CN103560207A - Organic thin-film solar cell and preparation method thereof - Google Patents
Organic thin-film solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic thin-film solar cell and a preparation method of the organic thin-film solar cell. The organic thin-film solar cell structurally comprises a substrate, transparent conductive anode ITO, an anode buffer layer, an optical active layer, a cathode buffer layer and a metal cathode, wherein the optical active layer is doped with the appropriate amount of ultraviolet sensitive glue, and the ultraviolet sensitive glue comprises unsaturated polyester resin or acrylic resin, styrene, derivatives of the styrene, photoinitiators, photosensitizers and additives. According to the organic thin-film solar cell and the preparation method of the organic thin-film solar cell, adhesive force between the anode buffer layer and the optical active layer of the organic thin-film solar cell is improved, the problem of interface mismatch between the anode buffer layer and the optical active layer is solved, stability of a device is improved, and the service life of the device is prolonged.
Description
Technical field
The invention belongs to organic polymer photovoltaic device or organic semiconductor thin-film area of solar cell, be specifically related to a kind of organic thin film solar cell and preparation method thereof.
Background technology
The problem such as energy scarcity and ecological deterioration has become the major issue that human survival and development faces.Due to the excessive limited non-renewable energy resources of exploitation of the mankind, make current the relied on traditional energy of the mankind occur resource exhaustion as coal, oil and natural gas etc., and consequent global energy fight is reached the decisive stage the stage day by day.As everyone knows, the kind of clean energy resource has wind energy, water energy, geothermal energy and solar energy etc., but former three is limited to region or development cost, and spread is not used at present.And more than solar energy occupies 99 % of earth gross energy, and do not pollute, become one of new forms of energy of scientist's development and utilization.Although silicon single crystal solar cell photoelectric conversion efficiency is very high and technology is comparatively ripe, its processing technology is very complicated, and material requirements is harsh and be difficult for carrying out large area flexible processing, and some material has toxicity and makes preparation cost high.Organic thin film solar cell is synthetic easily with its material, raw material sources are extensive, manufacture craft is simple and with low cost, power consumption less, can make flexible device and be easy to the advantages such as large-scale production, obtained scientist's great attention and great interest.
Through development for many years, the theoretical research of organic thin film solar cell and performance optimization are day by day abundant, yet for the research of its commercial applications, shortcoming relatively also.In the face of environment complicated and changeable, people have proposed more requirement to the job stability of organic thin film solar cell.In numerous factors that affect organic thin film solar cell stability, the mismatch problem of anode modification layer and photoactive layer is a masty difficult problem always.Conventionally the anode modification layer material PEDOT:PSS adopting is hydrophilic material, and the material of photoactive layer is hydrophobic material, obviously, between the two, exist in conjunction with unstable problem, thereby the phenomenon that the interface that can cause anode modification layer and photoactive layer produces disengaging, peels off under the effect of stress, the parameters such as short circuit current, fill factor, curve factor of device are reduced, cause the quick decline of device performance.Therefore, solve the matching problem at interface between anode buffer layer and photoactive layer, to improving the working life of organic thin film solar cell, have very important effect.
Summary of the invention
The present invention is directed to above-mentioned weak point a kind of organic thin film solar cell and preparation method thereof is provided, object is the adhesive force improving between organic thin film solar cell anode buffer layer and photoactive layer, solve the interface mismatch problem between anode buffer layer and photoactive layer, increase the stability of device simultaneously, improve the working life of device.
To achieve these goals, technical scheme of the present invention is: a kind of organic thin film solar cell, it is characterized in that, this solar battery structure is followed successively by from top to bottom: substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode, in described photoactive layer, be mixed with ultraviolet sensitivity glue, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5 %
Styrene and its derivatives 0.2-2 %
Light trigger 0.1-2 %
Sensitising agent and auxiliary agent 0.2-3 %
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler.
Further, described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate.
Further, described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of decanedioic acid two (2-ethyl), Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene.
Further, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.02-5 %.
Further, described photoactive layer is mixed with and is formed by electron donor material PTB7 and electron acceptor material PCBM, and described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, and described solution concentration is 1-30 mg/ml, and thickness is 40-250 nm.
Further, described anode buffer layer material is poly-(the sub-second dioxy thiophene of 3,4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in a kind of, thickness is 10-80 nm.
Further, described cathode cushioning layer material is a kind of in TPBi, BCP, Bphen, LiF, and thickness is 1-10 nm.
Further, described metallic cathode material is a kind of in Ag, Al, Cu, and thickness is 100-300 nm.
Further, described substrate is rigid substrate or flexible substrate, described rigid substrate is glass or sapphire, and described flexible substrate is the thin polymer films such as metal forming, polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid.
A preparation method for organic thin film solar cell, comprises the following steps:
1. first the substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying PEDOT:PSS solution, prepare anode buffer layer, or at transparent conductive anode ITO surface rotary coating, printing or spraying MoO
xsolution is prepared anode buffer layer, and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5 %
Styrene and its derivatives 0.2-2 %
Light trigger 0.1-2 %
Sensitising agent and auxiliary agent 0.2-3 %
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light;
5. in photoactive layer surface evaporation, rotary coating or spraying, prepare cathode buffer layer;
6. at cathode buffer layer surface evaporation metal negative electrode.
Compared with prior art, beneficial effect of the present invention is: (1) adds the photoactive layer of ultraviolet sensitivity glue by treatment with ultraviolet light, can strengthen significantly the tack between anode buffer layer and photoactive layer; (2) photoactive layer that is mixed with appropriate ultraviolet sensitivity glue after treatment with ultraviolet light, makes this layer of structure that formation is finer and close by crosslinked between unsaturated bond, effectively intercepts water oxygen and enters photoactive layer, increases performance and the stability of organic thin film solar cell.
Accompanying drawing explanation
Fig. 1 is organic thin film solar cell structural representation provided by the present invention, is followed successively by from top to bottom: substrate (1), transparent conductive anode ITO(2), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5), metallic cathode (6);
Fig. 2 is the life characteristic that does not adopt the organic thin film solar cell in ultraviolet sensitivity glue and embodiment 4.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described:
Technical scheme of the present invention is how a kind of organic thin film solar cell and preparation method thereof is provided, and as shown in Figure 1, device architecture is followed successively by from top to bottom: substrate 1, transparent conductive anode ITO 2, anode buffer layer 3, photoactive layer 4, cathode buffer layer 5, metallic cathode 6.
In organic thin film solar cell in the present invention, substrate 1 is the support of electrode and organic thin film layer, it has good light transmission in visible region, the ability that has certain anti-steam and oxygen infiltration, there is good profile pattern, it can be rigid substrate or flexible substrate, rigid substrate can be a kind of in glass or sapphire, and flexible substrate can be the thin polymer films such as metal forming or polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid; Anode buffer layer 2 is poly-(the sub-second dioxy thiophene of 3,4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in a kind of, thickness is 10-80 nm; Photoactive layer is mixed with and is formed by electron donor material PTB7 and electron acceptor material PCBM, and described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, and described solution concentration is 1-30 mg/ml, and thickness is 40-250 nm; In photoactive layer, be mixed with ultraviolet sensitivity glue, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5 %
Styrene and its derivatives 0.2-2 %
Light trigger 0.1-2 %
Sensitising agent and auxiliary agent 0.2-3 %
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler; Described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.02-5 %; Described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate; Described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of decanedioic acid two (2-ethyl), Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; Described cathode cushioning layer material is TPBi, BCP, Bphen or LiF, and described thickness of thin layer is 1-10 nm; Described metallic cathode material is Ag, Al or Cu, and thickness is 100-300 nm.During measurement, sunlight is from substrate surface incident, and electrode anode and cathode is connected with test circuit anode and cathode, the voltage-current curve of test component.
In the present invention, each composition is described as follows:
Unsaturated polyester resin: unsaturated polyester (UP) is by the mixed linear polyesters that reacts and make under the effect of initator with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols of undersaturated binary acid (or acid anhydrides).In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and the undersaturated vinyl monomer copolymerization of this class, crosslinking curing and become three-dimensional-structure.In general, the adhesive being obtained by this resin is because volume contraction in solidification process is larger, and the internal stress of gluded joint is very large.In the inside of glue-line, easily there is micro-crack and cause splicing power to diminish; Meanwhile, owing to containing ester bond in macromolecular chain, meet acid, alkali is easily hydrolyzed, thus resistance to medium and resistance to water poor, easily distortion under the environment of high temperature and humidity; In addition, its curing rate is slower, therefore, shows poor combination property, therefore mostly use as non-structure glue.By reducing unsatisfied chemical bond content, adopt monomer that polymerization shrinkage is low, add the means such as inorganic filler and thermal plastic high polymer, can improve its overall performance.
Acrylic resin: this resin system curing rate is fast, studies at present morely.
Monomer (Styrene and its derivatives etc.) conventionally and resin be used in conjunction with, one side, as diluent, makes glue have the viscosity of constructability; There is again on the other hand reactivity, solidify the laggard resin network that enters, the final performance of solidfied material is had to certain improvement.The monomer of early application is Styrene and its derivatives, and this class diluent crosslinking rate is slow, volatility is large and poisonous, poor heat resistance.Now, simple function group or polyfunctional group (methyl) acrylate of adopting more, as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc., the poor problem of adhesive ubiquity thermal endurance of these ester preparations, and also there is the defect that volatility is large in the lower ester of some molecular weight.If introduce aromatic rings in molecular structure, can improve intensity and the resistance to water of glue, extend the storage period of glue.To the requirement of monomer mainly: the respond of low viscosity, highly diluted effect and height, also to take into account volatility, toxicity and peculiar smell little simultaneously, good etc. to the compatibility of resin.In order to regulate various performance parameters, often adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
Free radical activity diluent is divided into exploitation first generation acrylic acid polyfunctional monomer, the second generation acrylic acid polyfunctional monomer of recent development and more excellent third generation acrylic monomers early.
Simple function reactive diluent has: styrene, NVP, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, latter two is the good toughness reinforcing monomer of plasticising.
Difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol (200) diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, acrylate-functional monomer mainly contains 1,6-hexanediyl ester (HDDA), BDO diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA) and trifunctional three through methylpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation three is through methylpropane triacrylate, pentaerythrite three propylene alcohol esters and pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene glycolbismethyl-acrylate, long-chain fat hydrocarbon glycidol ether acrylic acid, resorcinol bisglycidyl ether, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate.They have replaced active little first generation acrylic acid monofunctional monomer.But along with the develop rapidly of UV curing technology, they reveal the large shortcoming of the excitant of skin.
Overcome the large shortcoming of excitant, also should there is higher activity and state of cure.Second generation acrylic acid polyfunctional monomer is mainly in molecule, to introduce ethyoxyl or propoxyl group, as ethoxylation trihydroxy methyl propane triol triacrylate (TMP (EO) TMA), propoxylation trihydroxy methyl propane triol triacrylate (TMP (PO) TMA), propoxylation glycerol triacrylate (G (PO) TA).Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester (HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester (TMP (PO) MEDA).In molecule, introduce after alkoxyl, can reduce the viscosity of monomer, reduce the excitant of monomer simultaneously.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, ring, vinyl ether monomers etc. can be as the diluent of cation photocuring resin.Therein ethylene pyridyl ethers compound and oligomer curing rate are fast, modest viscosity, tasteless, nontoxic advantage, can be used in conjunction with epoxy resin.Vinyl ether monomers has: 1, 2, 3-propanetriol-diglycidyl-ether (EPON-812), triethylene glycol divinyl ether (DVE-3), 1, 4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), perfluor n-propyl vinyl ether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, vinyl butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethene-perfluoro propyl vinyl ether, tetrafluoroethene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
Epoxy compounds monomer has: 3,4-epoxy radicals hexahydrobenzoid acid-3', 4'-epoxy radicals cyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Light trigger: in ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, to cause or the carrying out of accelerated reaction.By the difference of its mechanism of action, can be divided into light trigger and sensitising agent.Difference is that light trigger, when reaction starts, absorbs the luminous energy of suitable wavelength and intensity, photophysical process occurs and reach its a certain excitation state, if this excited energy is greater than the needed energy of breaking bonds, produces free radical polymerization; And sensitiser absorption luminous energy is to its a certain excitation state, just by energy in molecule or intermolecular transfer, by another molecule that obtains energy, produce free radical polymerization.Compare with light trigger, sensitising agent itself does not consume or change structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: the one, and energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, the photosensitive mechanism shifting through generating electric charge.The light trigger with practical value of having developed has benzoin and its derivatives and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initators, yellowing resistance, trigger rate are different, and in different resin systems, efficiency of initiation is also different, should be according to the reasonable selection that needs of different occasions.As cyanacrylate and C (CH
2oCCH
2cH
2sH) system, use respectively benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether causes, be respectively 18s, 20s and 25s curing time, and while causing with benzophenone, be only 15s curing time, and simultaneously the light transmittance of solidfied material also can due to wavelength difference, difference be larger, and this will be according to actual conditions reasonable selection.
The effect of light trigger is to absorb after ultraviolet light energy at it, through decomposing, produces free radical, thus the unsaturated bond polymerization in initiator system, and crosslinking curing becomes an integral body.Conventional radical photoinitiator has cracking and puies forward the large class of Hydrogen two.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is homolysis after absorbing ultraviolet light, produces two free radicals, and free radical causes unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether, acylphosphine oxide comprises: 2, 4, 6-trimethylbenzene formyl diphenyl phosphine oxide (TPO) and (2, 4, 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenylbis (2, 4, 6-trimethyl benzoyl) phosphine oxide), phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are more satisfactory light triggers, there is very high light-initiated activity, long wave near ultraviolet ray is had to absorption, be applicable to the situation that whitewash and film are thicker, and there is good stability, can variable color or fade.
Carry Hydrogen initator: carry Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein thioxanthone photoinitiator at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and hydrogen-taking capacity strong, there is higher efficiency of initiation.Carrying Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to application.Triplet state carbonyl free radical is than more likely extracting hydrogen on secondary carbon or on methyl from the tertiary carbon of hydrogen donor molecule, and the hydrogen being connected on the hetero-atoms such as oxygen or nitrogen more easily extracts than the hydrogen on carbon atom.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, N-diethyl-and to dimethylamino benzamide.
Benzophenone light initiation system, benzophenone need to be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.Mainly comprise: benzophenone, thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA), alpha-hydroxy-2, 2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as can eliminate oxygen in glued membrane to the benzophenone of the inhibition of Raolical polymerizable the initiator system that coordinates with tertiary ammonia; Michler's keton and benzophenone are used in conjunction with, and can obtain more cheap and effectively initiator system.
Cationic photoinitiator: this type of initator of aromatic sulfonium salts and salt compounded of iodine has excellent high-temperature stability, also has stability with epoxy resin after coordinating, so be widely used in cationic curing system.But their the longest absorbing wavelength does not absorb in ， near ultraviolet band, far-ultraviolet region, generally will add light sensitizer, as: radical initiator or light-sensitive coloring agent carry out sensitizing.
This type of initator comprises: xylyl iodine hexafluorophosphate (PI810), hydroxy phenyl salt compounded of iodine (HTIB), the two detergent alkylate iodine hexafluoro antimonates of 4,4-, xylyl salt compounded of iodine, diphenyl hexafluoroarsenate salt compounded of iodine, [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] the iodo-hexafluoro antimonate of benzene, [4-(is to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, 4-(is to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4,4'-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820), 4,4'-diacetylamino diphenyl iodine hexafluorophosphate, 3,7 one dinitro dibenzo ring-type salt compounded of iodine and 3,7 one dinitro dibenzo ring-type bromine salt, tetrafluoro boric acid diaryl group iodized salt, 3,3'-dinitro diphenyl salt compounded of iodine, 3,3'-dinitro diphenyl salt compounded of iodine and several 2,2'-bis-replaces (iodine, bromine, chlorine)-5,5'-dinitrophenyl salt compounded of iodine, iodate 2-[2-(3-indolizine) vinyl]-1-methylquinoline salt, iodate 4-(2-benzoxazole)-N-picoline salt, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triaryl phosphine glyoxalidine salt, triaryl phosphine 1,1'-dinaphthalene glyoxalidine ring salt, 3,7-dinitro dibenzo bromine five rings salt, p-methyl benzenesulfonic acid triphenyl sulfosalt, bromination triphenyl sulfosalt, (4-thiophenyl-phenyl) diphenyl sulphur hexafluorophosphate, 4-(thiophenyl) triphenyl sulphur hexafluorophosphate, 3,3'-dinitro diphenyl iodine hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triphenyl sulfosalt, 4-chlorphenyl diphenyl sulphur hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, 4-acetamido phenyl diphenyl sulphur hexafluorophosphate, 3-benzoylphenyl diphenyl sulphur hexafluorophosphate, triphenyl sulphur borofluoride, triphenyl sulphur hexafluorophosphate, triphenyl sulphur hexafluoro antimonate, 4-tolyl diphenyl sulphur hexafluorophosphate, phosphorus hexafluoride triaryl sulfonium salts, antimony hexafluoride triaryl sulfonium salts, [4-(is to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, the bromo-2'-luorobenzyl of 1-(4'-) pyridiniujm, [4-(is to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4-[4-(p-nitrophenyl formoxyl) and thiophenyl] benzene } phenyl-iodide hexafluorophosphate, 4-[4-(is to methyl benzoyl) and thiophenyl] benzene } phenyl-iodide hexafluorophosphate, 4-[4-(is to methyl benzoyl) and phenoxy group] benzene } phenyl-iodide hexafluorophosphate, [4-(is to benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, the two detergent alkylate iodine hexafluoro antimonates of 4,4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is a kind of new cation light initiator developing after two fragrant salt compounded of iodine and three aromatic sulfonium salts, under illumination, first luxuriant molysite ion forms aromatic radical ligand, produce the complex compound with the unsaturated iron of epoxy compounds molecule coordination simultaneously, the complex compound of the lewis acidic feature of this complex compound tool then formation and the coordination of three epoxy compounds molecules, one of them epoxy compounds can open loop form cation, it can cause cationic ring-opening polymerization, forms polymer.Formation due to ferrocene salt-epoxy radicals complex, epoxy compounds cationic species at normal temperatures needs the time, therefore need be under the condition of external world's heating, to improve polymerization speed.
This type of salt comprises: cyclopentadienyl group-iron-benzene salt, cyclopentadienyl group-iron-toluene salt, cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-naphthalene salts, cyclopentadienyl group-iron-biphenyl salt, cyclopentadienyl group-iron-2,4-dimethyl acetophenone salt, acetyl group-cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-2,4-diethoxybenzene salt, ferrocene tetrafluoroborate, the luxuriant iron tetrafluoroborate of toluene, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-Isosorbide-5-Nitrae-diethoxybenzene salt, cyclopentadienyl group-iron-chlorobenzene salt, cyclopentadienyl group-iron-(Isosorbide-5-Nitrae-diethoxybenzene) hexafluorophosphate, cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate, 1,10-phenanthrolene ferrous perchlorate salt, 1,10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, [two (diphenylphosphine) ferrocene of 1,1'-] Nickel Chloride, vinyl ferrocene, N, N'-di-ferrocene methylene butanediamine quaternary ammonium salt, ferrocene formamide, ferrocene acyl propionic acid, ferrocenyl methyl ketone, ethyl dicyclopentadienyl iron, Butyrylferrocene, butyl ferrocene, N, N-dimethyl-amine methyl ferrocene, 1,1'-dibenzoyl ferrocene, (3-carboxyl propionyl group) ferrocene, 1,1'-dibromo ferrocene, Aminoferrocene.
The light trigger of macromolecule loading: in photocuring system, light trigger is not often to exhaust completely in Light Curing, and the part of photodissociation can not move to coating surface, makes coating yellowing and aging, affects the quality of product; On the other hand, some initators and system are incompatible or compatibility is bad, and its application is restricted.For addressing these problems, people are by light trigger producing high-molecular.The relatively low molecular initator tool of the initator of producing high-molecular has the following advantages: A, in polymer chain, energy transfer and intermolecular reaction become and be more prone to, and make high-molecular optical initator have higher activity.B, by with nonactive group copolymerization, regulates and design the distance of photosensitive group, or change the distance of optical active group and main chain, thereby acquisition has different photoactive initators.C, can introduce different optical active groups at same macromolecular chain, utilize their cooperative effect to improve light sensitive effect.The producing high-molecular of D, initator, has limited the migration of initator, prevents coating flavescence and aging.E, because most of photolysis debris are still connected on macromolecule matrix, therefore, can reduce smell and the toxicity of system.
The producing high-molecular of initator can directly be connected in initator on the chain of macromolecule or oligomer, as thioxanthone or acidic group phosphine oxide etc. are introduced on macromolecular chain; Also can in initator, introduce the functional group that polymerization can occur, make it in Light Curing, realize producing high-molecular, as benzophenone structural is introduced in tetraacrylate.
The compatibility of various light triggers is also a research direction in recent years, after compatibility, re-uses, and both can reduce costs, and can expand again the region of absorbing wavelength, improves the absorption of ultraviolet radiation energy, thus the solidification effect obtaining.The compatibility of light trigger can be both between same type, as be both free radical type, for example the new Irgacure-1700 releasing of Ciba is exactly by (2 of 25 %, 4,6-trimethylbenzene formyl) alpha-hydroxy-2 of phenyl phosphine oxide (BAPO) and 75 %, 2 dimethyl acetophenones (1173) form, and Irgacure-1800 is exactly that Alpha-hydroxy cyclohexyl-phenyl ketone (184) by the BAPO of 25 % and 75 % forms etc.; Also can be formed by dissimilar initator, as light trigger compatibility free radical type and cationic, for example, triaryl thiaxanthene salt and benzophenone are coordinated, can make the curing rate of epoxy compounds be improved.
Auxiliary agent: in general, for adapting to the bonding requirement of varying environment, also need to add various auxiliary agents in ultraviolet photo-curing cementing agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc.Although their shared components in adhesive are few, sometimes the processing characteristics of glue or adhesive property produced to vital effect.As cyanacrylate and C (CH
2oCCH
2cH
2sH) under the initiation of benzophenone, if add the silicone couplet CH of l%
2=CHSi (OCH
2cH
2oCH
3)
3, after ultraviolet light polymerization, be placed under the environment of 80-100% humidity, after 1 year, find not change, and if do not add coupling agent, under the same terms, just after 2 days there is white erosion in bonded part, one week afterwards glue-line strip down completely.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), separate two dioctyl phthalates (DOS), hexanedioic acid dioctyl ester (DOA), three vinyl butyl ether base phosphates, hexanedioic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tri trimellitate (2-ethyl) own ester (TOTM), decanedioic acid two (2-ethyl) own ester (DOS), Diethylene Glycol Dibenzoate (DEDB), dipropylene glycol dibenzoate, separate diacid dibenzyl ester (DBS), BS (BS), chlorosulfonated polyethylene (toughening elastic body), triphenyl phosphate (TPP), tricresyl phosphate (dimethylbenzene) ester (TXP), poly-hexanedioic acid propylidene ester (PPA), epoxidized soybean oil (ESO), octyl epoxy stearate (OES2), chlorinated paraffin-42 (CP-42), chlorinated paraffin wax-48(CP-48), chlorinated paraffin-52 (CP-52), distearyl acid diethylene glycol (DEG) (DEDR), tricresyl phosphate benzene methyl (TCP), diphenyl octyl phosphate (DPO), poly-hexanedioic acid butylidene ester (PBA), butyl epoxy stearate (BES), askarel (CDP), dimethylbenzene methylal resin (plasticizer FH), pumice wax pattern base oil (PROCESS OIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium is coupling agent, WB215(aliphatic acid 18 %, fatty acid ester 52 %, calcium carbonate 20 %).
Coupling agent is the material that a class has both sexes structure, and a part of group in their molecules can react with the chemical group on inorganic matter surface, forms strong chemical bonding; Another part group has close organic character, can be wound around with reactive organic molecule or physics, thus the material strong bonded that two kinds of character are varied in size.The coupling agent of current industrial use is divided into silanes, acyl esters of gallic acid, zirconium class and the large class of Organic Chromium complex compound four by chemical constitution.Wherein in adhesive, applying more is silanes, as methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-aminopropyltrimethoxysilane, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid the third vinegar base trimethoxy silane (KH-570), gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycidol ether propyl trimethoxy silicane, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane.
Levelling agent is for improving the flow leveling of resin, prevents the generation of the defects of coatings such as shrinkage cavity and pinprick, makes smooth coating, and can improve glossiness, comprises mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber and nitrocellulose.Wherein silicone based, comprise diphenyl polysiloxanes, methyl phenyl silicone, organic group modified polyorganosiloxane, polyethers organosilicon.
Stabilizer is, for reducing while depositing, polymerization occurs, and improves the storage stability of resin.Conventional stabilizer has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
Defoamer is for preventing and eliminate coating to produce bubble in manufacture and use procedure, preventing that coating from producing the disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can be made defoamer.Specifically there is tributyl phosphate, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK 037), three (butoxyethyl group) phosphate, triethyl phosphate, Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers (light yellow to water white transparency thick liquid), dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene, polyethers, cithrol, metallic soap of stearic acid, polyureas, the fatty acid ester compounded thing of higher alcohols, silicone defoaming agent has organic silicon modified by polyether oxygen alkane, organopolysiloxane mixture, silicone emulsion.
Polymerization inhibitor is, for reducing while depositing, polymerization occurs, and improves the storage stability of resin.Conventional polymerization inhibitor is generally divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, and the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, the inorganic matters such as ferric trichloride and Sulfur etc. also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain 1, the bitter hydrazine (DPPH) of 1-diphenyl-2-, TEMPO (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidine alcohols, phosphorous acid (TEMPO) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8 % tri-(N-nitroso-N-Phenylhydroxylamine) aluminium salt: the 2-phenolic group ethoxy propylene acid esters of 92 %, 4 % tri-(N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96 % ethyoxyl list oil triacrylates, MEHQ hydroquinone monomethyl ether, polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, dimethyl hydroquinones, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, BHT, 2,5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1,4-naphthoquinone, phenthazine, TBHQ (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, benzene sulfonamide amine acid salt, p-t-butyl catechol, methyl methacrylate (MMA), 2,4,6-trinitrophenol (TNP), 2,4-dimethyl-6-tert-butyl phenol (TBX), N, N-diethyl hydroxylamine (DEHA), to t-butyl catechol, 2,5-ditert-butylhydro quinone, adjacent methyl is to the adjacent methyl 1,4-benzoquinone of benzene two, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, NO free radical piperidine alcohols, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in resin, can make resin adhesive liquid when static, have higher denseness, becomes again under external force the material of low denseness fluid.Organobentonite acrylonitrile-butadiene rubber (NBR), montmorillonite (Na<sub TranNum="159">x</sub>(H<sub TranNum="160">2</sub>o)<sub TranNum="161">4</sub> <(Al<sub TranNum="162">2-x</sub>mg<sub TranNum="163">0.33</sub>) [Si<sub TranNum="164">4</sub>o<sub TranNum="165">10</sub>] (OH)<sub TranNum="166">2</sub>), bentonite [(Na<sub TranNum="167">x</sub>(H<sub TranNum="168">2</sub>o)<sub TranNum="169">4</sub>(Al<sub TranNum="170">2-x</sub>mg<sub TranNum="171">0.83</sub>) Si<sub TranNum="172">4</sub>o<sub TranNum="173">10</sub>) (OH)<sub TranNum="174">2</sub>], diatomite (unbodied SiO<sub TranNum="175">2</sub>form, and contain a small amount of Fe<sub TranNum="176">2</sub>o<sub TranNum="177">3</sub>, CaO, MgO, Al<sub TranNum="178">2</sub>o<sub TranNum="179">3</sub>and organic impurities), asbestos, wollastonite (CaSiO<sub TranNum="180">3</sub>), muscovite (KAl<sub TranNum="181">2</sub>(AlSi<sub TranNum="182">3</sub>o<sub TranNum="183">10</sub>) (OH)<sub TranNum="184">2</sub>), phlogopite (KMg<sub TranNum="185">3</sub>(AlSi<sub TranNum="186">3</sub>o<sub TranNum="187">10</sub>) (F, OH)<sub TranNum="188">2</sub>), magnesium silicon muscovite [K<sub TranNum="189">2</sub>((Fe<sub TranNum="190">2</sub>+ Mg) (Fe<sub TranNum="191">3</sub>+ Al)<sub TranNum="192">3</sub>(Si<sub TranNum="193">7</sub>alO<sub TranNum="194">20</sub>) (OH)<sub TranNum="195">4</sub>)], montmorillonite [Na<sub TranNum="196">x</sub>(H<sub TranNum="197">2</sub>o)<sub TranNum="198">4</sub> <(Al<sub TranNum="199">2-x</sub>mg<sub TranNum="200">0.33</sub>) [Si<sub TranNum="201">4</sub>o<sub TranNum="202">10</sub>] (OH)<sub TranNum="203">2</sub>], bentonite [Na<sub TranNum="204">x</sub>(H<sub TranNum="205">2</sub>o)<sub TranNum="206">4</sub>(Al<sub TranNum="207">2-x</sub>mg<sub TranNum="208">0.83</sub>) Si<sub TranNum="209">4</sub>o<sub TranNum="210">10</sub>) (OH)<sub TranNum="211">2</sub>], rilanit special, fumed silica, metallic soap (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth).In water-based system, with cellulose derivatives such as hydroxyethylcelluloses, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect that reaches filling, reinforcement, anti-attrition and reduce costs.Filler requires particle thin and even, can be scattered in equably in slurries, good to binding agent and other component associativities.The consumption of filler should be suitable, otherwise also can affect serous coat quality.Comprise inorganic mineral bentonite acrylonitrile-butadiene rubber (NBR), potassium aluminosilicate sodium (nepheline), calcium carbonate, moisture Petimin [Mg<sub TranNum="213">3</sub>[Si<sub TranNum="214">4</sub>o<sub TranNum="215">10</sub>] (OH)<sub TranNum="216">2</sub>], wollastonite (CaSiO<sub TranNum="217">3</sub>), muscovite [KAl<sub TranNum="218">2</sub>(AlSi<sub TranNum="219">3</sub>o<sub TranNum="220">10</sub>) (OH)<sub TranNum="221">2</sub>)], phlogopite [KMg<sub TranNum="222">3</sub>(AlSi<sub TranNum="223">3</sub>o<sub TranNum="224">10</sub>) (F, OH)<sub TranNum="225">2</sub>], magnesium silicon muscovite [K<sub TranNum="226">2</sub>((Fe<sub TranNum="227">2</sub>+ Mg) (Fe<sub TranNum="228">3</sub>+ Al)<sub TranNum="229">3</sub>(Si<sub TranNum="230">7</sub>alO<sub TranNum="231">20</sub>) (OH)<sub TranNum="232">4</sub>)], montmorillonite [Na<sub TranNum="233">x</sub>(H<sub TranNum="234">2</sub>o)<sub TranNum="235">4</sub> <(Al<sub TranNum="236">2-x</sub>mg<sub TranNum="237">0.33</sub>) [Si<sub TranNum="238">4</sub>o<sub TranNum="239">10</sub>] (OH)<sub TranNum="240">2</sub>], bentonite [Na<sub TranNum="241">x</sub>(H<sub TranNum="242">2</sub>o)<sub TranNum="243">4</sub>(Al<sub TranNum="244">2-x</sub>mg<sub TranNum="245">0.83</sub>) Si<sub TranNum="246">4</sub>o<sub TranNum="247">10</sub>) (OH)<sub TranNum="248">2</sub>], kaolin, red mud (Al<sub TranNum="249">1-x</sub>o<sub TranNum="250">x</sub>), calcium sulfate, acrylate high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in medium, forms the reagent of stable suspension.Dispersant is generally divided into inorganic dispersant and the large class of organic dispersing agent two.Conventional inorganic dispersant has silicates (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1, 2, 4-tricarboxylic acids four sodium, hexamethylene diamine four methylenephosphonic acid sylvite, two 1, 6 hexylidene triamine five methylenephosphonic acid sodium, trimerization Alendronate, calgon and sodium pyrophosphate etc.).Organic dispersing agent comprises triethyl group hexyl phosphonic acids, Amino Trimethylene Phosphonic Acid, HEDP (HEDP), ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS), ethylene diamine tetra methylene phosphonic acid (EDTMPA), diethylene triamine pentamethylene phosphonic (DTPMP), 2-phosphonic acids butane-1,2,4-tricarboxylic acids (PBTCA), PAPE (PAPE), 2-HPAA (HPAA), hexamethylene diamine four methylenephosphonic acids (HDTMPA), polyamino polyether base methylenephosphonic acid (PAPEMP), two 1,6 hexylidene triamine five methylenephosphonic acids (BHMTPMPA), lauryl sodium sulfate, polyacrylic acid (PAA), Sodium Polyacrylate (PAAS), HPMA (HPMA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer (AA/AMPS), acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer, acrylic acid-acrylate-sulfonate terpolymer, copolymer of phosphono carboxylic acid (POCA), polyacrylate, carboxylate-sulfonate-nonionic terpolymer, polyepoxy sodium succinate (PESA), poly (sodium aspartate) (PASP), base amylalcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester etc.
Antioxidant be take and suppressed the auxiliary agent that fluoropolymer resin thermal oxidative degradation is major function, belongs to the category of anti-oxidant reagent.Antioxidant is the topmost type of plastics stabilizing additive, and nearly all fluoropolymer resin all relates to the application of antioxidant.According to the mechanism of action, traditional antioxidant systems generally comprises primary antioxidant, auxiliary antioxidant and heavy metal ion passivator etc.Primary antioxidant be take and caught polymer peroxy radical as major function, has again the title of " peroxy radical capturing agent " and " chain termination type antioxidant ", relates to aromatic amine compounds and the large series of products of hindered phenol compound two.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, and N-is two-[3-(3,5-di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, dihydroquinoline; Hinered phenols antioxidant has: 2,5-ditert-butylhydro quinone, 2,6-di-tert-butyl-4-methy phenol, TBHQ, 2,5-ditert-butylhydro quinone (DBHQ), 2, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether, four [β-(tri-grades of butyl-4-hydroxy phenyls of 3,5-) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi), phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-hydroxy benzenes methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used in conjunction with.The two octadecyl esters (DSTP) of two Lauryl Alcohol esters, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, the two lauryls of thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-bis--n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl group diphenyl.
Heavy metal ion passivator, is commonly called as " copper resistant agent ", can complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, and typical structure is as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, also there is certain variation in the classification of antioxidant, and the most outstanding feature is the concept of having introduced " carbon radicals capturing agent ".This radical scavenger is different from traditional primary antioxidant, and they can catch polymer alkyl diradical, is equivalent to set up one defence line in traditional antioxidant system.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, chlorination hydroxylammonium, hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves resin melt viscoelasticity and promote the mobile modified additive of resin melting, and this analog assistant be take acrylic acid esters co-polymer (ACR) as main.
Anti-impact modifier improves the auxiliary agent of rigid polymer goods shock resistance.Mainly comprise haloflex (CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS), ethene-thiazolinyl acetate copolymer (EVA) and acrylonitrile-diene-ethylene copolymer (ABS) etc.The ethylene propylene diene rubber of polypropylene toughness-increasing modified middle use (EPDM) also belongs to rubber toughened scope.
The function of antistatic agent is to reduce the sheet resistance of polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, and is mainly included as cationic surfactant and anion surfactant.Cationic surfactant has: alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-dodecyloxy-the 2 '-hydroxypropyls of N-) first ammonium Methylsulfate salt, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-bis-(octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, palmitate quaternary ammonium salt, alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, the polymer of poly-(oxygen-1, the 2-second two bases) phosphate of 2,2'-nitrilo-di-methylcarbinol and α-tri-decyl-ω-hydroxyl, polyethylene glycol tridecyl ether phosphate, diethanolamine salt, oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, N-dihydroxyethyl p-toluidine, alkylphenol-polyethenoxy based quaternary ammonium salt, ethoxyl quaternary ammonium salt, the fluorine-containing quaternary ammonium salt of oxa-, anion surfactant has: fatty alcohol ether phosphate, phenolic ether phosphate (TXP-4), phenolic ether phosphate (TXP-10), different tridecanol phosphate, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphate kalium salt (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite, Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS, non-ionic surface active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acid polyethenoxy ether, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyl) beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
Negative and positive amphoteric surfactant comprises: dodecyl-dimethyl quaternary ammonium second inner salt, dodecyl dimethyl quaternary ammonium second inner salt, alkyl dihydroxy ethyl ammonium second inner salt, N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, 3-chloro propyl amine hydrochloric acid salt, N-tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tertbutyloxycarbonyl-L-2-trifluoromethyl-phenylalanine, glyphosate isopropyl amine salt.
Polymer Antistatic Agent comprises: the amphipathic copolymer that poly(ethylene oxide) (PEO), polyether ester acid imide, polyethylene glycol methacrylic acid copolymer, polyether ester amides (PEEA), polyether ester acetamide (PEAI), polyethylene glycol oxide, epoxy propane copolymer (PEO-ECH), polyethylene glycol methacrylate-styrene polymer (PEGMA), methacrylic acid (MAA), methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) form.
In fire retardant, inorganic combustion inhibitor comprises antimonous oxide, zinc molybdate, zinc oxide, iron oxide, tin oxide, aluminium hydroxide, magnesium hydroxide, antimony oxide, Firebrake ZB and red phosphorus, organic fire-retardant comprises deca-BDE, three (2, 3-dibromopropyl) phosphate, HBCD, poly-2, 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, Dowspray 9 homopolymers, melamine, cyanurate, isodecyl diphenyl phosphoester, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropyl phenyl ester, two (2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 ethoxy) the AminomethylphosphoniAcid Acid diethylesters of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyazodiphenylene phenyiphosphonate, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor claims again microbial inhibitor, is the growth of microorganism such as a class mould fungus inhibition, prevents the stabilizing additive that fluoropolymer resin is degraded by microbial attack.Most polymeric materials are to mould insensitive, but have mould sensitivity because its goods work in-process has added the material that plasticizer, lubricant, fatty acid soaps class etc. can grow der Pilz.The chemical substance that plastics comprise with mould inhibitor is a lot, and more common kind comprises organo-metallic compound (as organic mercury, organotin, organic copper, organo-arsenic etc.), organic compounds containing nitrogen, organic compounds containing sulfur, organic halogen compound and phenol derivatives etc.Comprising phenol, pentachlorophenol, phenyl mercury oleate, copper 8-quinolinolate, chlorination three second or tributyl tin, copper sulphate, mercury chloride, sodium fluoride.
Sensitizer is to dimethylamino benzamide; In promoter, aminopropyl silsesquioxane and Versamid mass ratio are 3:1.
Below specific embodiments of the invention:
As shown in Figure 1, substrate (1) is glass, and anode buffer layer (3) is PEDOT:PSS(10 nm), cathode buffer layer (5) is TPBi(10 nm), metallic cathode (6) is Ag(100 nm).Photoactive layer (4) is PTB7:PCBM(1:20,40 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.02 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95 %
Styrene and its derivatives 2 %
Sensitising agent and auxiliary agent 1 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(40 nm), cathode buffer layer 5 is TPBi(1 nm), metallic cathode 6 is Ag(300 nm).Photoactive layer 4 is PTB7:PCBM(5:1,250 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.05 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 96 %
Styrene and its derivatives 2 %
Light trigger 0.5 %
Sensitising agent and auxiliary agent 1.5 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(80 nm), cathode buffer layer 5 is TPBi(8 nm), metallic cathode 6 is Ag(150 nm).Photoactive layer 4 is PTB7:PCBM(1:1,200 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.1 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 97 %
Styrene and its derivatives 1 %
Sensitising agent and auxiliary agent 1 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20 nm), cathode buffer layer 5 is TPBi(8 nm), metallic cathode 6 is Ag(150 nm).Photoactive layer 4 is PTB7:PCBM(1:1,200 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.5 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 98 %
Styrene and its derivatives 0.2 %
Light trigger 0.5 %
Sensitising agent and auxiliary agent 1.3 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20 nm), cathode buffer layer 5 is TPBi(8 nm), metallic cathode 6 is Ag(150 nm).Photoactive layer 4 is PTB7:PCBM(1:1,200 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 1 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 99 %
Styrene and its derivatives 0.3 %
Light trigger 0.1 %
Sensitising agent and auxiliary agent 0.6 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20 nm), cathode buffer layer 5 is TPBi(8 nm), metallic cathode 6 is Ag(150 nm).Photoactive layer 4 is PTB7:PCBM(1:1,200 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 3 %.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 99.5 %
Styrene and its derivatives 0.2 %
Light trigger 0.1 %
Sensitising agent and auxiliary agent 0.2 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 7
As shown in Figure 1, substrate 1 is flexible PETG (PET) substrate, and anode buffer layer 3 is PEDOT:PSS(20 nm), cathode buffer layer 5 is TPBi(8 nm), metallic cathode 6 is Ag(150 nm).Photoactive layer 4 is PTB7:PCBM(1:1,200 nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 5 %.
Preparation method is as follows:
1. first the PET substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95 %
Styrene and its derivatives 1 %
Sensitising agent and auxiliary agent 3 %;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Table 1 is for adopting PET as the Performance Ratio of the organic thin film solar cell of substrate, and a kind of is the device that adds ultraviolet sensitivity glue in photoactive layer, and a kind of is the device that does not add ultraviolet sensitivity glue.Wherein, bending radius is 10 mm, and direction is outwardly-bent.
Claims (10)
1. an organic thin film solar cell, it is characterized in that, this solar battery structure is followed successively by from top to bottom: substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode, is mixed with ultraviolet sensitivity glue in described photoactive layer, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5 %
Styrene and its derivatives 0.2-2 %
Light trigger 0.1-2 %
Sensitising agent and auxiliary agent 0.2-3 %
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler.
2. organic thin film solar cell according to claim 1, is characterized in that, described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate.
3. organic thin film solar cell according to claim 1, it is characterized in that, described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of decanedioic acid two (2-ethyl), Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene.
4. organic thin film solar cell according to claim 1, is characterized in that, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.02-5 %.
5. organic thin film solar cell according to claim 1, it is characterized in that, described photoactive layer is mixed with and is formed by electron donor material PTB7 and electron acceptor material PCBM, described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, described solution concentration is 1-30 mg/ml, and thickness is 40-250 nm.
6. organic thin film solar cell according to claim 1, is characterized in that, described anode buffer layer material is poly-(the sub-second dioxy thiophene of 3,4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in a kind of, thickness is 10-80 nm.
7. organic thin film solar cell according to claim 1, is characterized in that, described cathode cushioning layer material is a kind of in TPBi, BCP, Bphen, LiF, and thickness is 1-10 nm.
8. organic thin film solar cell according to claim 1, is characterized in that, described metallic cathode material is a kind of in Ag, Al, Cu, and thickness is 100-300 nm.
9. organic thin film solar cell according to claim 1, it is characterized in that, described substrate is rigid substrate or flexible substrate, described rigid substrate is glass or sapphire, and described flexible substrate is the thin polymer films such as metal forming, polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid.
10. a preparation method for organic thin film solar cell, is characterized in that, comprises the following steps:
1. first the substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying PEDOT:PSS solution, prepare anode buffer layer, or at transparent conductive anode ITO surface rotary coating, printing or spraying MoO
xsolution is prepared anode buffer layer, and formed film is carried out to annealing in process;
3. the PTB7:PCBM solution that is mixed with ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying is prepared photoactive layer, and formed film is carried out to annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5 %
Styrene and its derivatives 0.2-2 %
Light trigger 0.1-2 %
Sensitising agent and auxiliary agent 0.2-3 %
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light;
5. in photoactive layer surface evaporation, rotary coating or spraying, prepare cathode buffer layer;
6. at cathode buffer layer surface evaporation metal negative electrode.
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| WO2017118015A1 (en) * | 2016-01-06 | 2017-07-13 | 青岛大学 | Organic rare-earth solid micelle and preparation method therefor, and method for improving photoelectric conversion efficiency of solar cell |
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| CN110676391A (en) * | 2019-09-27 | 2020-01-10 | 苏州威格尔纳米科技有限公司 | Packaging method of perovskite thin film battery pack |
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