CN105226187B

CN105226187B - Film crystal silicon perovskite heterojunction solar battery and preparation method thereof

Info

Publication number: CN105226187B
Application number: CN201510785094.2A
Authority: CN
Inventors: 田汉民; 金慧娇; 毕文刚; 花中秋; 杨瑞霞; 戎小莹; 张天; 王伟
Original assignee: Hebei University of Technology
Current assignee: Hebei University of Technology
Priority date: 2015-11-15
Filing date: 2015-11-15
Publication date: 2018-01-30
Anticipated expiration: 2035-11-15
Also published as: CN105226187A

Abstract

Film crystal silicon perovskite heterojunction solar battery of the present invention and preparation method thereof, it is related to and is specially adapted for the semiconductor devices for converting light energy into electric energy, it is made up of electrically conducting transparent substrate, p-type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and back electrode, wherein, perovskite light absorbing layer possesses the energy level to match with p-type film crystal silicon hole transmission layer；Building form is：P-type film crystal silicon hole transport is placed on above electrically conducting transparent substrate, perovskite light absorbing layer is placed in above p-type film crystal silicon hole transmission layer, perovskite light absorbing layer forms film crystal silicon perovskite hetero-junctions with p-type film crystal silicon hole transmission layer, the electric transmission being made up of compact titanium dioxide is placed on above perovskite light absorbing layer, and back electrode is placed in above the electron transfer layer being made up of compact titanium dioxide.Overcome existing perovskite solar cell stability deficiency, prepare the defects of cost is high or silicon materials usage amount is big.

Description

Film crystal silicon perovskite heterojunction solar battery and preparation method thereof

Technical field

Technical scheme, which is related to, is specially adapted for the semiconductor devices for converting light energy into electric energy, specifically Film crystal silicon perovskite heterojunction solar battery and preparation method thereof.

Background technology

Relative to crystal silicon battery because crystal silicon material manufacturing cost is difficult to further lowering of situation, perovskite material is used CH₃NH₃PbX₃(X=Cl, Br, or I) is solar cell (hereinafter referred to as Ca-Ti ore type solar cell) light of main light absorbing layer Photoelectric transformation efficiency there is filming, solution at room temperature to prepare, the low manufacturing cost characteristic without rare element more than 20%, pole Has application prospect.In the Ca-Ti ore type solar cell of various structures, directly using traditional monocrystalline silicon and polycrystalline silicon solar cell Ca-Ti ore type solar cell of the p-type body silicon materials as hole transmission layer, because body silicon materials do not reduce making for silicon materials With can not realize that the cost of Ca-Ti ore type solar cell is substantially less than traditional monocrystalline silicon and polycrystalline silicon solar cell.And use non- Ca-Ti ore type solar cell of the polycrystal silicon film as hole transmission layer, then due to a large amount of dangling bonds etc. be present inside amorphous silicon membrane Defect, cause this cell photoelectric conversion performance opposite bank silion cell poor.CN201410568822.X discloses all solid state calcium Titanium ore microcrystal silicon composite solar cell and preparation method thereof, there is following deficiency in it：First, the sedimentation rate of microcrystal silicon compares Slowly, be usually no more than 5 angstroms it is per second, deposition velocity have impact on production efficiency and cost.Large-scale industrial production microcrystalline silicon film is wanted, Also need to microcrystalline silicon film technology of preparing and further improve speed；Second, microcrystal silicon be substantially silicon tiny crystals particle with The mixed phase of amorphous, dangling bonds and defect on its crystal boundary and inner surface are all the complex centres of photo-generated carrier.With crystalline silicon Material is compared, the open circuit electricity of the compound solar cell device for being prepared into microcrystalline silicon materials of the photo-generated carrier inside microcrystal silicon The performances such as pressure are restricted.

Therefore, the Ca-Ti ore type solar cell that its hole mobile material is made up of film crystal silicon material is developed, it is possible to achieve Silicon materials usage amount is fewer than body silicon materials while film quality and device performance ratio non-crystalline silicon and microcrystalline silicon film are excellent, helps Further improved in the performance of solar cell and production cost reduces.

The content of the invention

The technical problems to be solved by the invention are：Film crystal silicon perovskite heterojunction solar battery and its preparation side are provided Method, it is a kind of solar cell and preparation method of the hetero-junctions formed using film crystal silicon and perovskite, had both overcome existing general Logical Ca-Ti ore type solar cell because stability deficiency and preparing the defects of cost is high using organic cavity transmission layer material, and gram The defects of using body block crystal silicon material big for the Ca-Ti ore type solar cell silicon materials usage amount of hole mobile material is taken, simultaneously Also overcome the Ca-Ti ore type solar cell photoelectric conversion poor-performing for hole transmission layer using non-crystalline silicon and microcrystalline silicon film The defects of.

Technical scheme is used by the present invention solves the technical problem：Film crystal silicon perovskite heterojunction solar battery, By electrically conducting transparent substrate, p-type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electronics being made up of compact titanium dioxide Transport layer and back electrode are formed, wherein, perovskite light absorbing layer possesses the energy to match with p-type film crystal silicon hole transmission layer Level；It forms sequential system：P-type film crystal silicon hole transport is placed on above electrically conducting transparent substrate, perovskite light absorbing layer It is placed in above p-type film crystal silicon hole transmission layer, perovskite light absorbing layer forms film with p-type film crystal silicon hole transmission layer Crystal silicon perovskite hetero-junctions, the electric transmission being made up of compact titanium dioxide are placed on above perovskite light absorbing layer, back electrode It is placed in above the electron transfer layer being made up of compact titanium dioxide, five functional layers of the above are sequentially overlapped, and form this film crystal silicon Perovskite heterojunction solar battery.

Above-mentioned film crystal silicon perovskite heterojunction solar battery, the perovskite material used in the perovskite light absorbing layer are CH₃NH₃PbX₃, wherein X=Cl or/and I, thickness are 0.05~30 μm.

Above-mentioned film crystal silicon perovskite heterojunction solar battery, the electrically conducting transparent substrate be using glass as substrate AZO, ITO or FTO transparent oxide conductive layers.

Above-mentioned film crystal silicon perovskite heterojunction solar battery, the back electrode are the thin layer or grid that aluminium, silver or copper are formed Line.

The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar battery, its step are as follows：

The first step, prepare the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate：

The p type single crystal silicon piece of one layer of corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, in volume ratio hydrogen Fluoric acid: absolute ethyl alcohol=1: in 1 hydrofluoric acid ethanol solution, pass to the electric current that size is 1A~7.5A and carry out anodic oxidation, lead to Electrochemical process corrosion p type single crystal silicon piece is crossed, Porous Silicon structures are formed in monocrystalline silicon sheet surface, then by the formation Porous Silicon structures Monocrystalline silicon piece in H₂Lower 200 DEG C to 550 DEG C of atmosphere is annealed, the hole of the monocrystalline silicon piece top layer small porosity layer in annealing process Gradually closure template of the quasi- single crystalline layer as epitaxial device can be formed, using low-pressure chemical vapour deposition technique in the quasi- single crystalline layer Upper extension turns into p-type film polycrystal silicon film, and the p-type polycrystal silicon film formed is transferred into electrically conducting transparent substrate from monocrystalline silicon piece On, thus it is prepared into the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate；

Second step, the spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer：

The spin coating perovskite on the p-type film crystal silicon hole transmission layer made from the above-mentioned first step in electrically conducting transparent substrate Light absorbing layer, using any one in following two methods：

A. single spin-coating method：

A-1.CH₃NH₃X preparation, wherein X=Cl or I (similarly hereinafter)：

Prepare CH₃NH₃X raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen halide solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen halide solution=2~3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, steamed after stirring using Rotary Evaporators at 50 DEG C by rotating Hair removes solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First the white by foregoing acquisition is consolidated Body weight newly all dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, will finally obtained White solid be put into vacuum drying chamber, be 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃X, the hydrogen halide solution are hydrogen chloride solution or iodate hydrogen solution；

A-2. composition is CH₃NH₃PbX₃Perovskite precursor aqueous solution preparation：

It is the PbX that mass percent purity is 99.999% by mol ratio₂: CH made from above-mentioned A-1 steps₃NH₃X=1:3 is mixed Close, and be dissolved in the DMF that mass percent purity is 99.9% and obtain solution A -2, wherein PbX₂'s Concentration is 0.5~1M, CH₃NH₃X concentration is 1~2.5M, at room temperature, by the above-mentioned magnetic stirrer of solution A -2 12h, it is CH that composition, which is made,₃NH₃PbX₃Perovskite precursor aqueous solution, stand-by, above-mentioned PbX₂In X=Cl or I, and with CH₃NH₃X in X is consistent；

A-3. on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate spin coating perovskite light absorbing layer it is wet Film：

P-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate is integrally put into spin coating instrument On, for wherein p-type film crystal silicon hole transmission layer upper, it is CH to take the desired amount of composition as made from above-mentioned A-2 steps₃NH₃PbX₃'s Perovskite precursor aqueous solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated into 6000rpm and keeps this Rotating speed 10~30s of spin coating of sample, perovskite light is inhaled in spin coating on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate Receive the wet film of layer；

A-4. it is heat-treated：

By calcium titanium in spin coating on the obtained p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of above-mentioned A-3 steps The entirety of the wet film of ore deposit light absorbing layer, which is put into baking oven, to be heat-treated, and 0.5~1h is first heat-treated at 90 DEG C, is again heated to 100 DEG C and 25min is incubated, thus the spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer, the perovskite light is inhaled The thickness for receiving layer is 0.05~30 μm, and the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate and perovskite light Absorbed layer forms film crystal silicon perovskite hetero-junctions；

B. spin coating+infusion process

B-1.CH₃NH₃Cl and CH₃NH₃I preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=2~3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, steamed after stirring using Rotary Evaporators at 50 DEG C by rotating Hair removes solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First the white by foregoing acquisition is consolidated Body weight newly all dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, will finally obtained White solid be put into vacuum drying chamber, be 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃Cl；Prepare CH₃NH₃I raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% iodate hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend iodate hydrogen solution=2~3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, steamed after stirring using Rotary Evaporators at 50 DEG C by rotating Hair removes solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First the white by foregoing acquisition is consolidated Body weight newly all dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, will finally obtained White solid be put into vacuum drying chamber, be 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃I；

B-2. the spin coating PbI on the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate₂It is thin Film：

It is 99.999%PbI by mass percent purity₂It is dissolved in the N that mass percent purity is 99.9%, N- diformazans In base formamide so that the PbI₂The concentration of solution is 0.5~1M, and stirring clarifies bright yellow so that being formed at 70 DEG C PbI₂Solution, before spin coating, by the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate and upper State yellow PbI₂The temperature of solution is heated to 60~65 DEG C, then that the p-type made from the first step in electrically conducting transparent substrate is thin Film crystal silicon hole transmission layer is integrally placed on spin coating instrument, and wherein p-type film crystal silicon hole transmission layer is taken the desired amount of above-mentioned upper Obtained yellow PbI₂Solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated into 3000rpm and protected Such rotating speed 10~20s of spin coating is held, then through drying process 10 minutes, the p-type film crystal silicon hole in electrically conducting transparent substrate Spin coating PbI is obtained in transport layer₂Film, the film thickness are 10~800nm；

B-3. by spin coating on the p-type film crystal silicon hole transmission layer obtained by above-mentioned B-2 steps in electrically conducting transparent substrate PbI₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed：

By the desired amount of through CH made from above-mentioned B-1 steps₃NH₃Cl and CH₃NH₃I is dissolved in mass percent purity respectively In 99.9% DMF, the CH that respectively obtains₃NH₃Cl solution and CH₃NH₃I solution, its concentration is 1~ 10mg/mL, it is CH according to volume ratio₃NH₃I Rong Ye ︰ CH₃NH₃The ︰ 0.1~10 of Cl solution=1 takes CH respectively₃NH₃I solution and CH₃NH₃Cl solution mixes to obtain CH₃NH₃I and CH₃NH₃Cl mixed solution, first walked by the mixed solution and by B-2 obtained in P The PbI of spin coating on type film crystal silicon hole transmission layer₂Film is preheated to 60 DEG C, then by the PbI₂Film fully immerses above-mentioned mixed Close and reacted in solution, taken out after standing 5~30min, p-type film of the above-mentioned B-2 steps gained in electrically conducting transparent substrate is brilliant The PbI of spin coating on silicon hole transmission layer₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed；

B-4. it is heat-treated：

By on the obtained p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of the B-3 steps of above-mentioned second step Spin coating has by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂The entirety for mixing the film formed is put into It is heat-treated into baking oven, is first incubated 1 hour at 90 DEG C, is again heated to 100 DEG C and is incubated 25 minutes, it is thus thin in p-type Spin coating perovskite light absorbing layer on film crystal silicon hole transmission layer, the thickness of the perovskite light absorbing layer is 0.05~30 μm, and P-type film crystal silicon hole transmission layer and perovskite light absorbing layer formation film crystal silicon perovskite in electrically conducting transparent substrate is heterogeneous Knot；

3rd step, the electron transfer layer being made up of compact titanium dioxide is made on perovskite light absorbing layer：

The entirety of product obtained by above-mentioned second step is placed into magnetron sputtering apparatus, by magnetron sputtering method in calcium titanium The electron transfer layer being made up of compact titanium dioxide is prepared on ore deposit light absorbing layer, concrete operation method is：Target is purity Coriolis mass The TiO of percentage 99.99%₂Target, target diameter 60mm, thickness 5mm, before sputtering, with high-purity argon gas to magnetron sputtering apparatus Cavity carries out 5min cleanings, then vacuumizes, and base vacuum is 4.0 × 10^-3Pa, argon gas and oxygen are then passed through successively, pass through It is 9: 1 that regulation flow, which controls the volume ratio of argon gas and oxygen, and total pressure remains 2.0Pa, sputtering power 80W, sputtering time For 4h, growth is passed through 70 DEG C to 150 DEG C of annealing, is thus made on perovskite light absorbing layer by densification two again after terminating The electron transfer layer that titanium oxide is formed；

4th step, back electrode is prepared on the electron transfer layer being made up of compact titanium dioxide：

Back electrode is prepared on the electron transfer layer being made up of compact titanium dioxide that above-mentioned 3rd step is prepared into, specific behaviour It is to use any one in the following two kinds method as method：

A. magnetically controlled sputter method：

The entirety of product obtained by above-mentioned 3rd step is placed into ultravacuum DC magnetron sputtering device, to the 3rd step system It is standby into the electron transfer layer being made up of compact titanium dioxide carry out plated film, sputtering target uses mass percent purity>99.99% Aluminium, copper or silver, be passed through by 99.999% Ar of mass percent purity as sputter gas in sputtering chamber, be in vacuum 4.0×10^-4Pa, argon flow amount 20cm³Under conditions of/S, target-substrate distance are 10cm and operating current is 1A, 60~90min is sputtered Afterwards, i.e., be prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into aluminium, copper or silver form it is thin Layer back electrode or grid line back electrode；

B. hot evaporation method：

The entirety of product obtained by above-mentioned 3rd step is placed into vacuum coating equipment, the 3rd step is prepared into by densification The electron transfer layer that titanium dioxide is formed carries out plated film, and Resistant heating vacuum coating equipment is used under 150~175V voltage, It is 1 × 10 in vacuum^-4Pa~8.0 × 10^-4Pa and temperature are room temperature under the conditions of 150 DEG C, with evaporation plating aluminium, copper or silver Method, be deposited 2~60 seconds, i.e., be prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into aluminium, The thin layer back electrode that copper or silver are formed；

So far, it is final be made by electrically conducting transparent substrate, p-type film crystal silicon hole transmission layer, perovskite light absorbing layer, by causing The film crystal silicon perovskite heterojunction solar battery that the electron transfer layer and back electrode that close titanium dioxide is formed are formed.

The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar battery, the electrically conducting transparent substrate be using glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.

The preparation method of above-mentioned film crystal silicon perovskite heterojunction solar battery, wherein involved raw material, equipment and Process operation is known.

The beneficial effects of the invention are as follows：Compared with prior art, the substantive distinguishing features of protrusion of the invention are as follows：

(1) film crystal silicon perovskite heterojunction solar battery of the invention and preparation method thereof and CN201410568822.X Disclosed all solid state perovskite microcrystal silicon composite solar cell and preparation method thereof is compared, and substantial distinguishing feature is：, CN201410568822.X uses microcrystalline silicon film layer as hole transmission layer, and the present invention uses polycrystal silicon film as hole transport Layer.Microcrystal silicon is substantially the mixed phase of small granular silicon crystal and amorphous silicon, between small granular silicon crystal surface, crystal grain Crystal boundary and amorphous silicon in there is it is a large amount of the defects of, dangling bonds.And crystal silicon is that silicon atom is regularly arranged, have substantially complete Lattice structure crystal, it is internal substantially without defect, crystal boundary.Due to existing inside microcrystalline silicon film far more than polycrystal silicon film A large amount of crystal boundaries, dangling bonds the defects of, the Carrier recombination inside microcrystal silicon hole transmission layer is significantly higher than crystal silicon material, so Cause CN201410568822.X battery performances be weaker than the present invention use battery of the film crystal silicon material for hole transmission layer.Adopt With film crystal silicon cavitation layer substitute microcrystal silicon cavitation layer difficult point be design with perovskite material process matching, Performance Match and The film crystal silicon technique of cost matching.First, traditional crystalline silicon material by high-purity polycrystalline silicon raw material in 1450 degrees Celsius of height Just the disorderly arranged ordering rule that is converted to of liquid silicon atom is arranged under the conditions of temperature, and 1450 celsius temperatures are far above perovskite material Expect the equilibrium temperature of 200 degrees centigrades, hinder and crystal silicon is introduced into perovskite battery.Second, the monocrystalline silicon material of machine cuts The method that material obtains polycrystal silicon film is limited by silicon materials itself fragility and carborundum line intensity, can not economically obtain thickness Crystal silicon chip less than 150 microns, and crystal silicon chip of the thickness more than 150 microns is applied to perovskite battery hole transmission layer, both It is a large amount of compound so as to which device performance drastically declines or even can not realize photoelectricity because carrier transport distance in silicon chip is long Conversion, but it is suitable with conventional crystal silion cell and it is not possessed cost value because consuming silicon materials.The present inventor Team has done the research of hardships in order to overcome the defects of present in CN201410568822.X technology, meticulous design and a large amount of Experiment, just successfully obtain with perovskite material process matching, crystal silicon thickness much smaller than 150 μm and Performance Match, cost Film crystal silicon perovskite heterojunction solar battery matched somebody with somebody and preparation method thereof.Above-mentioned distinguishing feature prove it is of the invention with it is existing Technology CN201410568822.X is compared, and has prominent substantive distinguishing features and marked improvement.

(2) it is of the invention different from existing plane Ca-Ti ore type solar cell and film crystal silicon solar battery structure.It is existing The structure of plane Ca-Ti ore type solar cell be：1. electrically conducting transparent substrate, the electric transmission being 2. made up of compact titanium dioxide Layer, 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 too Positive electricity pond；The structure of existing polycrystal silicon film solar cell：1. p-type layer polycrystal silicon film, 2. I types (intrinsic layer) amorphous silicon membrane Layer, 3. N-type amorphous thin Film layers, this three stacking are added together, and plate respectively in film both sides conduction silver grating line and copper or After the conductive substrates that the films such as aluminium are formed, polycrystal silicon film solar cell is just formed；Existing perovskite micro crystal silicon solar battery Structure is：1. electrically conducting transparent substrate, the electron transfer layer being 2. made up of compact titanium dioxide, 3. calcium titanium ore bed, 4. microcrystal silicon is empty Cave transport layer, 5. back electrode.This five is partly superimposed together, and just constitutes perovskite micro crystal silicon solar battery；And the present invention The structure of film crystal silicon Ca-Ti ore type solar cell is：1. electrically conducting transparent substrate, 2. p-type film crystal silicon hole transmission layer, 3. calcium Titanium ore light absorbing layer, the electron transfer layer being 4. made up of compact titanium dioxide, 5. back electrode.This five part, which is mutually matched, to be compounded in Together, particularly perovskite light absorbing layer and p-type film crystal silicon hole transmission layer is combined into film crystal silicon perovskite hetero-junctions Film, thus constitute the film crystal silicon perovskite heterojunction solar battery of the present invention.

(3) essential step that suitable hole transport layer material is the development of Ca-Ti ore type solar cell is found and develops, so And needed suitable for the material of Ca-Ti ore type solar cell hole transmission layer with the best result with perovskite light absorption layer material Son occupies track (abbreviation HOMO) and what minimum molecule did not occupied that unoccupied orbital (abbreviation LUMO) matches leads valence-band level position, with Realize carrier transport, it is also necessary to there is the long-time stability in outdoor operation and cheap cost, to prepare meet at present The material of this requirement is highly difficult.The present invention is by perovskite light absorption layer material and p-type film crystal silicon hole transport layer material knot Close and film crystal silicon perovskite hetero-junction thin-film is made, possess the performance of level-density parameter, and both make use of perovskite light absorbs The low cost and excellent light absorbs, opto-electronic conversion performance of layer, obtain low cost optical absorbed layer, have drawn p-type film crystalline substance again The mature and stable characteristic of silicon, there are the substantive distinguishing features of the practical protrusion of the developing new solar cell of lower price high efficiency.

(4) in the prior art, polycrystal silicon film solar cell uses polycrystal silicon film as light absorbing layer, thick there is polycrystal silicon film The contradiction of degree and battery performance.Because the crystal silicon material absorption coefficient of light is low, during the thinner thickness of polycrystal silicon film, light absorbs deficiency； And the thickness of polycrystal silicon film it is thicker when, then can not realize that the cost of polycrystal silicon film solar cell is substantially less than traditional monocrystalline silicon and more Crystal silicon solar battery.In addition, polycrystal silicon film solar cell uses emitter stage of the amorphous silicon membrane as battery, then further increase Overall preparation cost, and due to the defects of a large amount of dangling bonds be present inside amorphous silicon membrane, cause this cell photoelectric to turn It is poor to change performance opposite bank silion cell.And it is of the invention using perovskite material as light absorbing layer, by light absorpting ability several times in crystalline substance The perovskite material of silicon materials realizes the function of light absorbs, and polycrystal silicon film only undertakes the effect in isolation electric transmission hole, institute Polycrystal silicon film solar cell is far below with the dosage of the crystal silicon material in the present invention.

Compared with prior art, marked improvement of the invention is：By perovskite light absorption layer material and p-type film crystal silicon Material be mutually matched compound, obtained film crystal silicon Ca-Ti ore type solar cell overcome existing Ca-Ti ore type solar cell because The shortcomings that existing stability is poor and expensive using organic hole transport material, film crystal silicon solar battery is overcome again The shortcomings that absorption coefficient of light is low be present by light absorbing layer of crystal silicon material；Meanwhile relative to perovskite micro crystal silicon solar battery, sheet The solar cell and its technology of preparing of invention use film crystal silicon, and for the hole mobile material in battery, its Carrier recombination is notable Better than microcrystalline silicon materials, and because it is the crystal silicon of filming, so having advantage of low cost, embody as follows：

(1) film crystal silicon perovskite heterojunction solar battery stability of the present invention is good：

The Ca-Ti ore type solar cell for the peak efficiency reported at present is all based on organic hole transport material.The present invention's adopts Mature and stable film crystal silicon layer substitutes the various organic hole transport materials reported at present, and its advantage is：Film is brilliant Silicon materials are mature and stable, have been successfully applied to film crystal silicon solar battery etc., therefore avoid oxidation operation, reduction and decomposition Influence to the steady operation life-span of Ca-Ti ore type solar cell.Therefore the film crystal silicon perovskite microcrystal silicon THIN COMPOSITE of the present invention One of the advantages of film solar cell and preparation method thereof, is：Ca-Ti ore type solar cell working life is extended, reduces electricity The efficiency decay in pond.

(2) the preparation speed of film crystal silicon perovskite heterojunction solar battery of the present invention is high, and it is low to prepare cost：

As above described in background section, the most important factor for restricting film crystal silicon solar battery at present is due to as light The crystal silicon material absorption coefficient of light of absorbed layer is low, and to ensure light absorbs, the thickness of film crystal silicon solar battery is stilled need tens of It is more than micron.And film crystal silicon perovskite heterojunction solar battery of the present invention is using calcium titanium ore bed as light absorbing layer, required film is brilliant The thickness of silicon hole transmission layer is greatly reduced, and is significantly reduced using silicon materials dosage；Again relative to crystal silicon light absorbing layer material Material, perovskite light absorbing layer is solution low temperature preparation, and it is fast low with cost is prepared to prepare speed.Film crystal silicon used in the present invention The material 2,2' also more expensive than gold, platinum with the price used in traditional Ca-Ti ore type solar cell, [(the 4- first of N, N- bis- of 7,7'- tetra- Phenyl) amino] two fluorenes (abbreviation SpiroOMeTAD) of-9,9'- spiral shells, polyase 13-hexyl thiophene (abbreviation P3HT) and fullerene Several organic hole transport materials of derivative (abbreviation PCBM) are compared, and have very big cost advantage.Therefore, film of the present invention is brilliant Another advantage of silico-calcium titanium ore heterojunction solar battery and preparation method thereof is：It is high to prepare speed, it is low to prepare cost.

(3) the photoelectric conversion performance of film crystal silicon perovskite heterojunction solar battery of the present invention is good：

P-type film crystal silicon in film crystal silicon perovskite heterojunction solar battery of the present invention has and perovskite light absorbing layer The highest molecule of material occupies the level of energy (- 5.43 electron-volts) of track and minimum molecule do not occupy unoccupied orbital energy level (- 3.93 electron-volts) match lead valence-band level position (be respectively -5.328 electron-volts and -4.17 electron-volts), realize Carrier transport and final photoelectric conversion, and relative to less using microcrystal silicon layer material, the Carrier recombination of crystal silicon material. Therefore, film crystal silicon Ca-Ti ore type solar cell of the invention and preparation method thereof it is a further advantage that：Photoelectric conversion performance It is good.

Brief description of the drawings

The present invention is further described with reference to the accompanying drawings and examples.

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 substrates, 2.P type film crystal silicon hole transmission layers, 3. perovskite light absorbing layers, 4. by densification The electron transfer layer that titanium dioxide is formed, 5. back electrodes.

Embodiment

Embodiment illustrated in fig. 1 shows that film crystal silicon perovskite heterojunction solar battery is thin by electrically conducting transparent substrate 1, p-type Film crystal silicon hole transmission layer 2, perovskite light absorbing layer 3, the electron transfer layer 4 being made up of compact titanium dioxide and the structure of back electrode 5 Into.Incident light injects electrically conducting transparent substrate 1, p-type film crystal silicon hole transmission layer 2, perovskite light absorbing layer 3 and by densification successively The electron transfer layer 4 that titanium dioxide is formed, photoelectric current is formed, resulting electric current can be from back electrode 5 and electrically conducting transparent base Bottom 1 exports.

Embodiment 1

The p type single crystal silicon piece of one layer of corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, in volume ratio hydrogen Fluoric acid: absolute ethyl alcohol=1: in 1 hydrofluoric acid ethanol solution, pass to the electric current that size is 1A and carry out anodic oxidation, pass through electrification Method corrodes p type single crystal silicon piece, Porous Silicon structures is formed in monocrystalline silicon sheet surface, then by the monocrystalline of the formation Porous Silicon structures Silicon chip is in H₂Lower 200 DEG C to 550 DEG C of atmosphere is annealed, and the hole of the monocrystalline silicon piece top layer small porosity layer can be gradual in annealing process Closure form template of the quasi- single crystalline layer as epitaxial device, using low-pressure chemical vapour deposition technique on the quasi- single crystalline layer extension As p-type film polycrystal silicon film, the p-type polycrystal silicon film formed is transferred to the AZO using glass as substrate from monocrystalline silicon piece In the electrically conducting transparent substrate that transparent oxide conductive layer is formed, the p-type film crystal silicon in electrically conducting transparent substrate is thus prepared into Hole transmission layer；

In the electrically conducting transparent base formed made from the above-mentioned first step in the AZO transparent oxide conductive layers using glass as substrate Spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer on bottom, using following steps：

A. single spin-coating method：

A-1.CH₃NH₃Cl preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=2 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C, Do not stopped to stir 1.5h with constant temperature blender with magnetic force, removed after stirring using Rotary Evaporators at 50 DEG C by rotary evaporation Solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：By the white solid of foregoing acquisition again first All dissolve in ethanol, then constantly add dry diethyl ether and separate out sediment, this process is repeated twice, the white that will finally obtain Solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, CH is made₃NH₃Cl；

A-2. composition is CH₃NH₃PbCl₃Perovskite precursor aqueous solution preparation：

It is the PbCl that mass percent purity is 99.999% by mol ratio₂: CH made from above-mentioned A-1 steps₃NH₃Cl=1:3 Mixing, and be dissolved in the DMF that mass percent purity is 99.9% and obtain solution A -2, wherein PbCl₂ Concentration be 0.5M, CH₃NH₃Cl concentration is 1M, and at room temperature, above-mentioned solution A -2 magnetic stirrer 12h is made Composition is CH₃NH₃PbCl₃Perovskite precursor aqueous solution, it is stand-by；

P-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate is integrally put into spin coating instrument On, for wherein p-type film crystal silicon hole transmission layer upper, it is CH to take the desired amount of composition as made from above-mentioned A-2 steps₃NH₃PbCl₃ Perovskite precursor aqueous solution be spun on p-type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated into 6000rpm and kept Such rotating speed spin coating 10s, the P in the electrically conducting transparent substrate that the AZO transparent oxide conductive layers using glass as substrate are formed On type film crystal silicon hole transmission layer in spin coating perovskite light absorbing layer wet film；

A-4. it is heat-treated：

The electrically conducting transparent base that will be formed made from above-mentioned A-3 steps in the AZO transparent oxide conductive layers using glass as substrate The entirety of the wet film of perovskite light absorbing layer is put into baking oven and carried out in spin coating on p-type film crystal silicon hole transmission layer on bottom Heat treatment, 0.5h first is heat-treated at 90 DEG C, 100 DEG C is again heated to and is incubated 25min, thus passed in p-type film crystal silicon hole Spin coating perovskite light absorbing layer on defeated layer, the thickness of the perovskite light absorbing layer is 10nm, and in the AZO using glass as substrate The p-type film crystal silicon hole transmission layer and perovskite light absorbing layer shape in electrically conducting transparent substrate that transparent oxide conductive layer is formed Into film crystal silicon perovskite hetero-junctions；

The entirety of product obtained by above-mentioned second step is placed into magnetron sputtering apparatus, by magnetron sputtering method in calcium titanium The electron transfer layer being made up of compact titanium dioxide is prepared on ore deposit light absorbing layer, concrete operation method is：Target is purity Coriolis mass The TiO of percentage 99.99%₂Target, target diameter 60mm, thickness 5mm, before sputtering, with high-purity argon gas to magnetron sputtering apparatus Cavity carries out 5min cleanings, then vacuumizes, and base vacuum is 4.0 × 10^-3Pa, argon gas and oxygen are then passed through successively, pass through It is 9: 1 that regulation flow, which controls the volume ratio of argon gas and oxygen, and total pressure remains 2.0Pa, sputtering power 80W, sputtering time For 4h, growth is passed through 70 DEG C of annealing, is thus made on perovskite light absorbing layer by compact titanium dioxide again after terminating The electron transfer layer of composition；

Back electrode is prepared on the electron transfer layer being made up of compact titanium dioxide that above-mentioned 3rd step is prepared into, specific behaviour It is with the following method as method：

A. magnetically controlled sputter method：

The entirety of product obtained by above-mentioned 3rd step is placed into ultravacuum DC magnetron sputtering device, without using mask Version, the electron transfer layer being made up of compact titanium dioxide being prepared into the 3rd step carry out plated film, and sputtering target uses quality percentage Compare purity>99.99% aluminium, it is passed through by 99.999% Ar of mass percent purity as sputter gas in sputtering chamber, Vacuum is 4.0 × 10^-4Pa, argon flow amount 20cm³Under conditions of/S, target-substrate distance are 10cm and operating current is 1A, sputtering After 60min, i.e., the thin layer that aluminium is formed is prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into Back electrode；

So far, it is final that the electrically conducting transparent substrate being made up of the AZO transparent oxide conductive layers using glass as substrate, P is made What type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and aluminium were formed The film crystal silicon perovskite heterojunction solar battery that thin layer back electrode is formed.

Embodiment 2

The p type single crystal silicon piece of one layer of corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, in volume ratio hydrogen Fluoric acid: absolute ethyl alcohol=1: in 1 hydrofluoric acid ethanol solution, pass to the electric current that size is 4.5A and carry out anodic oxidation, pass through electricity Chemical method corrodes p type single crystal silicon piece, Porous Silicon structures is formed in monocrystalline silicon sheet surface, then by the list of the formation Porous Silicon structures Crystal silicon chip is in H₂The annealing of lower 200 DEG C to 550 DEG C of atmosphere, the hole of the monocrystalline silicon piece top layer small porosity layer can be by annealing process Gradually closure form template of the quasi- single crystalline layer as epitaxial device, using low-pressure chemical vapour deposition technique on the quasi- single crystalline layer outside Prolonging turns into p-type film polycrystal silicon film, and the p-type polycrystal silicon film formed is transferred to from monocrystalline silicon piece using glass as substrate In the electrically conducting transparent substrate that transparent oxide conducting layer is formed, the p-type film being thus prepared into electrically conducting transparent substrate is brilliant Silicon hole transmission layer；

In the electrically conducting transparent base formed made from the above-mentioned first step in the transparent oxide conducting layer using glass as substrate Spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer on bottom, using following steps：

A. single spin-coating method：

A-1.CH₃NH₃I preparation：

Prepare CH₃NH₃I raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% iodate hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend iodate hydrogen solution=2.5 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stopped to stir 1.8h with constant temperature blender with magnetic force, pass through rotary evaporation at 50 DEG C using Rotary Evaporators after stirring Solvent is removed, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First by the white solid of foregoing acquisition Again all dissolving in ethanol, then constantly adds dry diethyl ether and separates out sediment, this process is repeated twice, and will finally obtain White solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃I；

A-2. composition is CH₃NH₃PbI₃Perovskite precursor aqueous solution preparation：

It is the PbI that mass percent purity is 99.999% by mol ratio₂: CH made from above-mentioned A-1 steps₃NH₃I=1:3 is mixed Close, and be dissolved in the DMF that mass percent purity is 99.9% and obtain solution A -2, wherein PbI₂It is dense Spend for 0.8M, CH₃NH₃I concentration is 1.8M, and at room temperature, above-mentioned solution A -2 magnetic stirrer 12h is made into It is divided into CH₃NH₃PbI₃Perovskite precursor aqueous solution, it is stand-by；

A-3. the p-type film in the electrically conducting transparent substrate that the transparent oxide conducting layer using glass as substrate is formed The wet film of spin coating perovskite light absorbing layer on crystal silicon hole transmission layer：

By made from the first step in the electrically conducting transparent substrate that the transparent oxide conducting layer using glass as substrate is formed P-type film crystal silicon hole transmission layer be integrally put on spin coating instrument, wherein p-type film crystal silicon hole transmission layer upper, take needed for The composition as made from above-mentioned A-2 steps of amount is CH₃NH₃PbI₃Perovskite precursor aqueous solution be spun to p-type film crystal silicon hole transport On layer, spin coating instrument rotating speed is accelerated into rotating speed spin coating 15s as 6000rpm and holding, the p-type in electrically conducting transparent substrate is thin On film crystal silicon hole transmission layer in spin coating perovskite light absorbing layer wet film；

A-4. it is heat-treated：

The electrically conducting transparent base that will be formed made from above-mentioned A-3 steps in the transparent oxide conducting layer using glass as substrate The entirety of the wet film of perovskite light absorbing layer is put into baking oven and carried out in spin coating on p-type film crystal silicon hole transmission layer on bottom Heat treatment, 0.8h first is heat-treated at 90 DEG C, 100 DEG C is again heated to and is incubated 25min, thus passed in p-type film crystal silicon hole Spin coating perovskite light absorbing layer on defeated layer, the thickness of the perovskite light absorbing layer is 500nm, and using glass as substrate The p-type film crystal silicon hole transmission layer and perovskite light absorbs in electrically conducting transparent substrate that transparent oxide conducting layer is formed Layer forms film crystal silicon perovskite hetero-junctions；

With embodiment 1；

A. magnetically controlled sputter method：

The entirety of product obtained by above-mentioned 3rd step is placed into ultravacuum DC magnetron sputtering device, without using mask Version, the electron transfer layer being made up of compact titanium dioxide being prepared into the 3rd step carry out plated film, and sputtering target uses quality percentage Compare purity>99.99% copper, it is passed through by 99.999% Ar of mass percent purity as sputter gas in sputtering chamber, Vacuum is 4.0 × 10^-4Pa, argon flow amount 20cm³Under conditions of/S, target-substrate distance are 10cm and operating current is 1A, sputtering After 75min, i.e., the thin layer that copper is formed is prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into Back electrode；

So far, it is final that the electrically conducting transparent substrate being made up of the transparent oxide conducting layer using glass as substrate, P is made What type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and copper were formed The film crystal silicon perovskite heterojunction solar battery that thin layer back electrode is formed.

Embodiment 3

The p type single crystal silicon piece of one layer of corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, in volume ratio hydrogen Fluoric acid: absolute ethyl alcohol=1: in 1 hydrofluoric acid ethanol solution, pass to the electric current that size is 7.5A and carry out anodic oxidation, pass through electricity Chemical method corrodes p type single crystal silicon piece, Porous Silicon structures is formed in monocrystalline silicon sheet surface, then by the list of the formation Porous Silicon structures Crystal silicon chip is in H₂The annealing of lower 200 DEG C to 550 DEG C of atmosphere, the hole of the monocrystalline silicon piece top layer small porosity layer can be by annealing process Gradually closure form template of the quasi- single crystalline layer as epitaxial device, using low-pressure chemical vapour deposition technique on the quasi- single crystalline layer outside Prolonging turns into p-type film polycrystal silicon film, and the p-type polycrystal silicon film formed is transferred to from monocrystalline silicon piece using glass as substrate In the electrically conducting transparent substrate that FTO transparent oxides conductive layer is formed, the p-type film being thus prepared into electrically conducting transparent substrate is brilliant Silicon hole transmission layer；

In the electrically conducting transparent base formed made from the above-mentioned first step in the FTO transparent oxide conductive layers using glass as substrate Spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer on bottom, using following steps：

A. single spin-coating method：

A-1.CH₃NH₃Cl preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C, Do not stopped to stir 2h with constant temperature blender with magnetic force, removed after stirring at 50 DEG C by rotary evaporation using Rotary Evaporators molten Agent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：It is first that the white solid of foregoing acquisition is again complete Portion dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, finally consolidates obtained white Body is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, CH is made₃NH₃Cl；

It is the PbCl that mass percent purity is 99.999% by mol ratio₂: CH made from above-mentioned A-1 steps₃NH₃Cl=1:3 Mixing, and be dissolved in the DMF that mass percent purity is 99.9% and obtain solution A -2, wherein PbCl₂ Concentration be 1M, CH₃NH₃Cl concentration is 2.5M, and at room temperature, above-mentioned solution A -2 magnetic stirrer 12h is made Composition is CH₃NH₃PbCl₃Perovskite precursor aqueous solution, it is stand-by；

A-3. the p-type film in the electrically conducting transparent substrate that the FTO transparent oxide conductive layers using glass as substrate are formed The wet film of spin coating perovskite light absorbing layer on crystal silicon hole transmission layer：

By made from the first step in the electrically conducting transparent substrate that the FTO transparent oxide conductive layers using glass as substrate are formed P-type film crystal silicon hole transmission layer be integrally put on spin coating instrument, wherein p-type film crystal silicon hole transmission layer upper, take needed for The composition as made from above-mentioned A-2 steps of amount is CH₃NH₃PbCl₃Perovskite precursor aqueous solution be spun to p-type film crystal silicon hole biography On defeated layer, spin coating instrument rotating speed is accelerated into rotating speed spin coating 30s as 6000rpm and holding, the p-type in electrically conducting transparent substrate On film crystal silicon hole transmission layer in spin coating perovskite light absorbing layer wet film；

A-4. it is heat-treated：

The electrically conducting transparent base that will be formed made from above-mentioned A-3 steps in the FTO transparent oxide conductive layers using glass as substrate The entirety of the wet film of perovskite light absorbing layer is put into baking oven and carried out in spin coating on p-type film crystal silicon hole transmission layer on bottom Heat treatment, 1h first is heat-treated at 90 DEG C, 100 DEG C is again heated to and is incubated 25min, thus in p-type film crystal silicon hole transport Spin coating perovskite light absorbing layer on layer, the thickness of the perovskite light absorbing layer is 1000nm, and in the FTO using glass as substrate The p-type film crystal silicon hole transmission layer and perovskite light absorbing layer shape in electrically conducting transparent substrate that transparent oxide conductive layer is formed Into film crystal silicon perovskite hetero-junctions；

With embodiment 1；

A. magnetically controlled sputter method：

The entirety of product obtained by above-mentioned 3rd step is placed into ultravacuum DC magnetron sputtering device, uses mask Version, the electron transfer layer being made up of compact titanium dioxide being prepared into the 3rd step carry out plated film, and sputtering target uses quality percentage Compare purity>99.99% silver, it is passed through by 99.999% Ar of mass percent purity as sputter gas in sputtering chamber, Vacuum is 4.0 × 10^-4Pa, argon flow amount 20cm³Under conditions of/S, target-substrate distance are 10cm and operating current is 1A, sputtering After 90min, i.e., the grid line that silver is formed is prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into Back electrode；

So far, it is final that the electrically conducting transparent substrate being made up of the FTO transparent oxide conductive layers using glass as substrate, P is made What type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and silver were formed The film crystal silicon perovskite heterojunction solar battery that grid line back electrode is formed.

Embodiment 4

With embodiment 1；

B. spin coating+infusion process

B-1.CH₃NH₃Cl and CH₃NH₃I preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=2 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C, Do not stopped to stir 1.5h with constant temperature blender with magnetic force, removed after stirring using Rotary Evaporators at 50 DEG C by rotary evaporation Solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：By the white solid of foregoing acquisition again first All dissolve in ethanol, then constantly add dry diethyl ether and separate out sediment, this process is repeated twice, the white that will finally obtain Solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, CH is made₃NH₃Cl；System Standby CH₃NH₃I raw material is the iodine that the methylethylolamine solution that mass percent concentration is 33% and mass percent concentration are 57% Change hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent concentration is 57% Iodate hydrogen solution=2: 1, it is put into after both solution are mixed in 250mL round-bottomed flask, at 0 DEG C, with constant temperature magnetic force Agitator does not stop to stir 1.5h, removes solvent by rotary evaporation at 50 DEG C using Rotary Evaporators after stirring, will obtain The white solid obtained is cleaned three times with ether, and specific cleaning step is：First the white solid of foregoing acquisition is all dissolved again In ethanol, then constantly add dry diethyl ether and separate out sediment, this process is repeated twice, is finally put into obtained white solid It is 5 × 10 in 60 DEG C and vacuum into vacuum drying chamber⁴24h is dried under conditions of Pa, CH is made₃NH₃I；

B-2. in the electrically conducting transparent base formed made from the first step in the AZO transparent oxide conductive layers using glass as substrate Spin coating PbI on p-type film crystal silicon hole transmission layer on bottom₂Film：

It is 99.999%PbI by mass percent purity₂It is dissolved in the N that mass percent purity is 99.9%, N- diformazans In base formamide so that the PbI₂The concentration of solution is 0.5M, and stirring clarifies bright yellow PbI so that being formed at 70 DEG C₂ Solution, before spin coating, by the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate and above-mentioned Huang Color PbI₂The temperature of solution is heated to 60 DEG C, then that the p-type film crystal silicon made from the first step in electrically conducting transparent substrate is empty Cave transport layer is integrally placed on spin coating instrument, and wherein p-type film crystal silicon hole transmission layer takes the desired amount of Huang obtained above upper Color PbI₂Solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated to as 3000rpm and holding Rotating speed spin coating 10s, then through drying process 10 minutes, formed in the AZO transparent oxide conductive layers using glass as substrate transparent Spin coating PbI is obtained on p-type film crystal silicon hole transmission layer in conductive substrates₂Film, the film thickness are 10nm；

B-3. the electrically conducting transparent above-mentioned B-2 step gained formed in the AZO transparent oxide conductive layers using glass as substrate The PbI of spin coating on p-type film crystal silicon hole transmission layer in substrate₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、 CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed：

By the desired amount of through CH made from above-mentioned B-1 steps₃NH₃Cl and CH₃NH₃I is dissolved in mass percent purity respectively In 99.9% DMF, the CH that respectively obtains₃NH₃Cl solution and CH₃NH₃I solution, its concentration are 1mg/ ML, it is CH according to volume ratio₃NH₃I Rong Ye ︰ CH₃NH₃The ︰ 0.1 of Cl solution=1 takes CH respectively₃NH₃I solution and CH₃NH₃Cl solution mixes Close to obtain CH₃NH₃I and CH₃NH₃Cl mixed solution, first walked by the mixed solution and by B-2 obtained in p-type film crystal silicon hole The PbI of spin coating in transport layer₂Film is preheated to 60 DEG C, then by the PbI₂Film fully immerses anti-therewith in above-mentioned mixed solution Should, taken out after standing 5min, the spin coating on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of above-mentioned B-2 steps gained PbI₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed；

B-4. it is heat-treated：

Formed the B-3 of above-mentioned second step step is obtained in the AZO transparent oxide conductive layers using glass as substrate Spin coating has CH on p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl And CH₃NH₃PbICl₂The entirety for the film that mixing is formed, which is put into baking oven, to be heat-treated, and is first incubated 1 hour at 90 DEG C, It is again heated to 100 DEG C and is incubated 25 minutes, thus the spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer, should The thickness of perovskite light absorbing layer is 10nm, and is formed in the AZO transparent oxide conductive layers using glass as substrate transparent P-type film crystal silicon hole transmission layer in conductive substrates forms film crystal silicon perovskite hetero-junctions with perovskite light absorbing layer；

With embodiment 1；

B. hot evaporation method：

The entirety of product obtained by above-mentioned 3rd step is placed into vacuum coating equipment, the 3rd step is prepared into by densification The electron transfer layer that titanium dioxide is formed carries out plated film, Resistant heating vacuum coating equipment is used under 150V voltage, true Reciprocal of duty cycle is 1 × 10^-4Pa and temperature are room temperature under the conditions of 150 DEG C, with the method for evaporation plating aluminium, are deposited 2 seconds, i.e., in the 3rd step system It is standby into the electron transfer layer being made up of compact titanium dioxide on be prepared into the thin layer back electrode that aluminium forms；

Embodiment 5

With embodiment 1；

B. spin coating+infusion process

B-1.CH₃NH₃Cl and CH₃NH₃I preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=2.5 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stopped to stir 1.8h with constant temperature blender with magnetic force, pass through rotary evaporation at 50 DEG C using Rotary Evaporators after stirring Solvent is removed, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First by the white solid of foregoing acquisition Again all dissolving in ethanol, then constantly adds dry diethyl ether and separates out sediment, this process is repeated twice, and will finally obtain White solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃Cl；Prepare CH₃NH₃I raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% iodate hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend iodate hydrogen solution=2.5 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stopped to stir 1.8h with constant temperature blender with magnetic force, pass through rotary evaporation at 50 DEG C using Rotary Evaporators after stirring Solvent is removed, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First by the white solid of foregoing acquisition Again all dissolving in ethanol, then constantly adds dry diethyl ether and separates out sediment, this process is repeated twice, and will finally obtain White solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃I；

It is 99.999%PbI by mass percent purity₂It is dissolved in the N that mass percent purity is 99.9%, N- diformazans In base formamide so that the PbI₂The concentration of solution is 0.8M, and stirring clarifies bright yellow PbI so that being formed at 70 DEG C₂ Solution, before spin coating, by the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate and above-mentioned Huang Color PbI₂The temperature of solution is heated to 62 DEG C, then that the p-type film crystal silicon made from the first step in electrically conducting transparent substrate is empty Cave transport layer is integrally placed on spin coating instrument, and wherein p-type film crystal silicon hole transmission layer takes the desired amount of Huang obtained above upper Color PbI₂Solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated to as 3000rpm and holding Rotating speed spin coating 15s, then through drying process 10 minutes, obtained on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate Spin coating PbI₂Film, the film thickness are 400nm；

By the desired amount of through CH made from above-mentioned B-1 steps₃NH₃Cl and CH₃NH₃I is dissolved in mass percent purity respectively In 99.9% DMF, the CH that respectively obtains₃NH₃Cl solution and CH₃NH₃I solution, its concentration are 5mg/ ML, it is CH according to volume ratio₃NH₃I Rong Ye ︰ CH₃NH₃The ︰ 5 of Cl solution=1 takes CH respectively₃NH₃I solution and CH₃NH₃Cl solution mixes Obtain CH₃NH₃I and CH₃NH₃Cl mixed solution, first walked by the mixed solution and by B-2 obtained in p-type film crystal silicon hole biography The PbI of spin coating on defeated layer₂Film is preheated to 60 DEG C, then by the PbI₂Film, which is fully immersed in above-mentioned mixed solution, to be reacted, Taken out after standing 16min, the spin coating on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of above-mentioned B-2 steps gained PbI₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed；

B-4. it is heat-treated：

Formed the B-3 of above-mentioned second step step is obtained in the AZO transparent oxide conductive layers using glass as substrate Spin coating has CH on p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl And CH₃NH₃PbICl₂The entirety for the film that mixing is formed, which is put into baking oven, to be heat-treated, and is first incubated 1 hour at 90 DEG C, It is again heated to 100 DEG C and is incubated 25 minutes, thus the spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer, should The thickness of perovskite light absorbing layer is 500nm, and is formed in the AZO transparent oxide conductive layers using glass as substrate transparent P-type film crystal silicon hole transmission layer in conductive substrates forms film crystal silicon perovskite hetero-junctions with perovskite light absorbing layer；

With embodiment 1；

B. hot evaporation method：

The entirety of product obtained by above-mentioned 3rd step is placed into vacuum coating equipment, the 3rd step is prepared into by densification The electron transfer layer that titanium dioxide is formed carries out plated film, Resistant heating vacuum coating equipment is used under 165V voltage, true Reciprocal of duty cycle is 4.0 × 10^-4Pa and temperature are room temperature under the conditions of 150 DEG C, with evaporation copper coating, are deposited 31 seconds, i.e., the 3rd Walk and be prepared into the thin layer back electrode that copper is formed on the electron transfer layer being made up of compact titanium dioxide being prepared into；

So far, it is final that the electrically conducting transparent substrate being made up of the AZO transparent oxide conductive layers using glass as substrate, P is made What type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and copper were formed The film crystal silicon perovskite heterojunction solar battery that back electrode is formed.

Embodiment 6

With embodiment 1；

B. spin coating+infusion process

B-1.CH₃NH₃Cl and CH₃NH₃I preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend hydrogen chloride solution=3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C, Do not stopped to stir 2h with constant temperature blender with magnetic force, removed after stirring at 50 DEG C by rotary evaporation using Rotary Evaporators molten Agent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：It is first that the white solid of foregoing acquisition is again complete Portion dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, finally consolidates obtained white Body is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, CH is made₃NH₃Cl；Prepare CH₃NH₃I raw material is the iodate that the methylethylolamine solution that mass percent concentration is 33% and mass percent concentration are 57% Hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent concentration is 57% iodine Change hydrogen solution=3: 1, it will be put into 250mL round-bottomed flask after the mixing of both solution, at 0 DEG C, be stirred with constant temperature magnetic force Mix device not stop to stir 2h, solvent is removed by rotary evaporation at 50 DEG C using Rotary Evaporators after stirring, by acquisition White solid is cleaned three times with ether, and specific cleaning step is：First the white solid by foregoing acquisition is all dissolved in second again In alcohol, then constantly add dry diethyl ether and separate out sediment, this process is repeated twice, is finally put into obtained white solid very It is 5 × 10 in 60 DEG C and vacuum in empty drying box⁴24h is dried under conditions of Pa, CH is made₃NH₃I；

It is 99.999%PbI by mass percent purity₂It is dissolved in the N that mass percent purity is 99.9%, N- diformazans In base formamide so that the PbI₂The concentration of solution is 1M, and stirring clarifies bright yellow PbI so that being formed at 70 DEG C₂It is molten Liquid, before spin coating, by the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate and above-mentioned yellow PbI₂The temperature of solution is heated to 65 DEG C, then by the p-type film crystal silicon hole made from the first step in electrically conducting transparent substrate Transport layer is integrally placed on spin coating instrument, and wherein p-type film crystal silicon hole transmission layer takes the desired amount of yellow obtained above upper PbI₂Solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated into 3000rpm and such turn of holding Fast spin coating 20s, then through drying process 10 minutes, revolved on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate Apply PbI₂Film, the film thickness are 800nm；

By the desired amount of through CH made from above-mentioned B-1 steps₃NH₃Cl and CH₃NH₃I is dissolved in mass percent purity respectively In 99.9% DMF, the CH that respectively obtains₃NH₃Cl solution and CH₃NH₃I solution, its concentration are 10mg/ ML, it is CH according to volume ratio₃NH₃I Rong Ye ︰ CH₃NH₃The ︰ 10 of Cl solution=1 takes CH respectively₃NH₃I solution and CH₃NH₃Cl solution mixes Obtain CH₃NH₃I and CH₃NH₃Cl mixed solution, first walked by the mixed solution and by B-2 obtained in p-type film crystal silicon hole biography The PbI of spin coating on defeated layer₂Film is preheated to 60 DEG C, then by the PbI₂Film, which is fully immersed in above-mentioned mixed solution, to be reacted, Taken out after standing 30min, the spin coating on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of above-mentioned B-2 steps gained PbI₂Film becomes by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed；

B-4. it is heat-treated：

Formed the B-3 of above-mentioned second step step is obtained in the AZO transparent oxide conductive layers using glass as substrate Spin coating has CH on p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl And CH₃NH₃PbICl₂The entirety for the film that mixing is formed, which is put into baking oven, to be heat-treated, and is first incubated 1 hour at 90 DEG C, It is again heated to 100 DEG C and is incubated 25 minutes, thus the spin coating perovskite light absorbing layer on p-type film crystal silicon hole transmission layer, should The thickness of perovskite light absorbing layer is 1000nm, and is formed in the AZO transparent oxide conductive layers using glass as substrate saturating P-type film crystal silicon hole transmission layer in bright conductive substrates forms film crystal silicon perovskite hetero-junctions with perovskite light absorbing layer；

With embodiment 1；

B. hot evaporation method：

The entirety of product obtained by above-mentioned 3rd step is placed into vacuum coating equipment, the 3rd step is prepared into by densification The electron transfer layer that titanium dioxide is formed carries out plated film, Resistant heating vacuum coating equipment is used under 175V voltage, true Reciprocal of duty cycle is 8.0 × 10^-4Pa and temperature are room temperature under the conditions of 150 DEG C, with silver-plated method is evaporated, are deposited 60 seconds, i.e., the 3rd Walk and the thin layer back electrode that silver is formed is prepared on the electron transfer layer being made up of compact titanium dioxide being prepared into；

So far, it is final that the electrically conducting transparent substrate being made up of the AZO transparent oxide conductive layers using glass as substrate, P is made What type film crystal silicon hole transmission layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and silver were formed The film crystal silicon perovskite heterojunction solar battery that back electrode is formed.

Involved raw material, equipment and process operation are known in above-described embodiment.

Claims

1. film crystal silicon perovskite heterojunction solar battery, it is characterised in that：By electrically conducting transparent substrate, p-type film crystal silicon hole Transport layer, perovskite light absorbing layer, the electron transfer layer being made up of compact titanium dioxide and back electrode are formed, wherein, perovskite Light absorbing layer possesses the energy level to match with p-type film crystal silicon hole transmission layer；It forms sequential system：P-type film crystal silicon Hole transport is placed on above electrically conducting transparent substrate, and perovskite light absorbing layer is placed in above p-type film crystal silicon hole transmission layer, Perovskite light absorbing layer forms film crystal silicon perovskite hetero-junctions with p-type film crystal silicon hole transmission layer, by compact titanium dioxide The electric transmission of composition is placed on above perovskite light absorbing layer, and back electrode is placed in the electric transmission being made up of compact titanium dioxide Above, five functional layers of the above are sequentially overlapped layer, form this film crystal silicon perovskite heterojunction solar battery.

2. the preparation method of film crystal silicon perovskite heterojunction solar battery, its step are as follows described in claim 1：

The p type single crystal silicon piece of one layer of corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, in volume ratio hydrofluoric acid : absolute ethyl alcohol=1: in 1 hydrofluoric acid ethanol solution, pass to the electric current that size is 1A~7.5A and carry out anodic oxidation, pass through electricity Chemical method corrodes p type single crystal silicon piece, Porous Silicon structures is formed in monocrystalline silicon sheet surface, then by the list of the formation Porous Silicon structures Crystal silicon chip is in H₂The annealing of lower 200 DEG C to 550 DEG C of atmosphere, the hole of the monocrystalline silicon piece top layer small porosity layer can be by annealing process Gradually closure form template of the quasi- single crystalline layer as epitaxial device, using low-pressure chemical vapour deposition technique on the quasi- single crystalline layer outside Prolonging turns into p-type film polycrystal silicon film, and the p-type polycrystal silicon film formed is transferred to from monocrystalline silicon piece in electrically conducting transparent substrate, Thus it is prepared into the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate；

Spin coating perovskite light is inhaled on the p-type film crystal silicon hole transmission layer made from the above-mentioned first step in electrically conducting transparent substrate Layer is received, using any one in following two methods：

A. single spin-coating method：

A-1.CH₃NH₃X preparation, wherein X=Cl or I (similarly hereinafter)：

Prepare CH₃NH₃X raw material is the methylethylolamine solution that mass percent concentration is 33% and mass percent concentration is 57% hydrogen halide solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent concentration Hydrogen halide solution=2~3 for 57%: 1, it is put into after both solution are mixed in 250mL round-bottomed flask, at 0 DEG C, Do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, pass through rotary evaporation at 50 DEG C using Rotary Evaporators after stirring Solvent is removed, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First by the white solid of foregoing acquisition Again all dissolving in ethanol, then constantly adds dry diethyl ether and separates out sediment, this process is repeated twice, and will finally obtain White solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃X, the hydrogen halide solution are hydrogen chloride solution or iodate hydrogen solution；

It is the PbX that mass percent purity is 99.999% by mol ratio₂: CH made from above-mentioned A-1 steps₃NH₃X=1:3 mixing, And it is dissolved in the DMF that mass percent purity is 99.9% and obtains solution A -2, wherein PbX₂Concentration For 0.5~1M, CH₃NH₃X concentration is 1~2.5M, at room temperature, by above-mentioned solution A -2 magnetic stirrer 12h, system It is CH to obtain composition₃NH₃PbX₃Perovskite precursor aqueous solution, stand-by, above-mentioned PbX₂In X=Cl or I, and and CH₃NH₃X in X It is consistent；

A-3. on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate spin coating perovskite light absorbing layer wet film：

P-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate is integrally put on spin coating instrument, its For middle p-type film crystal silicon hole transmission layer upper, it is CH to take the desired amount of composition as made from above-mentioned A-2 steps₃NH₃PbX₃Calcium titanium Ore deposit precursor aqueous solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated to as 6000rpm and holding Rotating speed 10~30s of spin coating, perovskite light absorbing layer in spin coating on the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate Wet film；

A-4. it is heat-treated：

By perovskite light in spin coating on the obtained p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of above-mentioned A-3 steps The entirety of the wet film of absorbed layer, which is put into baking oven, to be heat-treated, and 0.5~1h is first heat-treated at 90 DEG C, is again heated to 100 DEG C and be incubated 25min, thus spin coating perovskite light absorbing layer, the perovskite light absorbs on p-type film crystal silicon hole transmission layer The thickness of layer is 0.05~30 μm, and the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate is inhaled with perovskite light Receive layer and form film crystal silicon perovskite hetero-junctions；

B. spin coating+infusion process

B-1.CH₃NH₃Cl and CH₃NH₃I preparation：

Prepare CH₃NH₃Cl raw material is the methylethylolamine solution that mass percent concentration is 33% and mass percent concentration is 57% hydrogen chloride solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent concentration Hydrogen chloride solution=2~3 for 57%: 1, it is put into after both solution are mixed in 250mL round-bottomed flask, at 0 DEG C, Do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, pass through rotary evaporation at 50 DEG C using Rotary Evaporators after stirring Solvent is removed, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First by the white solid of foregoing acquisition Again all dissolving in ethanol, then constantly adds dry diethyl ether and separates out sediment, this process is repeated twice, and will finally obtain White solid is put into vacuum drying chamber, is 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃Cl；Prepare CH₃NH₃I raw material is the methylethylolamine solution and mass percent concentration that mass percent concentration is 33% For 57% iodate hydrogen solution, the methylethylolamine solution for being by volume 33% for mass percent concentration:Mass percent is dense Spend iodate hydrogen solution=2~3 for 57%: 1, will both solution mix after be put into 250mL round-bottomed flask, at 0 DEG C Under, do not stop 1.5~2h of stirring with constant temperature blender with magnetic force, steamed after stirring using Rotary Evaporators at 50 DEG C by rotating Hair removes solvent, the white solid of acquisition is cleaned three times with ether, specific cleaning step is：First the white by foregoing acquisition is consolidated Body weight newly all dissolves in ethanol, then constantly adds dry diethyl ether and separate out sediment, and this process is repeated twice, will finally obtained White solid be put into vacuum drying chamber, be 5 × 10 in 60 DEG C and vacuum⁴24h is dried under conditions of Pa, is made CH₃NH₃I；

B-2. the spin coating PbI on the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate₂Film：

It is 99.999%PbI by mass percent purity₂It is dissolved in the N that mass percent purity is 99.9%, N- dimethyl formyls In amine so that the PbI₂The concentration of solution is 0.5~1M, and stirring clarifies bright yellow PbI so that being formed at 70 DEG C₂It is molten Liquid, before spin coating, by the p-type film crystal silicon hole transmission layer made from the first step in electrically conducting transparent substrate and above-mentioned yellow PbI₂The temperature of solution is heated to 60~65 DEG C, then by the p-type film crystal silicon made from the first step in electrically conducting transparent substrate Hole transmission layer is integrally placed on spin coating instrument, and wherein p-type film crystal silicon hole transmission layer is taken the desired amount of obtained above upper Yellow PbI₂Solution is spun on p-type film crystal silicon hole transmission layer, and spin coating instrument rotating speed is accelerated into 3000rpm and kept so Rotating speed 10~20s of spin coating, then through drying process 10 minutes, the p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate On obtain spin coating PbI₂Film, the film thickness are 10~800nm；

B-3. by the PbI of spin coating on the p-type film crystal silicon hole transmission layer obtained by above-mentioned B-2 steps in electrically conducting transparent substrate₂Film Become by CH₃NH₃PbI₃、CH₃NH₃PbCl₃、CH₃NH₃PbI₂Cl and CH₃NH₃PbICl₂Mix the film formed：

B-4. it is heat-treated：

By spin coating on the obtained p-type film crystal silicon hole transmission layer in electrically conducting transparent substrate of the B-3 steps of above-mentioned second step There is CH₃NH₃PbI_3-yCl_yThe entirety of film, which is put into baking oven, to be heat-treated, and is first incubated 1 hour at 90 DEG C, is again heated to 100 DEG C and 25 minutes are incubated, thus spin coating perovskite light absorbing layer, the perovskite light on p-type film crystal silicon hole transmission layer The thickness of absorbed layer is 0.05~30 μm, and p-type film crystal silicon hole transmission layer and perovskite in electrically conducting transparent substrate Light absorbing layer forms film crystal silicon perovskite hetero-junctions；

The entirety of product obtained by above-mentioned second step is placed into magnetron sputtering apparatus, by magnetron sputtering method in perovskite light The electron transfer layer being made up of compact titanium dioxide is prepared on absorbed layer, concrete operation method is：Target is purity Coriolis mass percentage TiO than 99.99%₂Target, target diameter 60mm, thickness 5mm, before sputtering, with high-purity argon gas to magnetron sputtering apparatus cavity 5min cleanings are carried out, are then vacuumized, base vacuum is 4.0 × 10^-3Pa, argon gas and oxygen are then passed through successively, pass through regulation It is 9: 1 that flow, which controls the volume ratio of argon gas and oxygen, and total pressure remains 2.0Pa, sputtering power 80W, sputtering time 4h, 70 DEG C to 150 DEG C of annealing is passed through in growth again after terminating, be thus made on perovskite light absorbing layer by fine and close titanium dioxide The electron transfer layer that titanium is formed；

Back electrode, concrete operations side are prepared on the electron transfer layer being made up of compact titanium dioxide that above-mentioned 3rd step is prepared into Method is to use any one in the following two kinds method：

A. magnetically controlled sputter method：

The entirety of product obtained by above-mentioned 3rd step is placed into ultravacuum DC magnetron sputtering device, the 3rd step is prepared into The electron transfer layer that is made up of compact titanium dioxide carry out plated film, sputtering target uses mass percent purity>99.99% Aluminium, copper or silver, are passed through in sputtering chamber by 99.999% Ar of mass percent purity as sputter gas, are in vacuum 4.0×10^-4Pa, argon flow amount 20cm³Under conditions of/S, target-substrate distance are 10cm and operating current is 1A, 60~90min is sputtered Afterwards, i.e., be prepared on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into aluminium, copper or silver form it is thin Layer back electrode or grid line back electrode；

B. hot evaporation method：

The entirety of product obtained by above-mentioned 3rd step is placed into vacuum coating equipment, the 3rd step is prepared into by fine and close dioxy Change the electron transfer layer that titanium is formed and carry out plated film, Resistant heating vacuum coating equipment is used under 150~175V voltage, true Reciprocal of duty cycle is 1 × 10^-4Pa~8.0 × 10^-4Pa and temperature are room temperature under the conditions of 150 DEG C, with the method for evaporation plating aluminium, copper or silver, Evaporation 2~60 seconds, i.e., be prepared into aluminium, copper or silver on the electron transfer layer being made up of compact titanium dioxide that the 3rd step is prepared into The thin layer back electrode of composition；

So far, it is final be made by electrically conducting transparent substrate, p-type film crystal silicon hole transmission layer, perovskite light absorbing layer, by densification two The film crystal silicon perovskite heterojunction solar battery that the electron transfer layer and back electrode that titanium oxide is formed are formed.