CN105226187A - Film crystal silicon perovskite heterojunction solar cell and preparation method thereof - Google Patents

Film crystal silicon perovskite heterojunction solar cell and preparation method thereof Download PDF

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CN105226187A
CN105226187A CN201510785094.2A CN201510785094A CN105226187A CN 105226187 A CN105226187 A CN 105226187A CN 201510785094 A CN201510785094 A CN 201510785094A CN 105226187 A CN105226187 A CN 105226187A
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crystal silicon
film crystal
hole transmission
solution
transmission layer
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CN105226187B (en
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田汉民
金慧娇
毕文刚
花中秋
杨瑞霞
戎小莹
张天
王伟
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Hebei University of Technology
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED]
    • H01L51/5048Carrier transporting layer
    • HELECTRICITY
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED]
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED]
    • H01L51/56Processes or apparatus specially adapted for the manufacture or treatment of such devices or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H01L2251/301Inorganic materials
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    • H01L2251/50Organic light emitting devices
    • H01L2251/53Structure

Abstract

Film crystal silicon perovskite heterojunction solar cell of the present invention and preparation method thereof, relate to and be specially adapted for transform light energy being the semiconductor device of electric energy, be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode, wherein, perovskite light absorbing zone and P type film crystal silicon hole transmission layer possess the energy level matched; Building form is: P type film crystal silicon hole transport is placed on electrically conducting transparent substrate, perovskite light absorbing zone is placed in above P type film crystal silicon hole transmission layer, perovskite light absorbing zone and P type film crystal silicon hole transmission layer form film crystal silicon perovskite heterojunction, the electric transmission be made up of compact titanium dioxide is placed on above perovskite light absorbing zone, and back electrode is placed in by above the electron transfer layer that compact titanium dioxide is formed.Overcome the defect that existing perovskite solar cell stability is not enough, preparation cost is high or silicon materials use amount is large.

Description

Film crystal silicon perovskite heterojunction solar cell and preparation method thereof
Technical field
Technical scheme of the present invention relates to and is specially adapted for transform light energy being the semiconductor device of electric energy, specifically film crystal silicon perovskite heterojunction solar cell and preparation method thereof.
Background technology
Be difficult to further situation about declining relative to crystal silicon battery because of crystal silicon material manufacturing cost, use perovskite material CH 3nH 3pbX 3(X=Cl, Br, orI) for solar cell (hereinafter referred to as the Ca-Ti ore type solar cell) photoelectric conversion efficiency of main light absorbing zone is more than 20%, and there is filming, solution at room temperature preparation, without the low manufacturing cost characteristic of rare element, have application prospect.In the Ca-Ti ore type solar cell of various structure, the P type body silicon materials of the traditional monocrystalline silicon of direct employing and polycrystalline silicon solar cell are as the Ca-Ti ore type solar cell of hole transmission layer, because body silicon materials do not reduce the use of silicon materials, the cost of Ca-Ti ore type solar cell cannot be realized significantly lower than traditional monocrystalline silicon and polycrystalline silicon solar cell.And adopt amorphous silicon membrane as the Ca-Ti ore type solar cell of hole transmission layer, then because amorphous silicon membrane inside exists the defects such as a large amount of dangling bonds, cause this cell photoelectric conversion performance poor relative to body silion cell.CN201410568822.X discloses all solid state perovskite microcrystal silicon composite solar cell and preparation method thereof, and it exists following not enough: the first, and the deposition rate of microcrystal silicon is slow, is generally no more than 5 dusts per second, and deposition velocity have impact on production efficiency and cost.Want large-scale industrial production microcrystalline silicon film, also need microcrystalline silicon film technology of preparing to improve speed further; The second, microcrystal silicon is the tiny crystals particle of silicon and the mixed phase of amorphous in essence, and the dangling bonds on its crystal boundary and inner surface and defect are all the complex centres of photo-generated carrier.Compared with crystalline silicon material, the performance such as open circuit voltage of the solar cell device that the compound of the photo-generated carrier of microcrystal silicon inside makes microcrystalline silicon materials be prepared into is restricted.
Therefore, exploitation is made up of the Ca-Ti ore type solar cell of its hole mobile material film crystal silicon material, can realize silicon materials use amount fewer than body silicon materials, simultaneously film quality and device performance than amorphous silicon and microcrystalline silicon film excellent, the performance contributing to solar cell improves further and production cost reduces.
Summary of the invention
Technical problem to be solved by this invention is: provide film crystal silicon perovskite heterojunction solar cell and preparation method thereof, a kind of solar cell and preparation method of the heterojunction adopting film crystal silicon and perovskite to form, both the existing common Ca-Ti ore type solar cell defect that stability is not enough and preparation cost is high because using organic cavity transmission layer material had been overcome, overcome again the defect using Ca-Ti ore type solar cell silicon materials use amount that body block crystal silicon material is hole mobile material large, also overcome the defect using Ca-Ti ore type solar cell photoelectric conversion poor-performing that amorphous silicon and microcrystalline silicon film are hole transmission layer simultaneously.
The present invention solves this technical problem adopted technical scheme: film crystal silicon perovskite heterojunction solar cell, be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode, wherein, perovskite light absorbing zone and P type film crystal silicon hole transmission layer possess the energy level matched; Its composition sequential system is: P type film crystal silicon hole transport is placed on electrically conducting transparent substrate, perovskite light absorbing zone is placed in above P type film crystal silicon hole transmission layer, perovskite light absorbing zone and P type film crystal silicon hole transmission layer form film crystal silicon perovskite heterojunction, the electric transmission be made up of compact titanium dioxide is placed on above perovskite light absorbing zone, back electrode is placed in by above the electron transfer layer that compact titanium dioxide is formed, above five functional layers superpose successively, form this film crystal silicon perovskite heterojunction solar cell.
Above-mentioned film crystal silicon perovskite heterojunction solar cell, described perovskite light absorbing zone perovskite material used is CH 3nH 3pbX 3, wherein X=Cl is or/and I, and thickness is 0.05 ~ 30um.
Above-mentioned film crystal silicon perovskite heterojunction solar cell, described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.
Above-mentioned film crystal silicon perovskite heterojunction solar cell, described back electrode is thin layer or the grid line of aluminium, silver or copper formation.
The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar cell, its step is as follows:
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 1A ~ 7.5A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H 2lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, formed P type polycrystal silicon film is transferred in electrically conducting transparent substrate from monocrystalline silicon piece, is prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the above-mentioned first step is obtained, adopt in following two kinds of methods any one:
A. single spin-coating method:
A-1.CH 3nH 3the preparation of X, wherein X=Cl or I (lower same):
Preparation CH 3nH 3the raw material of X to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen halide solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen halide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3x, described hydrogen halide solution is hydrogen chloride solution or hydrogen iodide solution,
A-2. composition is CH 3nH 3pbX 3the preparation of perovskite precursor aqueous solution:
To be mass percent by mol ratio be 99.999% PbX 2: the CH that above-mentioned A-1 step is obtained 3nH 3x=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbX 2concentration be 0.5 ~ 1M, CH 3nH 3the concentration of X is 1 ~ 2.5M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH 3nH 3pbX 3perovskite precursor aqueous solution, stand-by, above-mentioned PbX 2in X=Cl or I, and and CH 3nH 3x in X is consistent;
A-3. the wet film of spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
Be put on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH 3nH 3pbX 3perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 10 ~ 30s, the wet film of perovskite light absorbing zone in spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer;
A-4. heat treatment:
By obtained for above-mentioned A-3 step on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer in spin coating the entirety of the wet film of perovskite light absorbing zone put in baking oven and heat-treat, first heat treatment 0.5 ~ 1h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;
B. spin coating+infusion process
B-1.CH 3nH 3cl and CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl, preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
B-2. at the spin coating PbI on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the first step is obtained 2film:
Be 99.999%PbI by mass percent purity 2being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI 2the concentration of solution is 0.5 ~ 1M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification 2solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI 2heating temperatures to 60 ~ 65 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum 2solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 10 ~ 20s, then drying process 10 minutes, and electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtains spin coating PbI 2film, this film thickness is 10 ~ 800nm;
B-3. above-mentioned B-2 is walked the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed:
By the CH obtained through above-mentioned B-1 step of aequum 3nH 3cl and CH 3nH 3it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively 3nH 3cl solution and CH 3nH 3i solution, its concentration is 1 ~ 10mg/mL, is CH according to volume ratio 3nH 3i Rong Ye ︰ CH 3nH 3cl solution=1 ︰ 0.1 ~ 10 gets CH respectively 3nH 3i solution and CH 3nH 3cl solution is mixed to get CH 3nH 3i and CH 3nH 3the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 2film is preheated to 60 DEG C, then by this PbI 2film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 5 ~ 30min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed;
B-4. heat treatment:
Spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtained by being walked by the B-3 of above-mentioned second step has by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the entirety of the film that mixing is formed is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
The entirety of goods obtained by above-mentioned second step is placed in magnetron sputtering apparatus, on perovskite light absorbing zone, prepared the electron transfer layer be made up of compact titanium dioxide by magnetron sputtering method, concrete operation method is: target is the TiO of purity Coriolis mass percentage 99.99% 2target, target diameter is 60mm, and thickness is 5mm, before sputtering, carries out 5min cleaning, then vacuumize with high-purity argon gas to magnetron sputtering apparatus cavity, and base vacuum is 4.0 × 10 -3pa, pass into argon gas and oxygen successively subsequently, the volume ratio being controlled argon gas and oxygen by adjust flux is 9: 1, total pressure remains 2.0Pa, sputtering power is 80W, sputtering time is 4h, again through the annealing in process of 70 DEG C to 150 DEG C after growth terminates, and the obtained electron transfer layer be made up of compact titanium dioxide on perovskite light absorbing zone thus;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, concrete operation method be adopt in the following two kinds method any one:
A. magnetically controlled sputter method:
The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the aluminium of mass percent purity >99.99%, copper or silver, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree -4pa, argon flow amount are 20cm 3/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 60 ~ 90min, is namely prepared into prepared by electron transfer layer in the 3rd step and back electrode is prepared into the thin layer back electrode or grid line back electrode that aluminium, copper or silver forms;
B. hot evaporation coating method:
The entirety of goods obtained by above-mentioned 3rd step is placed in vacuum coating equipment, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, under the voltage of 150 ~ 175V, use Resistant heating vacuum coating equipment, be 1 × 10 in vacuum degree -4pa ~ 8.0 × 10 -4pa and temperature are under room temperature to 150 DEG C condition, by the method for evaporation plating aluminium, copper or silver, evaporation 2 ~ 60 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into aluminium, copper or silver and forming;
So far, the final obtained film crystal silicon perovskite heterojunction solar cell be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode.
The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar cell, described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.
The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar cell, wherein involved raw material, equipment and process method of operation are all known.
The invention has the beneficial effects as follows: compared with prior art, outstanding substantive distinguishing features of the present invention is as follows:
(1) film crystal silicon perovskite heterojunction solar cell of the present invention and preparation method thereof is compared with perovskite microcrystal silicon composite solar cell all solid state disclosed in CN201410568822.X and preparation method thereof, substantial difference technical characteristic is:, CN201410568822.X adopts microcrystalline silicon film layer to be hole transmission layer, and the present invention adopts polycrystal silicon film to be hole transmission layer.Microcrystal silicon is the mixed phase of small granular silicon crystal and amorphous silicon in essence, there are a large amount of defects, dangling bonds in the crystal boundary between small granular silicon crystal surface, crystal grain and amorphous silicon.And crystal silicon to be silicon atom regularly arranged, have the crystal of substantially complete lattice structure, its inside does not have defect, crystal boundary substantially.Because microcrystalline silicon film inside exists the defect such as a large amount of crystal boundaries, dangling bonds far more than polycrystal silicon film, the Carrier recombination of microcrystal silicon hole transmission layer inside is significantly higher than crystal silicon material, so causing CN201410568822.X battery performance to be weaker than employing film crystal silicon material of the present invention is the battery of hole transmission layer.The difficult point adopting film crystal silicon cavitation layer to substitute microcrystal silicon cavitation layer is to design the film crystal silicon technique of mating with perovskite material process matching, Performance Match and cost.First, traditional crystalline silicon material is just converted to ordering rule arrangement liquid silicon atom lack of alignment by high-purity polycrystalline silicon raw material under 1450 celsius temperature conditions, and 1450 celsius temperatures are far above the stable temperature of perovskite material 200 degrees centigrade, hinder and crystal silicon is introduced perovskite battery.Second, the method of the single crystal silicon material acquisition polycrystal silicon film of machine cuts is subject to the restriction of silicon materials self fragility and carborundum line intensity, the crystal silicon chip that thickness is less than 150 microns cannot be obtained economically, and crystal silicon chip thickness being greater than 150 microns is applied to perovskite battery hole transmission layer, both because charge carrier transport distance in silicon chip is long, a large amount of compound thus device performance sharply declined and even cannot realize photoelectric conversion, again because institute to consume silicon materials suitable and make it not possess cost value with conventional crystal silion cell.The present inventor team in order to overcome CN201410568822.X technology existing for defect done hard research, meticulous design and great many of experiments, just successfully obtain film crystal silicon perovskite heterojunction solar cell that Performance Match, cost mate much smaller than 150um with perovskite material process matching, crystal silicon thickness and preparation method thereof.Above-mentioned difference technical characteristic proves that the present invention is compared with prior art CN201410568822.X, has outstanding substantive distinguishing features and marked improvement.
(2) the present invention is different with film crystal silicon solar battery structure from existing plane Ca-Ti ore type solar cell.The structure of existing plane Ca-Ti ore type solar cell is: 1. electrically conducting transparent substrate, the electron transfer layer be 2. made up of compact titanium dioxide, 3. calcium titanium ore bed, 4. organic cavity transmission layer, 5. back electrode.This five is partly superimposed together, and just constitutes Ca-Ti ore type solar cell; The structure of existing polycrystal silicon film solar cell: 1. P type layer polycrystal silicon film, 2. I type (intrinsic layer) amorphous thin Film layers, 3. N-type amorphous thin Film layers, this three to be stackedly added together, and after film both sides plate the silver grating line of conduction and the conductive substrates of the film such as copper or aluminium formation respectively, just form polycrystal silicon film solar cell; The structure of existing perovskite micro crystal silicon solar battery is: 1. electrically conducting transparent substrate, the electron transfer layer be 2. made up of compact titanium dioxide, 3. calcium titanium ore bed, 4. microcrystal silicon hole transmission layer, 5. back electrode.This five is partly superimposed together, and just constitutes perovskite micro crystal silicon solar battery; And the structure of film crystal silicon Ca-Ti ore type solar cell of the present invention is: 1. electrically conducting transparent substrate, 2. P type film crystal silicon hole transmission layer, 3. perovskite light absorbing zone, the electron transfer layer be 4. made up of compact titanium dioxide, 5. back electrode.This five part is mutually mated and is combined with each other, and particularly perovskite light absorbing zone and P type film crystal silicon hole transmission layer are combined into film crystal silicon perovskite hetero-junction thin-film, thus constitute film crystal silicon perovskite heterojunction solar cell of the present invention.
(3) find and develop the essential step that suitable hole transport layer material is the development of Ca-Ti ore type solar cell, but the material require being applicable to Ca-Ti ore type solar cell hole transmission layer have to occupy with best result of perovskite light absorption layer material that track (being called for short HOMO) and minimum molecule do not occupy that unoccupied orbital (being called for short LUMO) matches lead valence-band level position, to realize carrier transport, also need to have at the long-time stability of outdoor operation and cheap cost, the material met this requirement will be prepared at present very difficult.Perovskite light absorption layer material and P type film crystal silicon hole transport layer material are combined obtained film crystal silicon perovskite hetero-junction thin-film by the present invention, possesses the performance of level-density parameter, and both make use of the low cost of perovskite light absorbing zone and excellent light absorption, opto-electronic conversion performance, obtain low cost optical absorbed layer, draw again the characteristic that P type film crystal silicon is mature and stable, there is the outstanding substantive distinguishing features that the novel solar cell of developing lower price high efficiency is practical.
(4), in prior art, polycrystal silicon film solar cell adopts polycrystal silicon film to be light absorbing zone, there is the contradiction of polycrystal silicon film thickness and battery performance.Because the crystal silicon material absorption coefficient of light is low, during the thinner thickness of polycrystal silicon film, light absorption is not enough; And the thickness of polycrystal silicon film thicker time, then cannot realize the cost of polycrystal silicon film solar cell significantly lower than traditional monocrystalline silicon and polycrystalline silicon solar cell.In addition, polycrystal silicon film solar cell adopts amorphous silicon membrane as the emitter of battery, then increase overall preparation cost further, and there is the defects such as a large amount of dangling bonds due to amorphous silicon membrane inside, cause this cell photoelectric conversion performance poor relative to body silion cell.And the present invention take perovskite material as light absorbing zone, realized the function of light absorption several times in the perovskite material of crystal silicon material by light absorpting ability, and polycrystal silicon film only bears the effect in isolated electric transmission hole, so the consumption of crystal silicon material in the present invention is far below polycrystal silicon film solar cell.
Compared with prior art, marked improvement of the present invention is: perovskite light absorption layer material and P type film crystal silicon material are mated compound mutually, obtained film crystal silicon Ca-Ti ore type solar cell overcomes the poor stability and expensive shortcoming that existing Ca-Ti ore type solar cell exists because using organic hole transport material, and overcoming again film crystal silicon solar battery is that light absorbing zone exists the low shortcoming of the absorption coefficient of light with crystal silicon material; Simultaneously, relative to perovskite micro crystal silicon solar battery, solar cell of the present invention and technology of preparing employing film crystal silicon thereof are the hole mobile material in battery, its Carrier recombination is significantly better than microcrystalline silicon materials, and be the crystal silicon of filming because of it, so have advantage of low cost, imbody is as follows:
(1) film crystal silicon perovskite heterojunction solar cell good stability of the present invention:
The Ca-Ti ore type solar cell of the peak efficiency of current report is all based on organic hole transport material.The mature and stable film crystal silicon layer of employing of the present invention substitutes the various organic hole transport material of report at present, its advantage is: film crystal silicon material is mature and stable, be successfully applied to film crystal silicon solar battery etc., therefore avoid oxidation operation, reduction Sum decomposition to the impact in the steady operation life-span of Ca-Ti ore type solar cell.Therefore one of the advantage of film crystal silicon perovskite microcrystal silicon composite film solar cell of the present invention and preparation method thereof is: extend Ca-Ti ore type solar cell working life, reduces the efficiency decay of battery.
(2) the preparation speed of film crystal silicon perovskite heterojunction solar cell of the present invention is high, and preparation cost is low:
As above described in background technology part, the most important factor of restriction film crystal silicon solar battery is because the crystal silicon material absorption coefficient of light as light absorbing zone is low at present, and for ensureing light absorption, the thickness of film crystal silicon solar battery still needs more than some tens of pm.And film crystal silicon perovskite heterojunction solar cell of the present invention take calcium titanium ore bed as light absorbing zone, the thickness of required film crystal silicon hole transmission layer greatly reduces, and significantly reduces and uses silicon materials consumption; Again relative to crystal silicon light absorption layer material, perovskite light absorbing zone is solution low-temperature growth, and preparation speed is fast and preparation cost is low.The cost ratio gold used in film crystal silicon material used in the present invention and traditional Ca-Ti ore type solar cell, platinum also expensive 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes (being called for short SpiroOMeTAD), polyase 13-hexyl thiophene (being called for short P3HT) are compared with fullerene derivate (being called for short PCBM) several organic hole transport material, have very large cost advantage.Therefore, another advantage of film crystal silicon perovskite heterojunction solar cell of the present invention and preparation method thereof is: preparation speed is high, and preparation cost is low.
(3) the photoelectric conversion performance of film crystal silicon perovskite heterojunction solar cell of the present invention is good:
What the P type film crystal silicon in film crystal silicon perovskite heterojunction solar cell of the present invention had that the level of energy (-5.43 electron-volts) that occupies track with the best result of perovskite light absorption layer material and minimum molecule do not occupy that the energy level (-3.93 electron-volts) of unoccupied orbital matches lead valence-band level position (be respectively-5.328 electron-volts with-4.17 electron-volts), realize carrier transport and final photoelectric conversion, and relative to use microcrystal silicon layer material, the Carrier recombination of crystal silicon material is less.Therefore, another advantage of film crystal silicon Ca-Ti ore type solar cell of the present invention and preparation method thereof is: photoelectric conversion performance is good.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the structural representation of film crystal silicon Ca-Ti ore type solar cell of the present invention.
In figure, 1. electrically conducting transparent substrate, 2.P type film crystal silicon hole transmission layer, 3. perovskite light absorbing zone, the electron transfer layer be 4. made up of compact titanium dioxide, 5. back electrode.
Embodiment
Embodiment illustrated in fig. 1ly show that film crystal silicon perovskite heterojunction solar cell is made up of electrically conducting transparent substrate 1, P type film crystal silicon hole transmission layer 2, perovskite light absorbing zone 3, the electron transfer layer 4 be made up of compact titanium dioxide and back electrode 5.The electron transfer layer 4 that incident light is injected electrically conducting transparent substrate 1, P type film crystal silicon hole transmission layer 2, perovskite light absorbing zone 3 successively and is made up of compact titanium dioxide, form photoelectric current, consequent electric current can export from back electrode 5 and electrically conducting transparent substrate 1.
Embodiment 1
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 1A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H 2lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, by formed P type polycrystal silicon film from monocrystalline silicon piece transfer to glass be substrate AZO transparent oxide conductive layer form electrically conducting transparent substrate on, be prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
A. single spin-coating method:
A-1.CH 3nH 3the preparation of Cl:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.5h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl,
A-2. composition is CH 3nH 3pbCl 3the preparation of perovskite precursor aqueous solution:
To be mass percent by mol ratio be 99.999% PbCl 2: the CH that above-mentioned A-1 step is obtained 3nH 3cl=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbCl 2concentration be 0.5M, CH 3nH 3the concentration of Cl is 1M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH 3nH 3pbCl 3perovskite precursor aqueous solution, stand-by;
A-3. the wet film of spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
Be put on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH 3nH 3pbCl 3perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 10s, the wet film of perovskite light absorbing zone in spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the AZO transparent oxide conductive layer taking glass as substrate is formed;
A-4. heat treatment:
The entirety of the wet film of perovskite light absorbing zone in spin coating on obtained for the above-mentioned A-3 step electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer formed at the AZO transparent oxide conductive layer taking glass as substrate is put in baking oven and heat-treats, first heat treatment 0.5h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 10nm, and with glass be substrate AZO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction,
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
The entirety of goods obtained by above-mentioned second step is placed in magnetron sputtering apparatus, on perovskite light absorbing zone, prepared the electron transfer layer be made up of compact titanium dioxide by magnetron sputtering method, concrete operation method is: target is the TiO of purity Coriolis mass percentage 99.99% 2target, target diameter is 60mm, and thickness is 5mm, before sputtering, carries out 5min cleaning, then vacuumize with high-purity argon gas to magnetron sputtering apparatus cavity, and base vacuum is 4.0 × 10 -3pa, pass into argon gas and oxygen successively subsequently, the volume ratio being controlled argon gas and oxygen by adjust flux is 9: 1, total pressure remains 2.0Pa, sputtering power is 80W, sputtering time is 4h, again through the annealing in process of 70 DEG C after growth terminates, and the obtained electron transfer layer be made up of compact titanium dioxide on perovskite light absorbing zone thus;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, and concrete operation method adopts with the following method:
A. magnetically controlled sputter method:
The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, do not use mask, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the aluminium of mass percent purity >99.99%, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree -4pa, argon flow amount are 20cm 3/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 60min, is namely prepared into the thin layer back electrode prepared by electron transfer layer back electrode is prepared into aluminium formation in the 3rd step;
So far, the film crystal silicon perovskite heterojunction solar cell that the thin layer back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the aluminium be made up of the AZO transparent oxide conductive layer taking glass as substrate is formed is formed.
Embodiment 2
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 4.5A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H 2lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, by formed P type polycrystal silicon film from monocrystalline silicon piece transfer to glass be substrate ITO transparent oxide conductive layer form electrically conducting transparent substrate on, be prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of ITO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
A. single spin-coating method:
A-1.CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2.5 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.8h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
A-2. composition is CH 3nH 3pbI 3the preparation of perovskite precursor aqueous solution:
To be mass percent by mol ratio be 99.999% PbI 2: the CH that above-mentioned A-1 step is obtained 3nH 3i=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbI 2concentration be 0.8M, CH 3nH 3the concentration of I is 1.8M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH 3nH 3pbI 3perovskite precursor aqueous solution, stand-by;
A-3. the wet film of spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer formed at the ITO transparent oxide conductive layer taking glass as substrate:
What the first step obtained is put on spin coating instrument in the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety of the ITO transparent oxide conductive layer formation taking glass as substrate, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH 3nH 3pbI 3perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 15s, the wet film of perovskite light absorbing zone in spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer;
A-4. heat treatment:
The entirety of the wet film of perovskite light absorbing zone in spin coating on obtained for the above-mentioned A-3 step electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer formed at the ITO transparent oxide conductive layer taking glass as substrate is put in baking oven and heat-treats, first heat treatment 0.8h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 500nm, and with glass be substrate ITO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction,
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
With embodiment 1;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, and concrete operation method adopts with the following method:
A. magnetically controlled sputter method:
The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, do not use mask, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the copper of mass percent purity >99.99%, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree -4pa, argon flow amount are 20cm 3/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 75min, is namely prepared into the thin layer back electrode prepared by electron transfer layer back electrode is prepared into copper formation in the 3rd step;
So far, the film crystal silicon perovskite heterojunction solar cell that the thin layer back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the copper be made up of the ITO transparent oxide conductive layer taking glass as substrate is formed is formed.
Embodiment 3
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 7.5A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H 2lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, by formed P type polycrystal silicon film from monocrystalline silicon piece transfer to glass be substrate FTO transparent oxide conductive layer form electrically conducting transparent substrate on, be prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of FTO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
A. single spin-coating method:
A-1.CH 3nH 3the preparation of Cl:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 2h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl,
A-2. composition is CH 3nH 3pbCl 3the preparation of perovskite precursor aqueous solution:
To be mass percent by mol ratio be 99.999% PbCl 2: the CH that above-mentioned A-1 step is obtained 3nH 3cl=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbCl 2concentration be 1M, CH 3nH 3the concentration of Cl is 2.5M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH 3nH 3pbCl 3perovskite precursor aqueous solution, stand-by;
A-3. the wet film of spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer formed at the FTO transparent oxide conductive layer taking glass as substrate:
What the first step obtained is put on spin coating instrument in the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety of the FTO transparent oxide conductive layer formation taking glass as substrate, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH 3nH 3pbCl 3perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 30s, the wet film of perovskite light absorbing zone in spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer;
A-4. heat treatment:
The entirety of the wet film of perovskite light absorbing zone in spin coating on obtained for the above-mentioned A-3 step electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer formed at the FTO transparent oxide conductive layer taking glass as substrate is put in baking oven and heat-treats, first heat treatment 1h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 1000nm, and with glass be substrate FTO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction,
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
With embodiment 1;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, and concrete operation method adopts with the following method:
A. magnetically controlled sputter method:
The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, use mask, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the silver of mass percent purity >99.99%, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree -4pa, argon flow amount are 20cm 3/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 90min, is namely prepared into the grid line back electrode prepared by electron transfer layer back electrode is prepared into silver formation in the 3rd step;
So far, the film crystal silicon perovskite heterojunction solar cell that the grid line back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the silver be made up of the FTO transparent oxide conductive layer taking glass as substrate is formed is formed.
Embodiment 4
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
With embodiment 1;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
B. spin coating+infusion process
B-1.CH 3nH 3cl and CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.5h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl, preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.5h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
B-2. at the spin coating PbI on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the first step obtains 2film:
Be 99.999%PbI by mass percent purity 2being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI 2the concentration of solution is 0.5M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification 2solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI 2the heating temperatures to 60 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum 2solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 10s, drying process 10 minutes again, the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the AZO transparent oxide conductive layer taking glass as substrate is formed obtains spin coating PbI 2film, this film thickness is 10nm;
B-3. above-mentioned B-2 is walked the PbI of gained spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed:
By the CH obtained through above-mentioned B-1 step of aequum 3nH 3cl and CH 3nH 3it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively 3nH 3cl solution and CH 3nH 3i solution, its concentration is 1mg/mL, is CH according to volume ratio 3nH 3i Rong Ye ︰ CH 3nH 3cl solution=1 ︰ 0.1 gets CH respectively 3nH 3i solution and CH 3nH 3cl solution is mixed to get CH 3nH 3i and CH 3nH 3the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 2film is preheated to 60 DEG C, then by this PbI 2film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 5min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed;
B-4. heat treatment:
Spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate obtained by being walked by the B-3 of above-mentioned second step has CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the entirety of the film that mixing is formed is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 10nm, and with glass be substrate AZO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction;
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
With embodiment 1;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
B. hot evaporation coating method:
Be placed in vacuum coating equipment by the entirety of goods obtained by above-mentioned 3rd step, carrying out plated film to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, use Resistant heating vacuum coating equipment under the voltage of 150V, is 1 × 10 in vacuum degree -4pa and temperature are under room temperature to 150 DEG C condition, by the method for evaporation plating aluminium, evaporation 2 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into aluminium and forming;
So far, the film crystal silicon perovskite heterojunction solar cell that the thin layer back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the aluminium be made up of the AZO transparent oxide conductive layer taking glass as substrate is formed is formed.
Embodiment 5
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
With embodiment 1;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
B. spin coating+infusion process
B-1.CH 3nH 3cl and CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2.5 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.8h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl, preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2.5 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 1.8h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
B-2. at the spin coating PbI on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the first step obtains 2film:
Be 99.999%PbI by mass percent purity 2being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI 2the concentration of solution is 0.8M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification 2solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI 2the heating temperatures to 62 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum 2solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 15s, then drying process 10 minutes, and electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtains spin coating PbI 2film, this film thickness is 400nm;
B-3. above-mentioned B-2 is walked the PbI of gained spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed:
By the CH obtained through above-mentioned B-1 step of aequum 3nH 3cl and CH 3nH 3it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively 3nH 3cl solution and CH 3nH 3i solution, its concentration is 5mg/mL, is CH according to volume ratio 3nH 3i Rong Ye ︰ CH 3nH 3cl solution=1 ︰ 5 gets CH respectively 3nH 3i solution and CH 3nH 3cl solution is mixed to get CH 3nH 3i and CH 3nH 3the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 2film is preheated to 60 DEG C, then by this PbI 2film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 16min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed;
B-4. heat treatment:
Spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate obtained by being walked by the B-3 of above-mentioned second step has CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the entirety of the film that mixing is formed is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 500nm, and with glass be substrate AZO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction;
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
With embodiment 1;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
B. hot evaporation coating method:
Be placed in vacuum coating equipment by the entirety of goods obtained by above-mentioned 3rd step, carrying out plated film to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, use Resistant heating vacuum coating equipment under the voltage of 165V, is 4.0 × 10 in vacuum degree -4pa and temperature are under room temperature to 150 DEG C condition, with evaporation copper coating, evaporation 31 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into copper and forming;
So far, the film crystal silicon perovskite heterojunction solar cell that the back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the copper be made up of the AZO transparent oxide conductive layer taking glass as substrate is formed is formed.
Embodiment 6
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
With embodiment 1;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the above-mentioned first step obtains, adopt following steps:
B. spin coating+infusion process
B-1.CH 3nH 3cl and CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 2h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl, preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, do not stop to stir 2h by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
B-2. at the spin coating PbI on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate that the first step obtains 2film:
Be 99.999%PbI by mass percent purity 2being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI 2the concentration of solution is 1M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification 2solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI 2the heating temperatures to 65 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum 2solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 20s, then drying process 10 minutes, and electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtains spin coating PbI 2film, this film thickness is 800nm;
B-3. above-mentioned B-2 is walked the PbI of gained spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed:
By the CH obtained through above-mentioned B-1 step of aequum 3nH 3cl and CH 3nH 3it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively 3nH 3cl solution and CH 3nH 3i solution, its concentration is 10mg/mL, is CH according to volume ratio 3nH 3i Rong Ye ︰ CH 3nH 3cl solution=1 ︰ 10 gets CH respectively 3nH 3i solution and CH 3nH 3cl solution is mixed to get CH 3nH 3i and CH 3nH 3the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 2film is preheated to 60 DEG C, then by this PbI 2film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 30min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed;
B-4. heat treatment:
Spin coating on the electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer of AZO transparent oxide conductive layer formation taking glass as substrate obtained by being walked by the B-3 of above-mentioned second step has CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the entirety of the film that mixing is formed is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 1000nm, and with glass be substrate AZO transparent oxide conductive layer form electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone form film crystal silicon perovskite heterojunction;
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
With embodiment 1;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
B. hot evaporation coating method:
Be placed in vacuum coating equipment by the entirety of goods obtained by above-mentioned 3rd step, carrying out plated film to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, use Resistant heating vacuum coating equipment under the voltage of 175V, is 8.0 × 10 in vacuum degree -4pa and temperature are under room temperature to 150 DEG C condition, with the silver-plated method of evaporation, evaporation 60 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into silver and forming;
So far, the film crystal silicon perovskite heterojunction solar cell that the back electrode that final obtained electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and the silver be made up of the AZO transparent oxide conductive layer taking glass as substrate is formed is formed.
Raw material involved in above-described embodiment, equipment and process method of operation are all known.

Claims (6)

1. film crystal silicon perovskite heterojunction solar cell, it is characterized in that: be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode, wherein, perovskite light absorbing zone and P type film crystal silicon hole transmission layer possess the energy level matched; Its composition sequential system is: P type film crystal silicon hole transport is placed on electrically conducting transparent substrate, perovskite light absorbing zone is placed in above P type film crystal silicon hole transmission layer, perovskite light absorbing zone and P type film crystal silicon hole transmission layer form film crystal silicon perovskite heterojunction, the electric transmission be made up of compact titanium dioxide is placed on above perovskite light absorbing zone, back electrode is placed in by above the electron transfer layer that compact titanium dioxide is formed, above five functional layers superpose successively, form this film crystal silicon perovskite heterojunction solar cell.
2. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described perovskite light absorbing zone perovskite material used is CH 3nH 3pbX 3, wherein X=Cl is or/and I, and thickness is 0.05 ~ 30um.
3. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.
4. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described back electrode is the thin layer that forms of aluminium, silver or copper or grid line.
5. the preparation method of film crystal silicon perovskite heterojunction solar cell described in claim 1, its step is as follows:
The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 1A ~ 7.5A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H 2lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, formed P type polycrystal silicon film is transferred in electrically conducting transparent substrate from monocrystalline silicon piece, is prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;
Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:
At the spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the above-mentioned first step is obtained, adopt in following two kinds of methods any one:
A. single spin-coating method:
A-1.CH 3nH 3the preparation of X, wherein X=Cl or I (lower same):
Preparation CH 3nH 3the raw material of X to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen halide solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen halide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3x, described hydrogen halide solution is hydrogen chloride solution or hydrogen iodide solution,
A-2. composition is CH 3nH 3pbX 3the preparation of perovskite precursor aqueous solution:
To be mass percent by mol ratio be 99.999% PbX 2: the CH that above-mentioned A-1 step is obtained 3nH 3x=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbX 2concentration be 0.5 ~ 1M, CH 3nH 3the concentration of X is 1 ~ 2.5M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH 3nH 3pbX 3perovskite precursor aqueous solution, stand-by, above-mentioned PbX 2in X=Cl or I, and and CH 3nH 3x in X is consistent;
A-3. the wet film of spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:
Be put on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH 3nH 3pbX 3perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 10 ~ 30s, the wet film of perovskite light absorbing zone in spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer;
A-4. heat treatment:
By obtained for above-mentioned A-3 step on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer in spin coating the entirety of the wet film of perovskite light absorbing zone put in baking oven and heat-treat, first heat treatment 0.5 ~ 1h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;
B. spin coating+infusion process
B-1.CH 3nH 3cl and CH 3nH 3the preparation of I:
Preparation CH 3nH 3the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3cl, preparation CH 3nH 3the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree 4dry 24h under the condition of Pa, obtained CH 3nH 3i,
B-2. at the spin coating PbI on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the first step is obtained 2film:
Be 99.999%PbI by mass percent purity 2being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI 2the concentration of solution is 0.5 ~ 1M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification 2solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI 2heating temperatures to 60 ~ 65 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum 2solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 10 ~ 20s, then drying process 10 minutes, and electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtains spin coating PbI 2film, this film thickness is 10 ~ 800nm;
B-3. above-mentioned B-2 is walked the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed:
By the CH obtained through above-mentioned B-1 step of aequum 3nH 3cl and CH 3nH 3it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively 3nH 3cl solution and CH 3nH 3i solution, its concentration is 1 ~ 10mg/mL, is CH according to volume ratio 3nH 3i Rong Ye ︰ CH 3nH 3cl solution=1 ︰ 0.1 ~ 10 gets CH respectively 3nH 3i solution and CH 3nH 3cl solution is mixed to get CH 3nH 3i and CH 3nH 3the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 2film is preheated to 60 DEG C, then by this PbI 2film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 5 ~ 30min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer 2film becomes by CH 3nH 3pbI 3, CH 3nH 3pbCl 3, CH 3nH 3pbI 2cl and CH 3nH 3pbICl 2the film that mixing is formed;
B-4. heat treatment:
Spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtained by being walked by the B-3 of above-mentioned second step has CH 3nH 3pbI 3-ycl ythe entirety of film is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;
3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:
The entirety of goods obtained by above-mentioned second step is placed in magnetron sputtering apparatus, on perovskite light absorbing zone, prepared the electron transfer layer be made up of compact titanium dioxide by magnetron sputtering method, concrete operation method is: target is the TiO of purity Coriolis mass percentage 99.99% 2target, target diameter is 60mm, and thickness is 5mm, before sputtering, carries out 5min cleaning, then vacuumize with high-purity argon gas to magnetron sputtering apparatus cavity, and base vacuum is 4.0 × 10 -3pa, pass into argon gas and oxygen successively subsequently, the volume ratio being controlled argon gas and oxygen by adjust flux is 9: 1, total pressure remains 2.0Pa, sputtering power is 80W, sputtering time is 4h, again through the annealing in process of 70 DEG C to 150 DEG C after growth terminates, and the obtained electron transfer layer be made up of compact titanium dioxide on perovskite light absorbing zone thus;
4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:
What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, concrete operation method be adopt in the following two kinds method any one:
A. magnetically controlled sputter method:
The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the aluminium of mass percent purity >99.99%, copper or silver, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree -4pa, argon flow amount are 20cm 3/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 60 ~ 90min, is namely prepared into prepared by electron transfer layer in the 3rd step and back electrode is prepared into the thin layer back electrode or grid line back electrode that aluminium, copper or silver forms;
B. hot evaporation coating method:
The entirety of goods obtained by above-mentioned 3rd step is placed in vacuum coating equipment, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, under the voltage of 150 ~ 175V, use Resistant heating vacuum coating equipment, be 1 × 10 in vacuum degree -4pa ~ 8.0 × 10 -4pa and temperature are under room temperature to 150 DEG C condition, by the method for evaporation plating aluminium, copper or silver, evaporation 2 ~ 60 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into aluminium, copper or silver and forming;
So far, the final obtained film crystal silicon perovskite heterojunction solar cell be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode.
6. the preparation method of film crystal silicon perovskite heterojunction solar cell according to claim 5, is characterized in that: described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.
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