a terminal blocking agent of 0.01 mol of phthalic anhydride was added to perform a blocking reaction for 15 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于600克N-甲基吡咯烷酮，然后加入50克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料30克二氧化钛A-120，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 30 grams of titanium dioxide A-120 as an inorganic filler and stir well to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例3：Preparation Example 3:
聚酰亚胺树脂的制备：不分先后顺序，将1.1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.4摩尔3,3'-二氨基-4,4'-二羟基联苯、0.2摩尔1,3- 双(3-氨基苯氧基)苯和0.4摩尔1,3-二(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.01摩尔苯胺进行封端反应15分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1.1 moles of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 moles of 3,3' -Diamino-4,4'-dihydroxybiphenyl, 0.2 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 1,3-bis (3-aminopropyl) -1,1, 3,3-tetramethyldisiloxane was added to N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours, and then a capping agent of 0.01 mole of aniline was added for capping reaction for 15 minutes to obtain polyimide. Polyamic acid, the precursor of amines. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于600克N-甲基吡咯烷酮，然后加入50克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料50克平均粒径4微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 50 g of inorganic filler talc powder b with an average particle diameter of 4 μm was added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例4：Preparation Example 4:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔4,4'-二氨基-2,2'-二羟基联苯、0.5摩尔4,4’-二氨基二苯基甲烷和0.2摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.01摩尔邻苯二甲酸酐进行封端反应15分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole 4,4' -Diamino-2,2'-dihydroxybiphenyl, 0.5 mole 4,4'-diaminodiphenylmethane and 0.2 mole 3-bis (3-aminopropyl) -1,1,3,3-tetra Methyldisiloxane was added to N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours, and then a capping agent of 0.01 mole of phthalic anhydride was added for capping reaction for 15 minutes to obtain a polyimide Precursor of polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于600克N-甲基吡咯烷酮，然后加入50克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料15克平均粒径1微米球状二氧化硅a和60克平均粒径4微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 600 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 15 grams of inorganic filler with a mean particle diameter of 1 micrometer spherical silica a and 60 grams of talc powder with an average particle diameter of 4 micrometers b were added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例5：Preparation Example 5:
聚酰亚胺树脂的制备：不分先后顺序，将0.9摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.4摩尔1,3-双(3-氨基苯氧基)苯和0.3摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到900克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.05摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 0.9 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 900 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C. for 2 hours under a nitrogen stream, an end-capping agent was added to 0.05 mol of phthalic anhydride for end-capping In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮，然后加入80克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料108克平均粒径为0.4微米二氧化硅a和72克平均粒径为2.5微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of polyimide solid was dissolved in 200 g of N-methylpyrrolidone, and then 80 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then 108 g of inorganic filler having a mean particle diameter of 0.4 micron silica a and 72 g of talc powder b having an average particle diameter of 2.5 μm were added, and the mixture was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例6：Preparation Example 6:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.45摩尔1,3-双(3-氨基苯氧基)苯和0.25摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到900克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.11摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.45 moles of 1,3-bis (3-aminophenoxy) benzene and 0.25 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 900 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C. for 2 hours under a nitrogen stream, a blocking agent of 0.11 mole of phthalic anhydride was added to perform the blocking reaction. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合 物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于170克N-甲基吡咯烷酮，然后加入100克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料160克二氧化硅a(二氧化硅a：由144克平均粒径为0.5微米的二氧化硅、16克平均粒径为18纳米的二氧化硅组成)40克平均粒径为2.5微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to form a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 170 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 160 g of inorganic filler silica a (silica a: consisting of 144 g of silica with an average particle size of 0.5 μm, 16 g of silica with an average particle size of 18 nm) 40 g of average particle size It is talcum powder b of 2.5 micrometers, and it is fully mixed to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例7：Preparation Example 7:
聚酰亚胺树脂的制备：不分先后顺序，将1.1摩尔3,3',4,4'-联苯四羧酸二酐、0.2摩尔双(3-氨基-4-羟苯基)砜、0.4摩尔1,3-双(3-氨基苯氧基)苯和0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到750克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.15摩尔苯胺进行封端反应17分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1.1 moles of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 0.2 moles of bis (3-amino-4-hydroxyphenyl) sulfone, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 750 g of N In methylpyrrolidone, polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.15 mol of aniline, a capping agent, was added for capping reaction for 17 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于220克N-甲基吡咯烷酮，然后加入200克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料90克二氧化硅a(二氧化硅a：由85.5克平均粒径为0.7微米的二氧化硅、4.5克平均粒径为20纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of polyimide solid was dissolved in 220 g of N-methylpyrrolidone, and then 200 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 90 g of silica a, an inorganic filler (silica a: consisting of 85.5 g of silica with an average particle size of 0.7 μm, and 4.5 g of silica with an average particle size of 20 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例8：Preparation Example 8:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、0.2摩尔双(3-氨基-4-羟苯基)砜、0.5摩尔4,4’-二氨基二苯基甲烷和0.3摩尔 3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到700克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔苯胺进行封端反应17分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of bis (3-amino-4-hydroxyphenyl) sulfone, 0.5 mole of 4,4 '-Diaminodiphenylmethane and 0.3 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 700 g of N-methylpyrrolidone under nitrogen After polymerization at 70 to 80 ° C. for 2 hours, an end-capping agent, 0.1 mol of aniline was added, and the end-capping reaction was performed for 17 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于170克N-甲基吡咯烷酮，然后加入140克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由90克平均粒径为0.6微米的二氧化硅、10克平均粒径为14纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of a polyimide solid was dissolved in 170 g of N-methylpyrrolidone, and then 140 g of an epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 100 g of silica a, an inorganic filler (silica a: consisting of 90 g of silica having an average particle diameter of 0.6 μm and 10 g of silica having an average particle diameter of 14 nm) was added, and the mixture was thoroughly stirred to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例9：Preparation Example 9:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.3摩尔4,4’-二氨基二苯基甲烷和0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔苯胺进行封端反应17分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerized under nitrogen flow at 70-80 ° C for 2 hours. Then, an end-capping agent, 0.1 mole of aniline, was added for end-capping reaction for 17 minutes to obtain polyimide. Polyamic acid, the precursor of amines. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮和160克α-松油醇的混合溶剂中，然后加入140克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由90克平均粒径为0.8微米的二氧化硅、10克平均粒径为10纳 米的二氧化硅组成)和10克平均粒径为1微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of polyimide solid was dissolved in a mixed solvent of 200 g of N-methylpyrrolidone and 160 g of α-terpineol, and then 140 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 grams of inorganic filler silica a (silica a: consisting of 90 grams of silica with an average particle size of 0.8 microns, 10 grams of silica with an average particle size of 10 nanometers) and 10 grams of average particle size. The talc powder b having a diameter of 1 micron was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例10：Preparation Example 10:
聚酰亚胺树脂的制备：不分先后顺序，将1.2摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.35摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.35摩尔1,3-双(3-氨基苯氧基)苯和0.3摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.08摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1.2 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.08 mole of phthalic anhydride was added as a capping agent to perform a capping reaction. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于450克1,4-丁内酯，然后加入100克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料70克二氧化硅a(二氧化硅a：由63克平均粒径为0.4微米的二氧化硅、7克平均粒径为12纳米的二氧化硅组成)和30克平均粒径为4微米的滑石粉b，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 450 grams of 1,4-butyrolactone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 70 grams of inorganic filler silica a (silica a: consisting of 63 grams of silica with an average particle size of 0.4 microns, 7 grams of silica with an average particle size of 12 nm) and 30 grams of average particle size. The talc powder b having a diameter of 4 micrometers was thoroughly stirred to make the mixture uniform. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例11：Preparation Example 11:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.25摩尔双(3-氨基-4-羟苯基)砜、0.4摩尔3,3'-二氨基二苯砜和0.35摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩 尔苯胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.25 mole of bis (3- Amino-4-hydroxyphenyl) sulfone, 0.4 moles of 3,3'-diaminodiphenylsulfone, and 0.35 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisilazyl Alkane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.1 mol of aniline as a capping agent was added to the capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于60克N-甲基吡咯烷酮和100克1,4-丁内酯的混合溶剂中，然后加入100克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由85克平均粒径为0.5微米的二氧化硅、15克平均粒径为12纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of polyimide solid was dissolved in a mixed solvent of 60 g of N-methylpyrrolidone and 100 g of 1,4-butyrolactone, and then 100 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. . Then add 100 g of silica a, an inorganic filler (silica a: consisting of 85 g of silica with an average particle size of 0.5 μm, 15 g of silica with an average particle size of 12 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例12：Preparation Example 12:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、1摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.18摩尔苯胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4'-oxybisphthalic anhydride, 1 mole of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoro Propane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.18 mol of aniline was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于170克N-甲基吡咯烷酮中，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 170 grams of N-methylpyrrolidone to form the polyimide composition required for the present invention.
制备例13：Preparation Example 13:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、1摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.18摩尔苯胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～ 200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4'-oxybisphthalic anhydride, 1 mole of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoro Propane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen stream, and then 0.18 mol of aniline was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于220克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂NC6000并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 220 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
制备例14：Preparation Example 14:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.4摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.6摩尔1,3-双(3-氨基苯氧基)苯加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.11摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.6 mol of 1,3-bis (3-aminophenoxy) benzene was added to 800 g of N-methylpyrrolidone, and 70 to 80 under nitrogen flow. After polymerizing at 2 ° C for 2 hours, an end-capping agent, 0.11 mol of phthalic anhydride, was added for an end-capping reaction for 20 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于300克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂NC6000并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 300 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
制备例15：Preparation Example 15:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.3摩尔4,4’-二氨基二苯基甲烷、0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.2摩尔2-氨基苯磺酸进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺 树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.2 mol of 2-aminobenzenesulfonic acid was added as a capping agent to perform a capping reaction for 20 minutes. To obtain polyamic acid precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂NC6000并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
制备例16：Preparation Example 16:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.3摩尔4,4’-二氨基二苯基甲烷、0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔二乙胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of diethylamine was added as a capping agent to perform a capping reaction for 20 minutes to obtain a polymer. Polyamic acid, the precursor of imide. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂NC6000并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
制备例17：Preparation Example 17:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.3摩尔4,4’-二氨基二苯基甲烷、0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔苯胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of aniline as a capping agent was added for capping reaction for 20 minutes to obtain polyimide. Polyamic acid, the precursor of amines. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂NC6000并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin NC6000 was added and dissolved to form the polyimide composition required by the present invention.
制备例18：Preparation Example 18:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.3摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.3摩尔4,4’-二氨基二苯基甲烷、0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔苯胺进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.3 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.3 moles of 4,4'-diaminodiphenylmethane, 0.4 moles of 3-bis (3-aminopropyl) -1,1,3, 3-Tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.1 mol of aniline as a capping agent was added for capping reaction for 20 minutes to obtain polyimide. Polyamic acid, the precursor of amines. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于200克N-甲基吡咯烷酮中，然后加入100克环氧改性聚丁二烯树脂PB3600并使之溶解形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 200 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved to form the polyimide composition required by the present invention.
制备例19：Preparation Example 19:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.35摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.35摩尔1,3-双(3-氨基苯氧基)苯和0.3摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.01摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C. for 2 hours under a nitrogen flow, and then an end-capping agent was added to the reaction for end-capping with 0.01 mol of phthalic anhydride. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于190克N-甲基吡咯烷酮，然后加入70克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由85克平均粒径为0.6微米的二氧化硅、15克平均粒径为14纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of a polyimide solid was dissolved in 190 g of N-methylpyrrolidone, and then 70 g of an epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 g of silica a, an inorganic filler (silica a: consisting of 85 g of silica with an average particle size of 0.6 μm, 15 g of silica with an average particle size of 14 nm), and stir thoroughly to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例20：Preparation Example 20:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.4摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.4摩尔1,3-双(3-氨基苯氧基)苯和0.2摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.09摩尔邻苯二甲酸酐进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.4 mole of 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.2 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.09 mole of phthalic anhydride was added as a capping agent to perform a capping reaction. In 20 minutes, polyamic acid precursor polyamic acid was obtained. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于130克N-甲基吡咯烷酮，然后加入90克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由70克平均粒径为0.2微米的二氧化硅、30克平均粒径为15纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 g of polyimide solid was dissolved in 130 g of N-methylpyrrolidone, and then 90 g of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then, 100 g of silica a, an inorganic filler (silica a: consisting of 70 g of silica having an average particle size of 0.2 μm and 30 g of silica having an average particle size of 15 nm) was added, and the mixture was thoroughly stirred to make it well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例21：Preparation Example 21:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、0.35摩尔2,2-双(3-氨基-4-羟基苯基)-六氟丙烷、0.35摩尔1,3-双(3-氨基苯氧基)苯和0.3摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到800克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.01摩尔2-氨基苯磺酸进行封端反应20分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mol 4,4 '-(4,4'-isopropyldiphenoxy) bis (phthalic anhydride), 0.35 mol 2,2- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.35 moles of 1,3-bis (3-aminophenoxy) benzene and 0.3 moles of 3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane was added to 800 g of N-methylpyrrolidone, and after polymerization at 70 to 80 ° C for 2 hours under a nitrogen stream, a capping agent of 0.01 mole of 2-aminobenzenesulfonic acid was added for capping. The reaction was performed for 20 minutes to obtain polyamic acid precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于165克N-甲基吡咯烷酮，然后加入90克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料100克二氧化硅a(二氧化硅a：由70克平均粒径为1微米的二氧化硅、30克平均粒径为18纳米的二氧化硅组成)，充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 165 grams of N-methylpyrrolidone, and then 90 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 100 g of inorganic filler silica a (silica a: consisting of 70 g of silica with an average particle size of 1 micron and 30 g of silica with an average particle size of 18 nm) and stir thoroughly well mixed. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例22：Preparation Example 22:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔4,4'-氧双邻苯二甲酸酐、0.2摩尔3,3'-二氨基-4,4'-二羟基联苯、0.5摩尔1,4-二氨基苯和0.3摩尔1,3-二(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.1摩尔邻苯二甲酸酐进行封端反应15分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 4,4'-oxybisphthalic anhydride, 0.2 mole of 3,3'-diamino-4,4'-dihydroxybiphenyl, 0.5 Moles of 1,4-diaminobenzene and 0.3 moles of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to N-methylpyrrolidone under nitrogen After polymerizing at 70 to 80 ° C. for 2 hours, an end-capping agent was added to 0.1 mol of phthalic anhydride to perform an end-capping reaction for 15 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于110克N- 甲基吡咯烷酮，然后加入50克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料50克二氧化钛A-120、15克无机粒子分散剂FLOWLENDOPA-100充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 110 grams of N-methylpyrrolidone, and then 50 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 50 grams of inorganic filler titanium dioxide A-120 and 15 grams of inorganic particle dispersant FLOWLENDOPA-100 and stir well to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
制备例23：Preparation Example 23:
聚酰亚胺树脂的制备：不分先后顺序，将1摩尔3,3',4,4'-联苯四羧酸二酐、0.2摩尔双(3-氨基-4-羟苯基)砜、0.4摩尔1,3-双(3-氨基苯氧基)苯和0.4摩尔3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷加入到750克N-甲基吡咯烷酮中，在氮气流下70～80℃聚合2小时后，添加封端剂0.5摩尔苯胺进行封端反应17分钟，得到聚酰亚胺的前驱体聚酰胺酸。将得到的聚酰胺酸继续在170～200℃加热闭环得到聚酰亚胺树脂。Preparation of polyimide resin: 1 mole of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 0.2 mole of bis (3-amino-4-hydroxyphenyl) sulfone, 0.4 moles of 1,3-bis (3-aminophenoxy) benzene and 0.4 moles of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 750 g of N -In methylpyrrolidone, polymerization was performed at 70 to 80 ° C for 2 hours under a nitrogen stream, and then 0.5 mol of aniline, a capping agent, was added for capping reaction for 17 minutes to obtain a polyimide precursor polyamic acid. The obtained polyamic acid was further subjected to ring closure at 170 to 200 ° C to obtain a polyimide resin.
得到的聚酰亚胺经过再沉淀、干燥做成固体，或者也可以直接使用聚合物溶液。这里列举使用固体的方法。将100克聚酰亚胺固体溶解于180克N-甲基吡咯烷酮，然后加入100克环氧改性聚丁二烯树脂PB3600并使之溶解。然后再加入无机填料90克二氧化硅a(二氧化硅a：由85.5克平均粒径为0.7微米的二氧化硅、4.5克平均粒径为20纳米的二氧化硅组成)、9克无机粒子分散剂FLOWLENDOPA-100充分搅拌使其混合均匀。然后使用三辊研磨机使无机填料均匀地分散，形成本发明所需的聚酰亚胺组合物。The obtained polyimide is reprecipitated and dried to make a solid, or a polymer solution may be directly used. Here are methods using solids. 100 grams of polyimide solid was dissolved in 180 grams of N-methylpyrrolidone, and then 100 grams of epoxy-modified polybutadiene resin PB3600 was added and dissolved. Then add 90 grams of inorganic filler silica a (silica a: consisting of 85.5 grams of silica with an average particle size of 0.7 microns, 4.5 grams of silica with an average particle size of 20 nm), 9 grams of inorganic particles The dispersant FLOWLENDOPA-100 is fully stirred to make it mix well. Then, a three-roll mill was used to uniformly disperse the inorganic filler to form the polyimide composition required by the present invention.
实施例1：Example 1:
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BCl 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B， 然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；印刷制备例1的聚酰亚胺(PI)绝缘材料，印刷图案的线宽150微米、邻接的线与线间距30微米、厚度10微米，烘干后再进行390℃固化4分钟；使用丝网印刷在空穴型半导体、以及电子型半导体的表面印刷电极材料，然后烧结完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BCl 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, mask B on one side of the mask is removed by one-sided cleaning, and then mask C is formed on the hole semiconductor formed by diffusion; POCl 3 diffusion is performed to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an antireflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print the polyimide (PI) insulating material of Preparation Example 1, and the line width of the printed pattern is 150 Micron, adjacent line and line spacing of 30 microns, thickness of 10 microns, dried and then cured at 390 ° C for 4 minutes; printed on the surface of the cavity type semiconductor and electronic type semiconductor by screen printing electrode material, and then sintered to complete the IBC Production of back contact batteries.
实施例2：Example 2:
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BBr 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；印刷制备例2的聚酰亚胺(PI)绝缘材料，印刷图案的线宽155微米、邻接的线与线间距20微米、厚度10微米，烘干后再进行120℃固化20分钟；使用丝网印刷在空穴型半导体、以及电子型半导体的表面印刷电极材料，然后烧结完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove barrier layer A and mask C; form anti-reflection layer on the side where barrier layer A is removed, and passivation layer on the other side; print polyimide (PI) insulation material of Preparation Example 2 with a line width of 155 Micron, adjacent line and line spacing of 20 microns, thickness of 10 microns, and then cured at 120 ° C for 20 minutes after drying; use screen printing to print electrode materials on the surface of hole-type semiconductors and electronic semiconductors, and then sinter to complete IBC Production of back contact batteries.
实施例3：Example 3:
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BBr 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；在空穴半导体和电子型半导体上印刷线 宽为20～50微米的电极材料，然后烧结形成电极的细栅；然后再印刷制备例3的聚酰亚胺(PI)绝缘材料，印刷图案的如图5的3绝缘材料所示，直接进行260℃固化10分钟；然后在相对应的位置印刷如图5所示汇流电极6a和7a，烧结后完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then, the fine grid of the electrode is sintered; then, the polyimide (PI) insulation material of Preparation Example 3 is printed, and the printed pattern is shown in FIG. 5 as the 3 insulation material, and it is directly cured at 260 ° C for 10 minutes; The bus electrodes 6a and 7a are printed as shown in FIG. 5, and the production of the IBC back-contact battery is completed after sintering.
实施例4～23中，依次使用制备例4～23所制备的聚酰亚胺(PI)绝缘材料，其余参数、方法与实施例3相同。In Examples 4 to 23, the polyimide (PI) insulating materials prepared in Preparation Examples 4 to 23 were used in order, and the remaining parameters and methods were the same as those in Example 3.
实施例24Example 24
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BBr 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；在空穴半导体和电子型半导体上印刷线宽为20～50微米的电极材料，然后烧结形成电极的细栅；然后再印刷热固性丙烯酸树脂TCA-7020C(台昌樹脂(佛山)有限公司)绝缘材料，印刷图案的如图5的3绝缘材料所示，直接进行200℃固化15分钟；然后在相对应的位置印刷如图5所示汇流电极6a和7a，烧结后完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin TCA-7020C (Taichang Resin (Foshan) Co., Ltd.) insulation material. The printed pattern is shown as 3 insulation material in Figure 5, and it is directly cured at 200 ° C for 15 minutes. ; Then, the bus electrodes 6a and 7a shown in FIG. 5 are printed at corresponding positions, and the production of the IBC back contact battery is completed after sintering.
实施例25Example 25
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BBr 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成 减反射层、在另外一面形成钝化层；在空穴半导体和电子型半导体上印刷线宽为20～50微米的电极材料，然后烧结形成电极的细栅；然后再印刷热固性丙烯酸树脂HK-100/W(广东三求光固材料股份有限公司)绝缘材料，印刷图案的如图5的3绝缘材料所示，直接进行200℃固化15分钟；然后在相对应的位置印刷如图5所示汇流电极6a和7a，烧结后完成IBC背接触电池的制作。注意：上述HK-100/W使用前需要将成套的两种液体(A、B液)混合均匀。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin HK-100 / W (Guangdong Sanqiu Guanggu Material Co., Ltd.) insulation material, and print the pattern as shown in 3 insulation material in Figure 5, and directly go to 200 ° C Cure for 15 minutes; then, bus electrodes 6a and 7a as shown in FIG. 5 are printed at corresponding positions, and the IBC back-contact battery is completed after sintering. Note: Before using the above HK-100 / W, the two sets of liquids (A and B liquids) need to be mixed uniformly.
实施例26Example 26
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外一面上根据设计的图案形成氧化硅掩膜B；然后进行BBr 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；在空穴半导体和电子型半导体上印刷线宽为20～50微米的电极材料，然后烧结形成电极的细栅；然后再印刷热固性丙烯酸树脂LR-7568(日本三菱化学)绝缘材料，印刷图案的如图5的3绝缘材料所示，直接进行200℃固化15分钟；然后在相对应的位置印刷如图5所示汇流电极6a和7a，烧结后完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BBr 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove the barrier layer A and the mask C; form an anti-reflection layer on the side where the barrier layer A is removed, and a passivation layer on the other side; print electrode materials with a line width of 20 to 50 microns on hole semiconductors and electronic semiconductors, Then sinter to form the fine grid of the electrode; then print the thermosetting acrylic resin LR-7568 (Japan Mitsubishi Chemical) insulation material, and print the pattern as shown in 3 insulation material in Figure 5, and directly cure at 200 ° C for 15 minutes; The bus electrodes 6a and 7a are printed as shown in FIG. 5, and the production of the IBC back-contact battery is completed after sintering.
对比例1：Comparative Example 1:
对比例1中所使用的组合物选自UV光固化的芳香族聚氨酯丙烯酸酯UV-3722(东莞市井上化工科技有限公司)，此组成物中不含本发明的环氧树脂以及二氧化硅a和滑石粉b。The composition used in Comparative Example 1 was selected from UV-curable aromatic polyurethane acrylate UV-3722 (Dongguan Inshang Chemical Technology Co., Ltd.). This composition does not contain the epoxy resin and silica a of the present invention. And talcum powder b.
首先，在制绒、清洗后的硅片一面上制作氧化硅阻隔层A；然后在另外 一面上根据设计的图案形成氧化硅掩膜B；然后进行BCl 3扩散，在硅片制作了掩膜B的一侧形成局部空穴半导体；然后单面清洗去除掩膜一侧的掩膜B，然后再在扩散形成的空穴半导体上制作掩膜C；进行POCl 3扩散，形成电子型半导体；通过清洗去除阻隔层A以及掩膜C；在除去阻隔层A的一面形成减反射层、在另外一面形成钝化层；印刷作为对比材料的UV-3722绝缘材料，印刷图案的线宽150微米、邻接的线与线间距30微米、厚度10微米，然后再进行UV固化15分钟；使用丝网印刷在空穴型半导体、以及电子型半导体的表面印刷电极材料，然后烧结完成IBC背接触电池的制作。 First, a silicon oxide barrier layer A was made on one side of the flocked and cleaned silicon wafer; then a silicon oxide mask B was formed on the other side according to the designed pattern; then BCl 3 diffusion was performed to make a mask B on the silicon wafer. A local hole semiconductor is formed on one side; then, the mask B on one side of the mask is removed by one-sided cleaning, and then a mask C is formed on the hole semiconductor formed by diffusion; POCl 3 is diffused to form an electronic semiconductor; Remove barrier layer A and mask C; form anti-reflection layer on the side where barrier layer A is removed, and passivation layer on the other side; print UV-3722 insulation material as a contrast material, the line width of the printed pattern is 150 microns, and The line-to-line spacing is 30 micrometers and the thickness is 10 micrometers, and then UV curing is performed for 15 minutes. Screen printing is used to print electrode materials on the surface of hole-type semiconductors and electronic semiconductors, and then sintering is completed to make the IBC back-contact battery.
具体的测试结果如下表1和2所示。其中表1为电池刚制作完成后的性能，表2为将表格1中电池片在300℃加热240分钟后的性能。The specific test results are shown in Tables 1 and 2 below. Table 1 shows the performance immediately after the battery is manufactured, and Table 2 shows the performance of the battery sheet in Table 1 after being heated at 300 ° C for 240 minutes.
表1Table 1
Figure PCTCN2019096270-appb-000004
Figure PCTCN2019096270-appb-000004
Figure PCTCN2019096270-appb-000005
Figure PCTCN2019096270-appb-000005
表2Table 2
Figure PCTCN2019096270-appb-000006
Figure PCTCN2019096270-appb-000006
从上述实验结果可以看出，本发明所采用的绝缘材料所制备的电池比对 比例1中使用其它绝缘材料制备的电池片性能优异。而且，在测试高温耐受性的实验中，其稳定性也要优于对比材料。因为太阳能电池的使用温度比较高，而且一般电池的寿命在25年左右。想要确保使用寿命，必须采用绝缘性优异、稳定性优异的绝缘材料。而本发明所选的PI绝缘材料无疑可以提供更好的保障。From the above experimental results, it can be seen that the battery prepared by the insulating material used in the present invention has superior performance to the battery sheet prepared by using other insulating materials in Comparative Example 1. Moreover, in experiments testing high temperature resistance, its stability is also better than that of comparative materials. Because the use temperature of solar cells is relatively high, and the life of the general battery is about 25 years. In order to ensure the service life, an insulating material with excellent insulation and stability must be used. The PI insulation material selected by the present invention can undoubtedly provide better protection.

Claims (17)

  1. 一种半导体器件，其特征在于：所述半导体器件中包含绝缘材料；所述绝缘材料为热固性树脂组合物热固化后的材料。A semiconductor device, characterized in that the semiconductor device includes an insulating material; the insulating material is a material after thermosetting of a thermosetting resin composition.
  2. 根据权利要求1所述的半导体器件，其特征在于：所述热固性树脂组合物包含可溶性聚酰亚胺、环氧改性聚丁二烯以及有机溶剂，相对于100重量份的所述可溶性聚酰亚胺而言，所述环氧改性聚丁二烯为20～200重量份。The semiconductor device according to claim 1, wherein the thermosetting resin composition comprises a soluble polyimide, an epoxy-modified polybutadiene, and an organic solvent, with respect to 100 parts by weight of the soluble polyacrylic acid. In terms of imines, the epoxy-modified polybutadiene is 20 to 200 parts by weight.
  3. 根据权利要求2所述的半导体器件，其特征在于：所述可溶性聚酰亚胺为具有0.55mol/kg～1.0mol/kg苯酚羟基的可溶性聚酰亚胺。The semiconductor device according to claim 2, wherein the soluble polyimide is a soluble polyimide having a phenolic hydroxyl group of 0.55 mol / kg to 1.0 mol / kg.
  4. 根据权利要求2所述的半导体器件，其特征在于：所述可溶性聚酰亚胺由式1所示的二酸酐和式2至式4所示的二胺中的至少三种聚合而成；其中将式1所示的二酸酐作为A摩尔、式2所示的二胺作为B摩尔、式3所示的二胺作为C摩尔、式4所示的二胺作为D摩尔时，满足A/(B+C+D)＝0.85～1.2、B/(B+C+D)＝0.2～0.5，并且，所述可溶性聚酰亚胺的末端至少由胺衍生物或者羧酸酐封端剂进行封端；The semiconductor device according to claim 2, wherein the soluble polyimide is polymerized from at least three of a dianhydride represented by Formula 1 and a diamine represented by Formula 2 to Formula 4; wherein When A mol is represented by A mol, diamine represented by Formula 2 is B mol, diamine represented by Formula 3 is C mol, and diamine represented by Formula 4 is D mol, A / ( B + C + D) = 0.85 to 1.2, B / (B + C + D) = 0.2 to 0.5, and the end of the soluble polyimide is at least blocked by an amine derivative or a carboxylic anhydride blocking agent. ;
    Figure PCTCN2019096270-appb-100001
    Figure PCTCN2019096270-appb-100001
    Figure PCTCN2019096270-appb-100002
    Figure PCTCN2019096270-appb-100002
    其中，式2中的Y为选自-CO-、-SO2-、-O-、-S-、-CH 2-、-NHCO-、-C(CH 3) 2-、-C(CF 3) 2-、-COO-或单键中的一种；式3中的a为0～5的整数；Z为2个以上的情况下可以相同或不同，分别选自-CO-、-SO2-、-O-、-S-、-CH 2-、-NHCO-、-C(CH 3) 2-、-C(CF 3) 2-、-COO-或单键中的一种；M为独立的取代基，为2个以上的情况下可以相同或不同，分别选自碳原子数1～3的烷基、氟化烷基、烷氧基或者氢原子中的一种；式4中的R为2个以上的情况下可以相同或不同，分别选自碳原子数1～3的烷基或含有一个苯环的芳基中的任意一个；l以及m各自独立地为1～6的整数；n为1～10的整数。 Wherein Y in Formula 2 is selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond; a in formula 3 is an integer from 0 to 5; when Z is 2 or more, they may be the same or different, and are selected from -CO-, -SO2-, -O-, -S-, -CH 2- , -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO- or a single bond; M is independent When there are two or more substituents, they may be the same or different, and are each selected from one of an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group, an alkoxy group, or a hydrogen atom; R in Formula 4 is In the case of two or more, they may be the same or different, and are respectively selected from any one of an alkyl group having 1 to 3 carbon atoms or an aryl group containing a benzene ring; l and m are each independently an integer of 1 to 6; n It is an integer from 1 to 10.
  5. 根据权利要求4所述的半导体器件，其特征在于：相对所述二胺而言，所述封端剂的摩尔量为二胺总摩尔量的5～15％。The semiconductor device according to claim 4, wherein the molar amount of the terminal blocking agent is 5 to 15% of the total molar amount of the diamine relative to the diamine.
  6. 根据权利要求4所述的半导体器件，其特征在于：所述胺衍生物封端剂为苯胺、2-氨基苯甲酸、3-氨基苯甲酸、4-氨基苯甲酸、4-氨基水杨酸、5-氨基水杨酸、6-氨基水杨酸、2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸、2-氨基苯酚、3-氨基苯酚、4-氨基苯酚、2-氨基苯硫酚、3-氨基苯硫酚、4- 氨基苯硫酚中的一种或多种；所述羧酸酐封端剂为邻苯二甲酸酐、马来酸酐、环己烷二羧酸酐、5-降冰片烯-2,3-二羧酸酐、1,2-二羧基萘酐或3-羟基邻苯二甲酸酐中的一种或多种。The semiconductor device according to claim 4, wherein the amine derivative blocking agent is aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, One or more of 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol; the carboxylic acid anhydride blocking agent is phthalic anhydride, maleic anhydride, cyclohexanedi One or more of carboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2-dicarboxynaphthalic anhydride, or 3-hydroxyphthalic anhydride.
  7. 根据权利要求2所述的半导体器件，其特征在于：所述环氧改性聚丁二烯为式5所示：The semiconductor device according to claim 2, wherein the epoxy-modified polybutadiene is represented by Formula 5:
    Figure PCTCN2019096270-appb-100003
    Figure PCTCN2019096270-appb-100003
    其中，式5中的x为5～20的整数；y为2～8的整数；z为3～12的整数。In the formula, x is an integer of 5 to 20; y is an integer of 2 to 8; z is an integer of 3 to 12.
  8. 根据权利要求4所述的半导体器件，其特征在于：所述热固性树脂组合物还包含无机粉末或染色剂中的至少一种或多种。The semiconductor device according to claim 4, wherein the thermosetting resin composition further comprises at least one or more of an inorganic powder or a colorant.
  9. 根据利要求8所述的半导体器件，其特征在于：所述无机粉末选自球状二氧化硅a、或滑石粉b中的一种或多种；相对于热固性树脂组合物中固体成分100重量％，所述无机粉末的含量为20重量％以上50重量％以下并且，所述无机粉末中，球状二氧化硅a的重量含量为60～100％。The semiconductor device according to claim 8, wherein the inorganic powder is selected from one or more of spherical silica a or talc b; and 100% by weight relative to the solid content of the thermosetting resin composition. The content of the inorganic powder is 20% by weight to 50% by weight, and the content of the spherical silica a in the inorganic powder is 60 to 100%.
  10. 根据权利要求9所述的半导体器件，其特征在于：所述球状二氧化硅a的平均粒径为1微米以下；所述滑石粉b的平均粒径为3微米以下。The semiconductor device according to claim 9, wherein the average particle diameter of the spherical silica a is 1 μm or less; and the average particle diameter of the talc powder b is 3 μm or less.
  11. 根据权利要求10所述的半导体器件，其特征在于：所述球状二氧化硅a由重量含量为80～95％的平均粒径为0.4～0.8微米的球状二氧化硅、和重量含量为5～20％的平均粒径为10～20纳米的球状二氧化硅组成。The semiconductor device according to claim 10, wherein the spherical silica a comprises a spherical silica having an average particle diameter of 0.4 to 0.8 micrometers in a weight content of 80 to 95% and a weight content of 5 to 20% spherical silica composition with an average particle diameter of 10-20 nm.
  12. 根据权利要求4所述的半导体器件，其特征在于：所述绝缘材料可以在110～400℃进行固化。The semiconductor device according to claim 4, wherein the insulating material can be cured at 110 to 400 ° C.
  13. 根据权利要求12所述的半导体器件，其特征在于：所述绝缘材料可以在220～350℃进行固化。The semiconductor device according to claim 12, wherein the insulating material can be cured at 220-350 ° C.
  14. 根据权利要求4所述的半导体器件，其特征在于：所述可溶性聚酰亚胺的重均分子量为10000～32000。The semiconductor device according to claim 4, wherein a weight average molecular weight of the soluble polyimide is 10,000 to 32,000.
  15. 根据权利要求8所述的半导体器件，其特征在于所述热固性树脂组合物中还含有无机粒子分散剂，并且所述分散剂的添加重量为无机粒子重量的10～30％。The semiconductor device according to claim 8, wherein the thermosetting resin composition further contains an inorganic particle dispersant, and an added weight of the dispersant is 10 to 30% by weight of the inorganic particles.
  16. 根据权利要求1～15中任一项所述的半导体器件，其特征在于：所述半导体器件为太阳能电池。The semiconductor device according to any one of claims 1 to 15, wherein the semiconductor device is a solar cell.
  17. 根据权利要求16所述的半导体器件，其特征在于：所述太阳能电池为IBC背接触太阳能电池。The semiconductor device according to claim 16, wherein the solar cell is an IBC back-contact solar cell.
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