CN105489773B - The preparation method of organic inorganic hybridization perovskite thin film and solar cell - Google Patents

The preparation method of organic inorganic hybridization perovskite thin film and solar cell Download PDF

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CN105489773B
CN105489773B CN201511026606.3A CN201511026606A CN105489773B CN 105489773 B CN105489773 B CN 105489773B CN 201511026606 A CN201511026606 A CN 201511026606A CN 105489773 B CN105489773 B CN 105489773B
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杨松旺
曹启鹏
高潜潜
刘岩
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to the preparation method of organic inorganic hybridization perovskite thin film and solar cell, the chemical formula of the perovskite thin film is ABX3, wherein A is the cation of organic amine, preferably CH3NH3 +,NH2‑CH=NH2 +And C4H9NH3 +At least one of, B=Pb2+, Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+And Ni2+At least one of, X Cl‒, Br‒, I‒At least one of, the preparation method includes the following steps：（1）ABX is prepared in substrate3Film；（2）By step（1）The film of acquisition is made annealing treatment using microwave radiation processing mode, and wherein microwave power is 50~500W, and sample temperature is 50 ~ 150oC, microwave treatment time are 0.5 minute~5 minutes.The preparation method time provided by the present invention is short, energy consumption is small, production efficiency is high and simple for process, and preparation condition is mild, easily operated, has a extensive future.

Description

The preparation method of organic inorganic hybridization perovskite thin film and solar cell
Technical field
The invention belongs to technical field of solar batteries more particularly to a kind of preparation method of film used for solar batteries, More specifically, it is related to the preparation method of a kind of organic inorganic hybridization perovskite thin film and perovskite solar cell.
Background technology
It is growing day by day for the demand of the energy with the development of human society.Solar energy as it is a kind of cleaning, it is free of contamination The energy, by extensive concern both domestic and external and further investigation.Solar cell based on hybrid inorganic-organic perovskite thin film is A kind of novel solar battery that developed recently gets up, advantage are very prominent：1, hybrid inorganic-organic perovskite material makes Simply, cost is relatively low；2, with more suitable band gap width (1.5~2.3eV), light abstraction width is larger；3, charge is spread Length is up to micron order, and charge life is longer etc..Therefore, perovskite solar cell and associated materials have become photovoltaic art and grind Study carefully direction, obtain the photoelectric conversion efficiency more than 21% at present, application prospect is very wide.
Hybrid inorganic-organic perovskite ABX3The preparation method of film is to its structure, pattern, charge mobility, electronics longevity Life and opto-electronic conversion performance are affected.Current method reported in the literature has a step solwution method, two step solwution methods, vapor deposition Method and gas phase assisted solution process method etc..The annealing way of perovskite thin film is all based on traditional heating side in the above method Formula carries out on hot plate or in stove.Since the heat treatment temperature of perovskite thin film is not high, and crystallization speed at a certain temperature Degree is very fast, and traditional heat treatment mode so that this lower heat treatment temperature and heat treatment time are difficult to accurately control, because This, produces bigger effect the quality of film, but also the reproducibility of preparation process is problematic in that sometimes.For example, for most often One step solution heating anneal method, preparation process is although fairly simple, but gained film surface is more coarse, Pinhole-shaped lacks It falls into more, easily causes the compound of charge in film, seriously affected film performance.
Invention content
Present invention seek to address that the traditional heating annealing process in currently available technology prepares hydridization perovskite thin film method Heat treatment temperature and time are difficult to accurately control, and easily occur that film surface is coarse, problems, the utilization such as of low quality of film are micro- Wave radiation processing method prepares hydridization perovskite thin film and prepares perovskite solar cell using this method.
On the one hand, the present invention provides a kind of preparation method of organic inorganic hybridization perovskite thin film, the perovskite thin film Chemical formula be ABX3, wherein A is the cation of organic amine, preferably CH3NH3 +,NH2- CH=NH2 +And C4H9NH3 +In at least One kind, B=Pb2+, Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+And Ni2+At least one of, X Cl-, Br-, I-In extremely Few one kind,
The preparation method includes the following steps：
(1) ABX is formed in substrate3Film；
(2) film that step (1) obtains is made annealing treatment using microwave radiation processing mode, wherein microwave power is 50- 500W, sample temperature are 50~150 DEG C, and microwave treatment time is 0.5 minute~5 minutes.
The present invention prepares hydridization perovskite thin film using microwave radiation processing mode, in preparation process, due to microwave heating Film is heated more uniform in the process, and microwave irradiation time is shorter and is easier to accurately control processing time, and the short period is micro- Wave processing can reach the thermal effectiveness of conventional anneal process long period.Perovskite thin film surface prepared in accordance with the present invention It is more smooth, crystal grain is larger, crystal boundary is less, have excellent opto-electronic conversion performance.The preparation method time provided by the present invention It is short, energy consumption is small, production efficiency is high and simple for process, preparation condition is mild, easily operated, has a extensive future.
In the present invention, the ABX3The preparation method of film can be vapour deposition process or solution-deposition method.
In one preferred embodiment, ABX3Film is prepared by following methods：It is made in substrate by spin-coating method The halide film of B obtained, is then placed in the solution of the halide containing A and the first solvent and soaks by the halide film of standby B Steep or be placed in A halide steam in handle, to be made ABX3Film.
In another preferred embodiment, ABX3Film is prepared by following methods：By the halogen of the halide of A and B Compound is scattered in stirring synthesis ABX in the second solvent3Precursor solution, and by the ABX3Precursor solution is spun on shape in substrate At ABX3Film.
Preferably, first solvent is isopropanol, the second solvent is dimethyl sulfoxide, n,N-Dimethylformamide, γ-fourth At least one of lactone, N-Methyl pyrrolidone.
Preferably, the substrate is fine and close metal-oxide film, preferably titanium oxide, zinc oxide, cobalt oxide, oxidation At least one of nickel or its dopant film.
On the other hand, the present invention provides a kind of preparation method of perovskite solar cell, the perovskite solar-electricity Pond includes successively from bottom to top：Transparent conductive substrate, hole blocking layer, perovskite light absorbing layer, hole transmission layer and metal pair Electrode, the preparation method include the following steps：
(A) the spin coating hole blocking layer in clean transparent conductive substrate；
(B) calcium is prepared on the hole blocking layer of gained using the preparation method of above-mentioned organic inorganic hybridization perovskite thin film Titanium ore light absorbing layer；
(C) the spin coating hole transmission layer on the perovskite light absorbing layer of gained；
(D) on the hole transmission layer of gained evaporation metal to electrode.
Perovskite solar cell prepared according to the methods of the invention has higher photoelectric conversion efficiency, is suitable for big Large-scale production application.
Preferably, in step (A), the transparent conductive substrate is to be coated with F to adulterate SnO2Film or In adulterate SnO2Film Glass or plastics.
Preferably, in step (A), the hole blocking layer is the TiO of densification2Film, presoma is molten used by spin coating Liquid is the aqueous solution of pertitanic acid or the ethanol solution of tetraisopropyl titanate, the spin speed of hole blocking layer is 1000~ 4000rpm, preferably 2000~3000rpm after spin coating, are sintered 5~120 minutes in 250~600 DEG C.
Preferably, in step (C), the hole transmission layer is 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) Amino] two fluorenes of -9,9'- spiral shells, poly- (3- hexyl thiophene -2,5- diyls), in poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes) amine] At least one chlorobenzene solution, a concentration of 70~180mg/mL, the hole transmission layer spin speed be 1000~ 5000rpm, preferably 1500~4500rpm.
Description of the drawings
Fig. 1 shows CH made from embodiment and comparative example3NH3PbI3The SEM of perovskite thin film schemes；
Fig. 2 shows CH made from embodiment and comparative example3NH3PbI3The XRD diagram of perovskite thin film；
Fig. 3 shows CH made from embodiment and comparative example3NH3PbI3The J-V curves of perovskite solar cell.
Specific implementation mode
The present invention prepares hydridization perovskite thin film using microwave radiation processing method.The chemical formula of the perovskite thin film is ABX3.Wherein A is the cation of organic amine, including but not limited to CH3NH3 +,NH2- CH=NH2 +, C4H9NH3 +Deng.B=Pb2+, Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+And Ni2+At least one of.That is, B can be one of these ions, can also be Arbitrary two or more mixed structure in these ions.In one example, ABX3For ASn1-xPbxX3(0 ＜ x ＜ 1).X is Cl-, Br-, I-At least one of.Can also be mixed halogen that is, X can be single halogen, such as arbitrary two kinds of halogens Mixing.For example, the perovskite thin film includes but not limited to methylamine lead iodine, carbonamidine lead iodine etc..Specifically, as an example, it is prepared Method may include steps of.
First, not thermally treated perovskite thin film is obtained in substrate.
Substrate is not particularly limited in the present invention, such as substrate can be electron transfer layer (hole blocking layer), can be Fine and close metal-oxide film forms in including but not limited to dense oxide titanium, zinc oxide, cobalt oxide, nickel oxide at least It is a kind of.
The method that perovskite thin film is prepared in substrate is not particularly limited, such as vapour deposition process or solution may be used Sedimentation.From the point of view of reducing manufacturing cost and simplifying preparation process, preferably solution-deposition method.For example, may be used The methods of one step solwution method, two-step method obtain perovskite thin film.
The one step solwution method can be：The halide of the halide of A and B is scattered in the second solvent and stirs synthesis ABX3Precursor solution, and by the ABX3Precursor solution, which is spun in substrate, forms ABX3Film.
The two-step method can be：The halide film that spin-coating method prepares B in substrate is first passed through, then by B's obtained Halide film is placed in the steam for the halide that A is impregnated or be placed in the solution of the halide containing A and the first solvent and handles, To which ABX be made3Film.
The halide of the A includes but not limited to iodate methylamine (CH3NH3I), bromination methylamine (CH3NH3Br), chlorination methylamine (CH3NH3Cl), iodate carbonamidine (NH2CH=NH2I), bromination carbonamidine (NH2CH=NH2) and chlorination carbonamidine (NH Br2CH=NH2Cl) At least one of.The halide of A is purchased from commercialization, can also voluntarily prepare, such as iodate methylamine (CH3NH3I) preparation method It is as follows：By methylamine and hydroiodic acid in molar ratio 1~2:1 reacts in ice-water bath, is vigorously stirred 1~4h of mixed liquor.Later, it mixes Liquid rotates at 40~60 DEG C, obtains brown solid.After being washed for several times with ether, recrystallization.By the white powder of acquisition true Dry 12~36h at 50~70 DEG C, obtains iodate methylamine powder in empty baking oven.
The B is preferably Pb2+, i.e. the halide of B is preferably lead halide, may be, for example, lead iodide (PbI2), lead bromide (PbBr2), lead chloride (PbCl2At least one of).The X is preferably I-.In a preferred example, reactant is PbI2With CH3NH3I or NH2- CH=NH2I。
Above-mentioned first solvent is isopropanol；Second solvent may be, for example, dimethyl sulfoxide, N,N-dimethylformamide, γ-fourth At least one of lactone, N-Methyl pyrrolidone.
In one example, using a step solwution method, wherein the dosage of the halide of A and the halide of B is preferably by change Learn metering ratio.The concentration of the halide of A and/or the halide of B in a solvent can be 10-70wt%.By the halide of A and B After halide is scattered in solvent, it can be stirred at room temperature 0.25 hour or more, to form ABX3Precursor solution.Spin speed can be 2000~7000rpm, time can be 8~60s.Organic solvent (such as ether, petroleum ether, chlorine can be added dropwise in spin coating process Benzene, n-hexane and its mixed solvent) on the matrix of rotation, the same film of minute surface can be obtained, battery efficiency is substantially improved.
Then, the film of acquisition is made annealing treatment using microwave radiation processing mode, you can obtain required perovskite Film.
Wherein, microwave power can be 50-500W, and the perovskite thin film temperature of microwave treatment can reach 50~150 DEG C, be The normal heat treatment temperature of perovskite thin film, microwave power is too low or microwave treatment time is too short, and perovskite thin film can reach Temperature it is too low, film is difficult to effectively crystallize, and microwave power is too high or microwave treatment time is too long, and perovskite thin film can reach Temperature it is too high, lead to the decomposition of perovskite thin film.Microwave power is preferably 100-300W.Due to using microwave radiation processing, Therefore it is substantially shorter processing time.In the present invention, the microwave radiation processing time can be 0.5 minute~5 minutes, preferably 1~ 3 minutes.
In the present invention, with metal halide, organic amine halide is raw material, is with organic inorganic hybridization perovskite presoma Microwave inhales wave medium and under the conditions of microwave irradiation, it is thin quickly to prepare organic inorganic hybridization perovskite using microwave as heat source Film.The present invention prepares hydridization perovskite thin film using microwave radiation processing mode, in preparation process, due to microwave heating process In, sample is heated more uniform, and microwave treatment time is shorter and is easier to accurately control processing time, and at the microwave of short period Reason can reach the thermal effectiveness of conventional anneal process long period.Therefore film surface is more smooth, particle is larger, crystal boundary It is less, it effectively can collect and transmit the compound of electronics, blocking hole and electronics.High property prepared by the method for the present invention Energy film, has higher photoelectric conversion efficiency, is suitable for large-scale production and application.
Moreover, the heat treatment mode in the present invention is easier to realize, and heat treatment time greatly shortens, especially suitable for flowing water The large-scale production and application of perovskite solar cell are realized in line operation.
The present invention also provides a kind of organic inorganic hybridization perovskite electrode, electricity is sequentially formed on conducting base in the electrode Son transmission layer by layer with perovskite active layer.Wherein, the composition of electron transfer layer include but not limited to dense oxide titanium, zinc oxide, At least one of cobalt oxide, nickel oxide or its dopant.Perovskite active layer is above-mentioned perovskite thin film, including but unlimited In at least one of methylamine lead iodine or carbonamidine lead iodine.Since the film surface is more smooth, particle is larger, crystal boundary is less, because This effectively can collect and transmit the compound of electronics, blocking hole and electronics.Therefore the organic inorganic hybridization calcium titanium of the present invention Mine electrode has excellent performance.
The present invention also provides a kind of perovskite solar cells, include successively：Transparent conductive substrate (conductive substrates), sky Cave barrier layer, perovskite light absorbing layer, hole transmission layer, metal are to electrode.
The transparent conductive substrate can be to be coated with F doping SnO2(FTO) film or In adulterate SnO2(ITO) glass of film Glass or plastics.
The hole blocking layer is preferably the one layer of fine and close TiO prepared using spin coating proceeding2Film.
The perovskite light absorbing layer can be above-mentioned perovskite thin film ABX3(such as CH3NH3PbI3Film).
The hole transmission layer can be 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two The chlorobenzene of at least one of fluorenes, poly- (3- hexyl thiophene -2,5- diyls), poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes) amine] Solution, a concentration of 70-180mg/mL；It wherein may also include bis- (fluoroform) sulfimides of the 520mg/mL of 10-30 μ L/mL The acetonitrile solution of lithium salts and the 4- tert .-butylpyridines of 10-30 μ L/mL are as additive.
The metal can be gold or silver to electrode.
The preparation method of the perovskite solar cell may include following steps：
(A) cleaning, drying of transparent conductive substrate；
(B) the spin coating hole blocking layer on the sample that step (A) obtains；
(C) ABX is prepared on the sample that step (B) obtains using the above method3(such as CH3NH3PbI3) suction of perovskite light Receive layer；
(D) the spin coating hole transmission layer on the sample that step (C) obtains；
(E) gold evaporation or silver-colored to electrode on the sample that step (D) obtains.
Spin coating proceeding in step (B) prepares the precursor solution of hole blocking layer, can be the aqueous solution of pertitanic acid (TiO2Concentration can be 0.5%~1%) or the ethanol solution of tetraisopropyl titanate formed with acetylacetone,2,4-pentanedione, hydrochloric acid and aqueous solution TiO2Colloidal sol, a concentration of 0.1~0.5mol/L of Ti.The spin speed of hole blocking layer can be 1000-4000rpm, preferably 2000-3000rpm, spin-coating time can be 10~60s.After spin coating hole blocking layer, also it can be sintered 5~120 in 250~600 DEG C Minute.
In step (D), the hole transmission layer spin speed can be 1000-5000rpm, preferably 1500- 4500rpm, Spin-coating time can be 10 seconds~5 minutes.
The present invention is reached using the photoelectric conversion efficiency of the perovskite solar cell obtained by microwave radiation processing technique 14.47%, it is slightly higher compared with traditional heating processing mode transfer efficiency 14.02%, and heat treatment time greatly shortens.This explanation, it is micro- Wave radiation treatment process prepares the technique of perovskite solar cell light absorption layer, under the premise of ensureing battery efficiency, processing Time greatly shortens, and is more suitable for large-scale production and application.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1：
(1) preparation of not thermally treated perovskite thin film.Use acetone, alkalis, deionized water, acetone ultrasound clear respectively It washes FTO glass ten minutes, finally dries up.Then TiO is prepared on FTO glass substrates2Compacted zone, precursor solution solvent are Ethyl alcohol, including following component：Tetraisopropyl titanate (0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid (0.09 Mol/L), water (1.8mol/L).Precursor solution is drawn, is added dropwise on the FTO substrates cleaned up, solution is made to be paved with entirely The surfaces FTO, are formed a film using spin-coating method, spin speed 3000rpm, time 20s.Then 510 DEG C of sintering 30min in Muffle furnace. Then, 461 milligrams of lead iodide (PbI are measured2), 159 milligrams of CH3NH3I powders, 78 milligrams of dimethyl sulfoxides are mixed in 600 milligrams of N, N- Dimethylformamide (DMF) stirs 1 hour at room temperature, forms CH3NH3PbI3Perovskite precursor solution.It is molten with this presoma Liquid is spin coating liquid, and not thermally treated perovskite thin film is prepared using spin-coating method, spin speed 5000rpm, time 20s, wherein It was added dropwise at the 6th second on matrix of 0.5 milliliter of ether to rotation；
(2) perovskite thin film prepared by step (1) is placed on Teflon shelf, is placed in micro-wave oven, power setting is 160W, microwave treatment time 3 minutes, 110 DEG C of sample temperature obtain hybrid inorganic-organic perovskite CH3NH3PbI3Film；
(3) perovskite solar cell is prepared.The spin coating hole transmission layer solution on the sample that step (2) obtains, at It is divided into：The chlorobenzene of two fluorenes of the 2,2' of 72.3mg/mL, 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells is molten Liquid includes the 4- tertiary butyls of the acetonitrile solution and 20 μ L of bis- (fluoroform) sulfimide lithium salts of the 520mg/mL of 20 μ L/mL Pyridine is as additive, rotating speed 4000rpm, time 30s；Finally vapor deposition 120nm thickness Ag obtains CH to electrode3NH3PbI3Calcium titanium Mine solar cell.
Comparative example 1
(1) preparation of not thermally treated perovskite thin film.With embodiment 1；
(2) perovskite thin film prepared by step (1) is placed on hot plate and is heat-treated 10 minutes at 100 DEG C, obtain organic-nothing Machine hydridization perovskite CH3NH3PbI3Film；
(3) perovskite solar cell is prepared.With embodiment 1.
Fig. 1 shows CH made from embodiment and comparative example3NH3PbI3The SEM of perovskite thin film schemes, it can be seen that embodiment Unanimous on the whole with comparative example crystallite dimension, comparative example is slightly thick and solid compared with embodiment, real caused by this is two kinds of Different treatments Example microwave treatment, film thermally equivalent are applied, and comparative example uses traditional heating mode, from bottom to top heats.Fig. 2 shows implementations CH made from example and comparative example3NH3PbI3The XRD diagram of perovskite thin film, it can be seen that embodiment and comparative example has very strong allusion quotation The diffraction maximum of type perovskite structure, and embodiment is stronger compared with comparative example diffraction maximum, illustrates the perovskite thin film crystallinity of embodiment More preferably.Fig. 3 shows CH made from embodiment and comparative example3NH3PbI3The J-V curves of perovskite solar cell, it can be seen that real The short-circuit current density of example, open-circuit voltage are applied, fill factor and transfer efficiency are all slightly improved compared with comparative example.
Industrial applicability：The present invention prepares perovskite light absorbing layer, the gained perovskite sun using microwave radiation processing method The photoelectric conversion efficiency of energy battery is slightly higher compared with conventional heating methods.Moreover, heat treatment time greatly shortens, especially suitable for flowing water Line operation is conducive to the exploitation of related Equipment for Heating Processing, realizes the large-scale production and application of perovskite solar cell.

Claims (8)

1. a kind of preparation method of organic inorganic hybridization perovskite thin film, which is characterized in that the chemical formula of the perovskite thin film For ABX3, wherein A is the cation of organic amine, B=Pb2+, Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+And Ni2+In at least one Kind, X Cl‒, Br‒, I‒At least one of,
The preparation method includes the following steps：
（1）ABX is prepared in substrate3Film,
ABX3Film is prepared by following methods：The halide film of B is prepared in substrate by spin-coating method, then by B obtained Halide film be placed in the steam for the halide that A is impregnated or be placed in the solution of the halide containing A and the first solvent and handle, To which ABX be made3Film, or
ABX3Film is prepared by following methods：The halide of the halide of A and B is scattered in the second solvent and stirs synthesis ABX3Precursor solution, and by the ABX3Precursor solution, which is spun in substrate, forms ABX3Film,
The substrate is the metal-oxide film of densification,
First solvent is isopropanol, and the second solvent is dimethyl sulfoxide, n,N-Dimethylformamide, gamma-butyrolacton, N- methyl At least one of pyrrolidones；
（2）By step（1）The film of acquisition is placed on Teflon shelf and is made annealing treatment using microwave radiation processing mode, Middle microwave power is 50~500W, and sample temperature is 50~150 DEG C, and microwave treatment time is 0.5 minute~5 minutes.
2. preparation method according to claim 1, which is characterized in that A CH3NH3 +, NH2-CH=NH2 +And C4H9NH3 +In At least one.
3. a kind of preparation method of perovskite solar cell, which is characterized in that the perovskite solar cell is from bottom to top Include successively：Transparent conductive substrate, hole blocking layer, perovskite light absorbing layer, hole transmission layer and metal are described to electrode Preparation method includes the following steps：
（A）The spin coating hole blocking layer in clean transparent conductive substrate；
（B）Perovskite light absorbing layer is prepared on the hole blocking layer of gained using preparation method as claimed in claim 1 or 2；
（C）The spin coating hole transmission layer on the perovskite light absorbing layer of gained；
（D）Evaporation metal is to electrode on the hole transmission layer of gained.
4. preparation method according to claim 3, which is characterized in that step（A）In, the transparent conductive substrate is to be coated with F adulterates SnO2Film or In adulterate SnO2The glass or plastics of film.
5. preparation method according to claim 3, which is characterized in that step（A）In, the hole blocking layer is fine and close TiO2Film, precursor solution used by spin coating be pertitanic acid aqueous solution or tetraisopropyl titanate ethanol solution, The spin speed of hole blocking layer is 1000~4000rpm, after spin coating, is sintered 5~120 minutes in 250~600 DEG C.
6. preparation method according to claim 5, which is characterized in that the spin speed of hole blocking layer be 2000~ 3000rpm。
7. preparation method according to claim 3, which is characterized in that step（C）In, the hole transmission layer is 2, Two fluorenes of 2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells, gathers at poly- (3- hexyl thiophene -2,5- diyls) It is [double（4- phenyl）（2,4,6- trimethylphenyls）Amine] at least one of chlorobenzene solution, a concentration of 70~180mg/mL, institute The hole transmission layer spin speed stated is 1000~5000rpm.
8. preparation method according to claim 7, which is characterized in that the hole transmission layer spin speed be 1500~ 4500rpm。
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