CN105001778A - Fluorine-containing polyimide humidity-sensitive capacitor and preparation method therefor - Google Patents
Fluorine-containing polyimide humidity-sensitive capacitor and preparation method therefor Download PDFInfo
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Abstract
The invention relates to a fluorine-containing polyimide humidity-sensitive capacitor and a preparation method therefor. The humidity-sensitive capacitor consists of a substrate, a lower electrode, a fluorine-containing humidity-sensitive polyimide coating and an upper electrode, wherein fluorine-containing humidity-sensitive polyimide is prepared by reacting 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and aromatic diamine with aromatic dianhydride. The preparation method comprises the steps of: washing the substrate with washing liquid, drying the substrate in a drying box, performing vacuum evaporation to manufacture the lower electrode, guiding a lead wire of the lower electrode by JP-6 conductive adhesive, spin-coating with a fluorine-containing humidity-sensitive polyimide precursor solution, imidizing, performing vacuum evaporation to manufacture the upper electrode, cutting into slices, flushing with de-ionized water, drying, screening, performing surface modification, guiding a lead wire of the upper electrode by the JP-6 conductive adhesive, and preparing the fluorine-containing polyimide humidity-sensitive capacitor. The fluorine-containing polyimide humidity-sensitive capacitor has the advantages of high sensitivity, small humidity hysteresis, simple manufacturing process, low cost and the like, and has a good market prospect.
Description
Technical field
The invention belongs to functional high polymer material field, particularly a kind of fluorinated polyimide humicap and preparation method thereof.
Background technology
In fields such as meteorology, environmental protection, national defence, Aeronautics and Astronautics, navigation, industry, agricultural, medical treatment, electronics microelectronics, often need to measure ambient moisture and control.Want the measurement of comparison temperature much complicated to the measurement of humidity, this is mainly because temperature is individual independently measured, and the measurement of humidity cannot be measured due to water vapor in air dividing potential drop, therefore, have to be converted into the measurement second parameter relevant with humidity according to physics and chemistry law carry out again changing just trying to achieve humidity value.
Traditional moisture content measurement instrument mainly contains three kinds, i.e. telescopic wet bulb thermometer, wet-dry thermometer and dew point instrument.Traditional measurement method, except the characteristics such as sensitivity, accuracy and resolving power are poor, is difficult to be connected with modern communication recording control apparatus.Like this, the task of the task of moisture content measurement just drops on it humidity sensor.Humidity sensor and the proofing unit with premium propertiess such as highly sensitive, permanent stability are good, hygrometric wide ranges have become the target of chasing now.
The core of humidity sensor is wet sensory material, and the performance of wet sensory material decides the humidity sensing characteristic of humidity sensor.Wet sensory material mainly contains electrolytes, semiconductive ceramic class and macromolecular material class.Conventional sense wet polymer material mainly contains polystyrene, cellulose acetate, polyacrylic ester and polyimide etc.
Polyimide is the macromolecular material that a class over-all properties is very excellent, there is thermotolerance excellent especially, lower temperature resistance, flame retardant resistance, electric property and mechanical property, be widely used in the high-tech areas such as electronics microelectronics, aerospace, laser, photoelectricity.
The existing many reports of research and development about polyimide resin field:
Chinese invention patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, be primarily characterized in that: (1) mol ratio is that the phenolic hydroxy group aromatic dicarboxylic amine compound of 1:1 or the mixture of phenolic hydroxy group aromatic diamine and other diamine and aromatic dicarboxylic acid anhydride are in strong polar non-proton organic solvent, under nitrogen protection, react at 0 DEG C ~ 30 DEG C after 3 ~ 12 hours, obtain the polyhydroxyamide acid solution of clear viscous, wherein, strong polar non-proton organic solvent accounts for the mass percent of whole reaction system is 5% ~ 30%; (2) in nitrogen atmosphere, add azeotropy dehydrant, heat temperature raising, in the temperature range of 120 DEG C ~ 160 DEG C, backflow azeotropic dehydration imidization 5 ~ 18 hours, be cooled to room temperature, filter, washing, vacuum-drying, obtain phenolic hydroxyl group containing polyimide powder, wherein, the volume ratio of azeotropy dehydrant and strong polar non-proton organic solvent is 0.1 ~ 10:1.
The people such as the Yu Xinhai [development of high-temperature resistant single-component epoxy tackiness agent, bonding, 2008, 29 (12): 16-19] a kind of preparation method of polyimide is disclosed, be primarily characterized in that: with maleic anhydride (MA) for end-capping reagent, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) obtains the polyetherimide resin (HPEI) of phenolic hydroxy group for main raw material synthesis.
Chinese invention patent CN101560298A discloses a kind of thermoplastic fluorine-containing fully aromatic polyimide powder and preparation method thereof, principal character is, under the effect of catalyzer, mol ratio is that the fluorinated aromatic binary primary amine of 1:0.8 ~ 1.2 and aromatic dicarboxylic anhydride are in phenol solvent, after reacting 5-10 hour in the temperature range of 100 DEG C ~ 180 DEG C, pour in the precipitating agent under high-speed stirring state while hot, separate out pressed powder, filtration, washing, immersion, filtration, drying, acquisition thermoplastic fluorine-containing fully aromatic polyimide powder.
Chinese invention patent CN101580637A discloses a kind of alicyclic-containing polyimide film and preparation method thereof, principal character is: under room temperature, alicyclic ring binary primary amine, aromatic dicarboxylic primary amine are dissolved in strong polar non-proton organic solvent, stir after in homogeneous phase solution, add aromatic dicarboxylic anhydride, stir, react 1-3 hour under room temperature after, obtain homogeneous phase, transparent, thick containing alicyclic ring polyamic acid resin solution; Regulate the above-mentioned viscosity containing alicyclic ring polyamic acid resin solution with strong polar non-proton organic solvent, film forming in casting machine, heat temperature raising, carries out dehydration fever imidization, cooling, and demoulding obtains the alicyclic-containing polyimide film of homogeneous phase transparent.
Chinese invention patent CN101597428A discloses a kind of full aromatic fluorine containing transparent polyimide film and preparation method thereof, principal character is: add in polymerization bottle by fluorinated aromatic binary primary amine and strong polar non-proton organic solvent, stirred at ambient temperature, after dissolving completely, ice-water bath is cooled to less than 5 DEG C, adds aromatic dicarboxylic anhydride, stirs, react in the temperature range of 5 DEG C-10 DEG C after 3 hours, obtain homogeneous phase, transparent, thick fluorinated aromatic polyamic acid resin solution; Regulate the viscosity of above-mentioned fluorinated aromatic polyamic acid resin solution with strong polar non-proton organic solvent, film forming in casting machine, heat temperature raising, carries out dehydration fever imidization, cooling, and demoulding obtains full aromatic fluorine containing transparent polyimide film.
Chinese invention patent CN101585923A discloses a kind of polyimide film with high visible light permeability and preparation method thereof, principal character is: at room temperature, binary primary amine is dissolved in strong polar non-proton organic solvent system, ice-water bath is cooled in the temperature range of 5 DEG C-10 DEG C, add aromatic dicarboxylic anhydride, stir, react 4-10 hour in the temperature range of 5 DEG C-10 DEG C after, obtain homogeneous phase, transparent, thick polyamic acid resin solution; Regulate the viscosity of this polyamic acid resin solution, film forming in casting machine, hot imidization, obtain the Kapton of homogeneous phase transparent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of fluorinated polyimide humicap and preparation method thereof, this fluorinated polyimide humicap have highly sensitive, humidity hysteresis is little, manufacturing process is simple, low cost and other advantages, has good market-oriented prospect.
A kind of fluorinated polyimide humicap of the present invention, described humicap is made up of wet polyimide coating and top electrode of substrate, lower electrode, fluorine-containing sense; Wherein, the fluorine-containing sense polyimide that wets is reacted by two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and the aromatic dianhydride of 2,2-and forms; Wherein, the mol ratio of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-and aromatic diamine is 1:11-20; The ratio of the total mole number of two (3-amino-4-hydroxylphenyl) HFC-236fa of aromatic dianhydride mole number and 2,2-, aromatic diamine is 1.01-1.03:1.
The raw material that described lower electrode and top electrode adopt is selected from one or more in platinum, gold and silver, nickel, and purity is more than 99.9%, preferably gold.
Described substrate is silicon chip.
Described aromatic diamine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 2,4,6-trimethylammonium mphenylenediamine, 4,4 '-diamino-4 "-hydroxyl tritane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 4,4 '-diaminobenzophenone, DDS, 3,3 '-diaminodiphenylsulfone(DDS), two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) cyanobenzene of 2,6-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, one or more in Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene.
Described aromatic dianhydride is selected from pyromellitic acid anhydride, 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic biphenyl dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic benzophenone dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic diphenyl sulfone dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy) benzene dianhydride, 1, 3-two (3, 4-di carboxyl phenyloxy) benzene dianhydride, 4, 4 '-bis-(3, 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4, 4 '-bis-(3, 4-di carboxyl phenyloxy) benzophenone dianhydride, 4, 4 '-bis-(3, 4-di carboxyl phenyloxy) biphenyl dianhydride, 4, 4 '-bis-(3, 4-di carboxyl phenyloxy) one or more in diphenyl ether dianhydride.
The preparation method of a kind of fluorinated polyimide humicap of the present invention, comprising:
After scavenging solution cleaning substrate, put into loft drier and dry, drying 0.5 hour-1 hour at 70 DEG C-90 DEG C, vacuum evaporation subsequently makes lower electrode, and JP-6 conductive resin draws lower electrode lead-in wire, the more fluorine-containing sense of spin coating is wet polyimide precursor solution, imidization, vacuum evaporation makes top electrode, section, deionized water rinsing, drying 0.5 hour-1 hour at 70 DEG C-90 DEG C, screening, finishing, JP-6 conductive resin draws top electrode lead-in wire, obtained fluorinated polyimide humicap;
Wherein, the wet preparation method of polyimide precursor solution of fluorine-containing sense comprises the steps: 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-, aromatic diamine, aromatic dianhydride, strong polar non-proton organic solvent put into reactor, in 0 DEG C of-5 DEG C of stirring reaction after 2 hours-5 hours, obtain fluorine-containing sense and to wet polyimide precursor solution.
Described scavenging solution is selected from one or more in acetone, ethanol, ether, ammoniacal liquor, hydrogen peroxide, hydrochloric acid, sulfuric acid.
Described imidization concrete technology is: nitrogen atmosphere, is warming up to 100 DEG C from room temperature, keeps 1 hour, continues to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently.
Described strong polar non-proton organic solvent is selected from one or more in DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO); Wherein, described strong polar non-proton organic solvent and the total mass ratio of reactant are 4-6:1; The total mass of reactant refers to the quality sum of two (3-amino-4-carboxyl phenyl) HFC-236fa, aromatic diamine and the aromatic dianhydride of 2,2-.
beneficial effect
(1) preparation method's reaction conditions of the present invention is gentle, and reaction process is carried out at ambient pressure, simple to operate; Reaction raw materials convenient sources, cost is low, does not relate to and does not also produce corrosives;
(2) the synthesis technique equipment that preparation process is used is universal, the suite of equipment of existing production polyimide resin can be utilized completely to implement the present invention, be very beneficial for the industrialization of product;
(3) the material resin molecular weight adopted easily controls, and molecular structure also easily adjusts, and the sense being conducive to preparing ideal performance is wet polyimide functional materials.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 3.66 grams of (0.01 moles) 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP), 22.00 grams of (0.11 moles) 3,3 '-diaminodiphenyl oxide, 35.89 grams of (0.122 moles) 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 248 grams of N, N-N,N-DIMETHYLACETAMIDE puts into reactor, in 0 DEG C of stirring reaction after 2 hours, the fluorine-containing sense obtaining 309.55 grams of clear viscous homogeneous phases is wet polyimide precursor solution, is denoted as HSP-1.
Embodiment 2
By 3.66 grams of (0.01 moles) 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 20.00 grams of (0.10 moles) 3, 4 '-diaminodiphenyl oxide and 31.70 grams of (0.10 moles) 2, two (4-amino-benzene oxygen) cyanobenzene of 6-, 66.07 grams of (0.213 moles) 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride, 428 grams of N, N-N,N-DIMETHYLACETAMIDE and 300 grams of METHYLPYRROLIDONEs put into reactor, in 5 DEG C of stirring reactions after 5 hours, the fluorine-containing sense obtaining 849.43 grams of clear viscous homogeneous phases is wet polyimide precursor solution, be denoted as HSP-2.
Embodiment 3
By 3.66 grams of (0.01 moles) 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP), 29.7 grams of (0.15 moles) 4,4 '-diaminodiphenylmethane, 35.89 grams of (0.122 moles) 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride and 18.65 grams of (0.042 moles) 2,2-two (3,4-dicarboxyphenyi) hexafluoropropane dianhydride, 440 grams of N, N-N,N-DIMETHYLACETAMIDE puts into reactor, in 2 DEG C of stirring reactions after 4 hours, the fluorine-containing sense obtaining 527.90 grams of clear viscous homogeneous phases is wet polyimide precursor solution, is denoted as HSP-3.
Embodiment 4
Adopt acetone scavenging solution, after cleaning silicon substrate, put into loft drier to dry, drying 0.5 hour at 90 DEG C, vacuum evaporation gold (purity more than 99.9%) makes lower electrode subsequently, JP-6 conductive resin draws lower electrode lead-in wire, the fluorine-containing sense of spin coating HSP-1 is wet polyimide precursor solution again, (its concrete imidization technique is: nitrogen atmosphere in imidization, 100 DEG C are warming up to from room temperature, keep 1 hour, continue to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently), vacuum evaporation gold (purity more than 99.9%) makes top electrode, section, deionized water rinsing, drying 1 hour at 70 DEG C, screening, finishing, JP-6 conductive resin draws top electrode lead-in wire, obtained fluorinated polyimide humicap, be denoted as CHSP-1.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 1.
Embodiment 5
Adopt acetone, ethanol, hydrochloric acid is scavenging solution, after cleaning silicon substrate, put into loft drier to dry, drying 1 hour at 70 DEG C, vacuum evaporation gold (purity more than 99.9%) makes lower electrode subsequently, JP-6 conductive resin draws lower electrode lead-in wire, the fluorine-containing sense of spin coating HSP-2 is wet polyimide precursor solution again, (its concrete imidization technique is: nitrogen atmosphere in imidization, 100 DEG C are warming up to from room temperature, keep 1 hour, continue to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently), vacuum evaporation gold (purity more than 99.9%) makes top electrode, section, deionized water rinsing, drying 0.5 hour at 90 DEG C, screening, finishing, JP-6 conductive resin draws top electrode lead-in wire, obtained fluorinated polyimide humicap, be denoted as CHSP-2.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 1.
Embodiment 6
Adopt acetone, ammoniacal liquor, ethanol, hydrochloric acid is scavenging solution, after cleaning silicon substrate, put into loft drier to dry, drying 0.5 hour at 80 DEG C, vacuum evaporation gold (purity more than 99.9%) makes lower electrode subsequently, JP-6 conductive resin draws lower electrode lead-in wire, the fluorine-containing sense of spin coating HSP-3 is wet polyimide precursor solution again, (its concrete imidization technique is: nitrogen atmosphere in imidization, 100 DEG C are warming up to from room temperature, keep 1 hour, continue to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently), vacuum evaporation gold (purity more than 99.9%) makes top electrode, section, deionized water rinsing, drying 1 hour at 90 DEG C, screening, finishing, JP-6 conductive resin draws top electrode lead-in wire, obtained fluorinated polyimide humicap, be denoted as CHSP-3.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 1.
The performance data of table 1 fluorinated polyimide humicap
Embodiment 7
Get appropriate embodiment 1, embodiment 2, the fluorine-containing sense of embodiment 3 is wet polyimide precursor solution, i.e. HSP-1, HSP-2, HSP-3, be coated on equably respectively on clean flat glass film, put into air blast high temperature oven film-forming, concrete technology is: nitrogen atmosphere, 100 DEG C are warming up to from room temperature, keep 1 hour, continue to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently, poach demoulding, dry, obtain fluorine-containing sense to wet Kapton.The thermal gravimetric analyzer utilizing German NETZ company to produce surveys its initial heat decomposition temperature Tonset (nitrogen atmosphere, temperature rise rate 20 DEG C/min), the results are shown in Table 2; Its volume specific resistance ρ v (1MHz, 25 DEG C) tested by the megger utilizing Guilin Electro Scientific institute to produce, and the results are shown in Table 2; The electronic tensile machine utilizing the many will in Dongguan to produce tests its mechanical property, the results are shown in Table 2.
The fluorine-containing sense of table 2 is wet the performance data of Kapton
| Performance | HSP-1 | HSP-2 | HSP-3 |
| Tonset,℃ | 516.2 | 539.1 | 515.2 |
| ρv，Ω·cm | 3.1×10 16 | 1.5×10 16 | 1.1×10 16 |
| Tensile strength, MPa | 97.3 | 102.4 | 89.7 |
Comparative example 1
Adopt the Recipe of embodiment 1, only change the consumption of aromatic dianhydride, its mole number is made to equal 2, the total mole number of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and aromatic diamine, obtain the fluorinated polyimide precursor solution of clear viscous homogeneous phase, be denoted as HSP-C1.
Adopt the Recipe of embodiment 2, only change the consumption of aromatic dianhydride, its mole number is made to equal 2, the total mole number of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and aromatic diamine, obtain the fluorinated polyimide precursor solution of clear viscous homogeneous phase, be denoted as HSP-C2.
Adopt the Recipe of embodiment 3, only change the consumption of aromatic dianhydride, its mole number is made to equal 2, the total mole number of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and aromatic diamine, obtain the fluorinated polyimide precursor solution of clear viscous homogeneous phase, be denoted as HSP-C3.
Comparative example 2
Adopt the processing method of embodiment 4, replace the fluorine-containing sense of HSP-1 to wet polyimide precursor solution with the fluorinated polyimide precursor solution HSP-C1 of clear viscous homogeneous phase, obtained electric capacity, is denoted as CHSP-C1.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 3.
Adopt the processing method of embodiment 5, replace the fluorine-containing sense of HSBP-2 to wet polyimide precursor solution with the fluorinated polyimide precursor solution HSP-C2 of clear viscous homogeneous phase, obtained electric capacity, is denoted as CHSP-C2.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 3.
Adopt the processing method of embodiment 6, replace the fluorine-containing sense of HSP-3 to wet polyimide precursor solution with the fluorinated polyimide precursor solution HSP-C3 of clear viscous homogeneous phase, obtained electric capacity, is denoted as CHSP-C3.Utilize humidity generator, thermocouple temperature measurement instrument, capacitance measuring tester to measure its humidity sensing characteristic parameter, the results are shown in Table 3.
The performance data of table 3 fluorinated polyimide electric capacity
Visible, fluorinated polyimide electric capacity CHSP-C1, CHSP-C2, CHSP-C3, insensitive to humidity, therefore, fluorinated polyimide precursor solution HSP-C1, HSP-C2, HSP-C3, be difficult to the service requirements meeting humicap.
Claims (9)
1. a fluorinated polyimide humicap, is characterized in that: described humicap is made up of wet polyimide coating and top electrode of substrate, lower electrode, fluorine-containing sense; Wherein, the fluorine-containing sense polyimide that wets is reacted by two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and the aromatic dianhydride of 2,2-and forms; Wherein, the mol ratio of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-and aromatic diamine is 1:11-20; The ratio of the total mole number of two (3-amino-4-hydroxylphenyl) HFC-236fa of aromatic dianhydride mole number and 2,2-, aromatic diamine is 1.01-1.03:1.
2. a kind of fluorinated polyimide humicap according to claim 1, is characterized in that: the raw material that described lower electrode and top electrode adopt is selected from one or more in platinum, gold and silver, nickel, and purity is more than 99.9%.
3. a kind of fluorinated polyimide humicap according to claim 1, is characterized in that: described substrate is silicon chip.
4. a kind of fluorinated polyimide humicap according to claim 1, is characterized in that: described aromatic diamine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 2,4,6-trimethylammonium mphenylenediamine, 4,4 '-diamino-4 "-hydroxyl tritane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 4,4 '-diaminobenzophenone, DDS, 3,3 '-diaminodiphenylsulfone(DDS), two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) cyanobenzene of 2,6-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, one or more in Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene.
5. a kind of fluorinated polyimide humicap according to claim 1, is characterized in that: described aromatic dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, two (3, the 4-dicarboxyphenyi) hexafluoropropane dianhydride of 2,2-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride of 2,2-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) benzophenone dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl dianhydride, one or more in 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride.
6. a preparation method for fluorinated polyimide humicap as claimed in claim 1, comprising:
After scavenging solution cleaning substrate, put into loft drier and dry, drying 0.5 hour-1 hour at 70 DEG C-90 DEG C, vacuum evaporation subsequently makes lower electrode, and JP-6 conductive resin draws lower electrode lead-in wire, the more fluorine-containing sense of spin coating is wet polyimide precursor solution, imidization, vacuum evaporation makes top electrode, section, deionized water rinsing, drying 0.5 hour-1 hour at 70 DEG C-90 DEG C, screening, finishing, JP-6 conductive resin draws top electrode lead-in wire, obtained fluorinated polyimide humicap;
Wherein, the wet preparation method of polyimide precursor solution of fluorine-containing sense comprises the steps: 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-, aromatic diamine, aromatic dianhydride, strong polar non-proton organic solvent put into reactor, in 0 DEG C of-5 DEG C of stirring reaction after 2 hours-5 hours, obtain fluorine-containing sense and to wet polyimide precursor solution.
7. the preparation method of a kind of fluorinated polyimide humicap according to claim 6, is characterized in that: described scavenging solution is selected from one or more in acetone, ethanol, ether, ammoniacal liquor, hydrogen peroxide, hydrochloric acid, sulfuric acid.
8. the preparation method of a kind of fluorinated polyimide humicap according to claim 6, it is characterized in that: described imidization concrete technology is: nitrogen atmosphere, from room temperature, be warming up to 100 DEG C, keep 1 hour, continue to be warming up to 150 DEG C, keep 1 hour, continue to be warming up to 200 DEG C, keep 1 hour, continue to be warming up to 280 DEG C, keep 1 hour, naturally cool to room temperature subsequently.
9. the preparation method of a kind of fluorinated polyimide humicap according to claim 6, it is characterized in that: described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO); Wherein, described strong polar non-proton organic solvent and the total mass ratio of reactant are 4-6:1; The total mass of reactant refers to the quality sum of two (3-amino-4-carboxyl phenyl) HFC-236fa, aromatic diamine and the aromatic dianhydride of 2,2-.
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