CN103579504A - 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 thereof. The solar cell structure is provided with a substrate, a transparent conductive anode ITO (indium tin oxide), an anode buffer layer, an optical active layer, a cathode buffer layer and a metal cathode sequentially from bottom to up, wherein the optical active layer is doped with ultraviolet sensitive glue; the ultraviolet sensitive glue comprises the components in a mass ratio as follows: 93.5%-97% of photosensitive polysiloxane, 1.5%-5% of an photoinitiator, and 1.5%-3% of a diluent and auxiliaries; the diluent comprises toluene, dimethyl benzene, an active epoxy resin diluent, cyclic ether and vinyl ether monomers; and the auxiliaries comprise a filling agent, a stabilizing agent and a cross linking agent. With the adoption of the organic thin-film solar cell and the preparation method thereof, the problem of poor adhesiveness between the anode buffer layer and the optical active layer of the organic thin-film solar cell is solved, so that the interface compatibility between the anode buffer layer and the optical active layer is increased, meanwhile, the energy conversion efficiency is improved, and the attenuation speed is delayed.
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
Along with the increase year by year of global energy demand, energy problem becomes the matter of utmost importance that countries in the world economic development runs into.Solar energy is as a kind of green energy resource, one of new forms of energy of inexhaustible ，Shi various countries scientist development and utilization.The Bel research institute of the 1954 Nian， U.S. successfully develops silicon solar cell, has started the beginning of opto-electronic conversion research.Research about solar cell afterwards develops rapidly, mainly concentrates on the inorganic solar cell that monocrystalline silicon is active material at first.Developed again the devices such as GaAs, cadmium telluride and lamination GaInP/GaAs/Ge the nineties in 20 century, and they consist of monocrystalline, polycrystalline or noncrystal membrane.Because inorganic solar cell cost of material is high, the serious photoetch of complex manufacturing and narrow gap semiconductor makes the solar power generation can not spread.Make solar power generation obtain large-scale application, just must reduce costs.
Organic semiconducting materials is the most cheap solar cell material with there being most development potentiality, and its Heterosis is: on the one hand, because the synthetic cost of organic material is low, function and structure is easy to adjust, and pliability and film forming are all better; On the other hand, because the organic solar batteries course of processing is relatively simple, can low-temperature operation, element manufacturing cost also decreases.In addition, the potential advantages of organic solar batteries also comprise: can realize large area manufacture, can use flexible substrate, environmental friendliness, light portable etc., be expected to be applied in wrist-watch, hand-held calculator, toy, flexibility and can curling system etc. power in system.Through the development of two more than ten years, the conversion efficiency of organic thin film solar cell has had larger progress, and theory has also obtained further perfect, just progressively to mass market, strides forward.
Except efficiency, the stability of organic thin film solar cell is also the emphasis that researchers pay close attention to.A desirable solar photovoltaic device need to possess following speciality: under illumination, long-time retention is constant, insensitive to cold/heat, the repetitious variation such as bright/dark, dry/wet.Yet still there are at present many bottleneck problems, restricting the commercialization of organic thin film solar cell.The interphase match of anode buffer layer and photoactive layer is one of them significant problem.What because anode buffer layer is common, adopt is this hydrophilic material of PEDOT:PSS, and photoactive layer hydrophobic material normally, this causes in the middle of device preparation process, photoactive layer material is difficult for opening at anode buffer layer surface spreading, make the final photoactive layer film morphology forming poor, and can produce interfacial separation under the effect of interior external carbuncle, and then the efficiency of transmission of charge carrier is adversely affected, reduce the energy conversion efficiency of device.Therefore, solve the interphase match problem of anode buffer layer and photoactive layer, to the commercialization process of organic thin film solar cell, can play huge impetus.
Summary of the invention
Problem to be solved by this invention is how a kind of organic thin film solar cell and preparation method thereof is provided, object is to solve the poor problem of tack between organic thin film solar cell anode buffer layer and photoactive layer, increase the interphase match between anode buffer layer and photoactive layer, improve the energy conversion efficiency of device simultaneously, delayed the rate of decay of device performance.
To achieve these goals, the technical solution used in the present invention is:
A kind of organic thin film solar cell, it is characterized in that, the substrate that this solar battery structure sets gradually from bottom to up (1), transparent conductive anode ITO(2), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5) and metallic cathode (6), described photoactive layer is mixed with ultraviolet sensitivity glue in (4), and the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5～97% of light sensitivity
Light trigger 1.5～5%
Diluent and auxiliary agent 1.5～3%;
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
Further, the polysiloxanes of described light sensitivity comprises mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes and vinyl ether functional polysiloxanes.
Further, described light trigger comprises styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt and triaryl salt compounded of iodine.
Further, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.05～6.5%.
Further, described photoactive layer is mixed with and is formed by electron donor material P3HT and electron acceptor material ICBA, and described P3HT:ICBA mixed solution mass ratio is 1:20～5:1, and described solution concentration is 1～30mg/ml, and thickness is 40～250nm.
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 10～80nm.
Further, described cathode cushioning layer material is a kind of in TPBi, BCP, Bphen, LiF, and thickness is 1～10nm.
Further, described metallic cathode material is a kind of in Ag, Al, Cu, and thickness is 100～300nm.
Further, described substrate is a kind of in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
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, is dried and processes;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and formed film is carried out to annealing in process;
3. in anode buffer layer surface rotary coating, printing or spraying, be mixed with the photoactive layer of ultraviolet sensitivity glue, and formed film is carried out to annealing in process, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5～97% of light sensitivity
Light trigger 1.5～5%
Diluent and auxiliary agent 1.5～3%,
Diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent;
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, the present invention has following beneficial effect: (1) adds the photoactive layer of ultraviolet sensitivity glue by treatment with ultraviolet light, has improved the tack of anode buffer layer and photoactive layer; (2) photoactive layer after treatment with ultraviolet light, its degree of crystallinity is higher, and carrier mobility increases, and improves energy conversion efficiency; (3) photoactive layer after treatment with ultraviolet light, ultraviolet sensitivity glue crosslinked makes this layer of structure that formation is finer and close, effectively intercepts water oxygen and enters photoactive layer, improved performance and the stability of device; (4) adding of appropriate ultraviolet sensitivity glue, on not impact of the absorption of photoactive layer.
Accompanying drawing explanation
Fig. 1 is organic thin film solar cell structural representation provided by the present invention;
Fig. 2 does not adopt ultraviolet sensitivity glue and embodiment of the present invention 1(to adopt ultraviolet sensitivity glue) the current density voltage curve of organic thin film solar cell;
Mark in figure: 1, substrate, 2, transparent conductive anode ITO, 3, anode buffer layer, 4, photoactive layer, 5, cathode buffer layer, 6, metallic cathode.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments, and described embodiment is only the present invention's part embodiment, is not whole embodiment.Embodiment based in the present invention, those of ordinary skill in the art, not making other embodiment used that obtain under creative work prerequisite, belongs to protection scope of the present invention.
In conjunction with Fig. 1, organic thin film solar cell of the present invention, comprise the substrate 1, transparent conductive anode ITO2, anode buffer layer 3, photoactive layer 4, cathode buffer layer 5 and the metallic cathode 6 that set gradually from bottom to up, in described photoactive layer, be mixed with ultraviolet sensitivity glue, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5～97% of light sensitivity
Light trigger 1.5～5%
Diluent and auxiliary agent 1.5～3%,
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
Further, the polysiloxanes of light sensitivity comprises mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes and vinyl ether functional polysiloxanes.
Further, light trigger comprises styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt and triaryl salt compounded of iodine.
Further, photoactive layer is mixed with and is formed by electron donor material P3HT and electron acceptor material ICBA, and described P3HT:ICBA mixed solution mass ratio is 1:20～5:1, and described solution concentration is 1～30mg/ml, and thickness is 40～250nm.
Further, 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 10～80nm.
Further, cathode cushioning layer material is a kind of in TPBi, BCP, Bphen, LiF, and thickness is 1-10nm.
Further, metallic cathode material is a kind of in Ag, Al, Cu, and thickness is 100～300nm.
Further, substrate is a kind of in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
In the present invention, each composition is described as follows: ultraviolet curing organic silicon adhesive is owing to not only having the premium properties of organosilyl heatproof, weather-proof, electrical insulation capability, low surface tension and low-surface-energy, the excellent specific property of the ultraviolet photocureable material such as also having can cold curing, solidification rate is fast, pollution-free.Its prepolymer mainly comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes and vinyl ether functional polysiloxanes.
The early stage research of vinylated polysiloxanes UV curing system is more.The speed of photoresponse of this system is fast, particularly, under light trigger promotes, not disturbed by the inhibition of oxygen, can form softness and whippy cured film.Product can be applicable to fiber or other base material, comprises paper, metal, glass and polyethylene, polypropylene and polyester film etc.But this system exists dark reaction, the viscosity of system will increase gradually, and the hot strength of cured film declines.
Acrylate-basedization polysiloxanes UV curing system is good to the adhesiveness of base material, and solidification rate is high, and the chemistry of cured layer, physical stability are good, by adjustment, are filled a prescription and can be obtained desirable viscosity; But often with volume contraction, produce shrinkage stress in Light Curing.Under many occasions, shrinking is all a unfavorable factor.Acrylate-basedization polysiloxane coated is on the base materials such as metal, glass, plastics time, and contraction can cause coating adhesion to decline; While being coated on flexible substrate (as paper product, plastic film), contraction can cause rolls wrinkle.But one flaw cannot mar the jade, acrylate-basedization polysiloxanes with its high reaction activity and cheaply advantage won market, become the focus of study of UV-curable silicone prepolymers research field.
In the epoxy radicals of epoxy radicals polysiloxanes when there is cation photocuring, the epoxy radicals with ring strain is opened, and forms tension-free ehter bond, and volume contraction is very little, is even zero, becomes the major product in cation photocuring system.Epoxy compounds containing unsaturated double-bond is mainly containing vinyl or allylic epoxy compounds, as allyl glycidyl ether, glycidyl acrylate, dicyclohexyl pentadiene and 4-vinyl epoxidized cyclohexene, what wherein photocuring activity was the highest is epoxidized cyclohexene.For example, the end si-h bond of 4-vinyl epoxidized cyclohexene and polysiloxanes is carried out to hydrosilylation, obtain alicyclic epoxy radicals polysiloxanes.Epoxy radicals polysiloxanes can mix with Multiple components, and filler, pigment, crosslinking agent, catalyst, UV absorbers etc. can be applied in epoxy radicals polysiloxanes system.Now, the application of epoxy radicals polysiloxanes UV curing system is more and more extensive, becomes the main product in cation photocuring system.
The great advantage of styryl polysiloxanes UV curing system is inexpensive, wherein styryl is active owing to having higher photopolymerization reaction, styryl can be incorporated in silicon-oxygen backbone and carry out ultraviolet light polymerization, its object is mainly to improve the hardness of organosilicon material and the performance of other terms of mechanics.But the shortcoming that this system exists is also more, as high in volatility, inflammable, smell large, reaction speed is slower etc., curing performance is also not as other UV curing system.
The monomer of vinyl ether group polysiloxanes is the monomer that contains HZC=CH-O-base.Due to, the lone pair electrons of oxygen atom and two key generation conjugation, the cloud density of two keys is increased causing the C=C of vinyl ether group is electron rich group, polymerization activity is higher than general vinyl monomer, under ultraviolet light irradiation, can carry out the reactions such as radical polymerization, cationic charge transfer complex alternating copolymerization.Therefore, the uv curable oligomer of vinyl ethers can be applied in kind of photocuring system, as radically curing system, cationic curing system and mix curing system.Vinyl ethers prepolymer has that toxicity is low, smell is little, reactivity, and cured product has and shrinks the performances such as little, impact strength is high, and its potential application is extensive.But because the price of vinyl ethers monomer is higher, make vinyl ethers ultraviolet curing organic silicon material also not obtain generally application at home and abroad.
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 chapped 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 oxides (TPO) and (2, 4, 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenyl bis (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 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: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, also have 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-PI820), 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, 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 having obtained.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 be exactly by 25% (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) form, and Irgacure-1800 is comprised of 25% BAPO and 75% Alpha-hydroxy cyclohexyl-phenyl ketone (184) 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.
Reactive diluent, is mainly used in the viscosity of regulation system, also can affect solidification rate and material property, comprises toluene, dimethylbenzene, n-hexane, active epoxy diluent resin, cyclic ethers and vinyl ether monomers.
Catalyst can be selected two (2 ethyl hexanoic acid) dibutyl tin, dibutyltin diacetate or dibutyl tin laurate etc.Wherein dibutyltin diacetate catalytic activity is large, and curing rate is fast.The activity of dibutyl tin laurate is less, and curing rate is slow.
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), phthalic acid two is ester (DHP), separate two dioctyl phthalates (DOS), hexanedioic acid dioctyl ester (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral (DMP), diethyl phthalate (DEP), hexanedioic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), the own ester of phthalic acid two (2-ethyl), decanedioic acid two (2-ethyl) own ester (DOS), Diethylene Glycol Dibenzoate (DEDB), phthalic anhydride, 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 (PROCESSOIL637), 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, prevent the generation of the defects of coatings such as shrinkage cavity and pinprick, make smooth coating, and can improve glossiness, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenyl polysiloxanes, methyl phenyl silicone, organic group modified polyorganosiloxane, polyethers organosilicon.
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 (BYK037), 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% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: 92% 2-phenolic group ethoxy propylene acid esters, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, 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, 2.6-BHT, 2.5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1.4-naphthoquinones, 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
x(H
2o)
4{ (Al
2-xmg
0.33) [Si
4o
10] (OH)
2), bentonite [(Na
x(H
2o)
4(Al
2-xmg
0.83) Si
4o
10) (OH)
2], diatomite (unbodied SiO
2form, and contain a small amount of Fe
2o
3, CaO, MgO, Al
2o
3and organic impurities), asbestos, wollastonite (CaSiO
3), muscovite (KAl
2(AlSi
3o
10) (OH)
2), phlogopite (KMg
3(AlSi
3o
10) (FOH)
2), magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si
7alO
20) (OH)
4)], montmorillonite [Na
x(H
2o)
4{ (Al
2-xmg
0.33) [Si
4o
10] (OH)
2], bentonite [Na
x(H
2o)
4(Al
2-xmg
0.83) (Si
4o
10) (OH)
2], 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
3[Si
4o
10] (OH)
2], wollastonite (CaSiO
3), muscovite [KAl
2(AlSi
3o
10) (OH)
2)], phlogopite [KMg
3(AlSi
3o
10) (F, OH)
2], magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si7AlO
20) (OH)
4)], montmorillonite [Na
x(H
2o)
4{ (Al
2-xmg
0.33) [Si
4o
10] (OH)
2], bentonite [Na
x(H
2o)
4(Al
2-xmg
0.83) (Si
4o
10) (OH)
2], kaolin, red mud (Al
1-xo
x), 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.
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-di-t-butyl cresols, phenothiazine, anthraquinone, tertiary amine etc.
Below specific embodiments of the invention:
As shown in Figure 1, substrate (1) is glass, and anode buffer layer (3) is PEDOT:PSS(10nm), cathode buffer layer (5) is TPBi(10nm), metallic cathode (6) is Ag(100nm).Photoactive layer (4) is P3HT:ICBA(1:20,40nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 93.5% of light sensitivity
Diluent 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(40nm), cathode buffer layer (5) is TPBi(1nm), metallic cathode (6) is Ag(300nm).Photoactive layer (4) is P3HT:ICBA(5:1,250nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 94% of light sensitivity
Diluent 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.
As shown in Figure 1, substrate (1) is glass, and anode buffer layer (3) is PEDOT:PSS(80nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 0.3%.
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 P3HT:ICBA 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 component:
The polysiloxanes 95% of light sensitivity
Light trigger 3.5%
Diluent 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(20nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 95.5% of light sensitivity
Light trigger 1.5%
Diluent 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.
As shown in Figure 1, substrate (1) is glass, and anode buffer layer (3) is PEDOT:PSS(20nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 96% of light sensitivity
Light trigger 2.5%
Diluent 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(20nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 96.5% of light sensitivity
Light trigger 1.5%
Diluent and auxiliary agent 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(20nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 6.5%.
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 P3HT:ICBA 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 component:
The polysiloxanes 97% of light sensitivity
Light trigger 1.5%
Diluent 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.
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 10mm, and direction is outwardly-bent.
Claims (10)
1. an organic thin film solar cell, it is characterized in that, the substrate that this solar battery structure sets gradually from bottom to up (1), transparent conductive anode ITO(2), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5) and metallic cathode (6), described photoactive layer is mixed with ultraviolet sensitivity glue in (4), and the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5～97% of light sensitivity
Light trigger 1.5～5%
Diluent and auxiliary agent 1.5～3%;
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
2. organic thin film solar cell according to claim 1, is characterized in that, the polysiloxanes of described light sensitivity comprises mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes and vinyl ether functional polysiloxanes.
3. organic thin film solar cell according to claim 1, it is characterized in that, described light trigger comprises styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt and triaryl salt compounded of iodine.
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 0.05～6.5%.
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 P3HT and electron acceptor material ICBA, described P3HT:ICBA mixed solution mass ratio is 1:20～5:1, described solution concentration is 1～30mg/ml, and thickness is 40～250nm.
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-): a kind of in polystyrene-based benzene sulfonic acid or molybdenum oxide, thickness is 10～80nm.
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 1～10nm.
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 100～300nm.
9. organic thin film solar cell according to claim 1, is characterized in that, described substrate is a kind of in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
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, is dried and processes;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and formed film is carried out to annealing in process;
3. in anode buffer layer surface rotary coating, printing or spraying, be mixed with the photoactive layer of ultraviolet sensitivity glue, and formed film is carried out to annealing in process, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5～97% of light sensitivity
Light trigger 1.5～5%
Diluent and auxiliary agent 1.5～3%,
Diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent;
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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| CN106433147A (en) * | 2016-09-21 | 2017-02-22 | 武汉中开维电气有限公司 | Self-curing insulating material, preparation method and construction method |
| CN106867318A (en) * | 2017-04-24 | 2017-06-20 | 于军胜 | A kind of high-adhesion alcohol radical nano silver wire conductive ink containing ultraviolet sensitivity glue |
| CN108574045A (en) * | 2018-05-07 | 2018-09-25 | 太原理工大学 | A kind of organic photovoltaic battery of high-photoelectric transformation efficiency |
| CN112239195A (en) * | 2020-10-16 | 2021-01-19 | 南开大学 | Preparation method of artificial synapse electronic device based on nano oxide film/electrolyte vertical structure |
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| CN114843007A (en) * | 2021-02-02 | 2022-08-02 | 湖南文理学院 | Method for preparing poly (3, 4-ethylenedioxythiophene) nano pattern by micelle etching |
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| CN116247116B (en) * | 2023-03-09 | 2023-09-05 | 南开大学 | 2-amino-5-bromobenzamide material passivated inorganic perovskite-based solar cell and preparation method thereof |
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