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

Abstract

The invention relates to a thin-film crystalline silicon perovskite heterojunction solar cell and a preparation method thereof, which relate to a semiconductor device specially suitable for converting light energy into electrical energy, which consists of a transparent conductive substrate, a P-type thin-film crystalline silicon hole transport layer, and a perovskite The light absorbing layer, the electron transport layer made of dense titanium dioxide and the back electrode are composed of the perovskite light absorbing layer and the P-type thin film crystalline silicon hole transport layer with matching energy levels; the composition method is: P-type thin film crystal The silicon hole transport layer is placed on the transparent conductive substrate, the perovskite light absorbing layer is placed on the top of the P-type thin film crystalline silicon hole transport layer, and the perovskite light absorbing layer and the P-type thin film crystalline silicon hole transport layer form a thin film In the crystalline silicon perovskite heterojunction, the electron transport layer composed of dense titanium dioxide is placed on the perovskite light absorbing layer, and the back electrode is placed on the electron transport layer composed of dense titanium dioxide. It overcomes the shortcomings of the existing perovskite solar cells, such as insufficient stability, high manufacturing cost or large amount of silicon materials used.

Description

Thin film crystalline silicon perovskite heterojunction solar cell and preparation method thereof

technical field

The technical solution of the invention relates to a semiconductor device specially suitable for converting light energy into electric energy, specifically a thin-film crystal silicon perovskite heterojunction solar cell and a preparation method thereof.

Background technique

Compared with the situation that the manufacturing cost of crystalline silicon cells is difficult to further reduce, solar cells using perovskite materials CH ₃ NH ₃ PbX ₃ (X=Cl, Br, orI) as the main light-absorbing layer (hereinafter referred to as Ca Titanium-type solar cells) have a photoelectric conversion efficiency of more than 20%, and have the characteristics of thin film, room temperature solution preparation, and low manufacturing cost without rare elements, and have great application prospects. In perovskite solar cells with various structures, the P-type bulk silicon material of traditional monocrystalline silicon and polycrystalline silicon solar cells is directly used as the perovskite solar cell of the hole transport layer, because the bulk silicon material does not reduce the silicon material. However, the cost of perovskite solar cells cannot be significantly lower than that of traditional monocrystalline silicon and polycrystalline silicon solar cells. However, the perovskite solar cells using amorphous silicon thin films as the hole transport layer have poor photoelectric conversion performance compared with bulk silicon cells due to the existence of a large number of dangling bonds and other defects in the amorphous silicon thin films. CN201410568822.X discloses an all-solid-state perovskite microcrystalline silicon composite solar cell and its preparation method, which has the following disadvantages: first, the deposition rate of microcrystalline silicon is relatively slow, generally no more than 5 angstroms per second, and the deposition rate affects the Production efficiency and cost. In order to produce microcrystalline silicon thin films on a large scale, it is necessary to further increase the speed of the preparation technology of microcrystalline silicon thin films; secondly, microcrystalline silicon is essentially a mixed phase of tiny crystal particles of silicon and amorphous. Both dangling bonds and defects are recombination centers for photogenerated carriers. Compared with crystalline silicon materials, the recombination of photogenerated carriers inside microcrystalline silicon limits the open circuit voltage and other properties of solar cell devices made of microcrystalline silicon materials.

Therefore, the development of perovskite solar cells whose hole transport materials are composed of thin-film crystalline silicon materials can realize that the amount of silicon materials used is less than that of bulk silicon materials, and at the same time, the film quality and device performance are better than amorphous silicon and microcrystalline silicon films. , contribute to the further improvement of the performance of the solar cell and the reduction of the production cost.

Contents of the invention

The technical problem to be solved by the present invention is to provide a thin-film crystalline silicon perovskite heterojunction solar cell and a preparation method thereof, which is a solar cell and a preparation method using a heterojunction composed of thin-film crystalline silicon and perovskite. It overcomes the shortcomings of the existing ordinary perovskite solar cells due to the lack of stability and high manufacturing cost due to the use of organic hole transport layer materials, and overcomes the perovskite solar cells that use bulk crystalline silicon materials as hole transport materials. The defect of using a large amount of silicon material for the battery also overcomes the defect of poor photoelectric conversion performance of perovskite solar cells using amorphous silicon and microcrystalline silicon thin films as hole transport layers.

The technical scheme adopted by the present invention to solve the technical problem is: a thin-film crystalline silicon perovskite heterojunction solar cell, which consists of a transparent conductive substrate, a P-type thin-film crystalline silicon hole transport layer, a perovskite light-absorbing layer, and a dense titanium dioxide Composed of an electron transport layer and a back electrode, in which the perovskite light absorbing layer and the P-type thin film crystalline silicon hole transport layer have matching energy levels; the composition sequence is: P-type thin film crystalline silicon hole transport layer Placed on a transparent conductive substrate, the perovskite light-absorbing layer is placed on the top of the P-type thin-film crystalline silicon hole transport layer, and the perovskite light-absorbing layer and the P-type thin-film crystalline silicon hole-transport layer form a thin-film crystalline silicon perovskite Heterojunction, the electron transport layer made of dense titanium dioxide is placed on the perovskite light absorbing layer, the back electrode is placed on the electron transport layer made of dense titanium dioxide, and the above five functional layers are stacked in sequence to form this thin film crystalline calcium silicon Titanium heterojunction solar cells.

For the above-mentioned thin film crystalline silicon perovskite heterojunction solar cell, the perovskite material used in the perovskite light absorbing layer is CH ₃ NH ₃ PbX ₃ , where X=Cl or/and I, and the thickness is 0.05-30 um.

For the above-mentioned thin-film crystalline silicon perovskite heterojunction solar cell, the transparent conductive substrate is an AZO, ITO or FTO transparent oxide conductive layer based on glass.

In the above-mentioned thin-film crystalline silicon perovskite heterojunction solar cell, the back electrode is a thin layer or grid line made of aluminum, silver or copper.

The preparation method of the above-mentioned thin film crystalline silicon perovskite heterojunction solar cell, its steps are as follows:

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

Use a P-type single crystal silicon wafer coated with a layer of corrosion-resistant metal on the back as the anode, and use platinum as the cathode. _The current of ~7.5A is used for anodic oxidation, and the P-type single crystal silicon wafer is corroded by electrochemical method to form a porous silicon structure on the surface of the single crystal silicon wafer. ℃ to 550℃ for annealing. During the annealing process, the pores of the small porosity layer on the surface of the single crystal silicon wafer will gradually close to form a quasi-single crystal layer as a template for epitaxial devices. Epitaxy on this quasi-single crystal layer Become a P-type thin film crystalline silicon film, transfer the formed P-type crystalline silicon film from a single crystal silicon wafer to a transparent conductive substrate, thereby preparing a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step above, and adopt any one of the following two methods:

A. Single spin coating method:

A-1. Preparation of CH ₃ NH ₃ X, wherein X=Cl or I (the same below):

The raw material for preparing CH ₃ NH ₃ X is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen halide solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage Hydrogen halide solution with a concentration of 57% = 2-3:1, mix the two solutions and put them into a 250mL round-bottomed flask. After completion, use a rotary evaporator to remove the solvent by rotary evaporation at 50°C, and wash the obtained white solid with ether three times. Precipitate was precipitated with diethyl ether, and this process was repeated twice. Finally, the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ X , the hydrogen halide solution is a hydrogen chloride solution or a hydrogen iodide solution;

A-2. Preparation of perovskite precursor solution whose composition is CH ₃ NH ₃ PbX ₃ :

Mix the molar ratio of PbX ₂ with a mass percentage of 99.999%: CH ₃ NH ₃ X obtained in the above step A-1 = 1:3, and dissolve it in N,N-dimethylformaldehyde with a mass percentage of 99.9% purity A solution A-2 was obtained in amide, wherein the concentration of PbX ₂ was 0.5-1M, and the concentration of CH ₃ NH ₃ X was 1-2.5M. At room temperature, the above solution A-2 was stirred with a magnetic stirrer for 12h to obtain A perovskite precursor solution whose composition is CH ₃ NH ₃ PbX ₃ is ready for use, X in the above PbX ₂ = Cl or I, and is consistent with X in CH ₃ NH ₃ X;

A-3. Wet film of spin-coated perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate:

Put the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step as a whole on a spin coater, wherein the P-type thin-film crystalline silicon hole-transport layer is on top, and take the required amount of the above-mentioned The perovskite precursor solution whose composition is CH ₃ NH ₃ PbX ₃ prepared in step A-2 is spin-coated on the P-type thin-film crystalline silicon hole transport layer, and the speed of the spin coater is accelerated to 6000rpm and maintained at this speed for spin coating 10-30s, spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate;

A-4. Heat treatment:

Put the whole wet film of the perovskite light-absorbing layer spin-coated on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the above A-3 step into an oven for heat treatment, first at 90 Heat treatment at ℃ for 0.5~1h, then heat to 100℃ and hold for 25min, thus spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer, the thickness of the perovskite light-absorbing layer is 0.05~ 30um, and the P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate form a thin-film crystalline silicon perovskite heterojunction;

B. Spin coating + dipping method

B-1. Preparation of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution=2～3:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.5～2h at 0°C. Use a rotary evaporator to remove the solvent by rotary evaporation at 50°C, and wash the obtained white solid with ether three times. The specific cleaning steps are: first re-dissolve the white solid obtained above in ethanol, and then continuously add dry ether to precipitate Precipitation, this process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl; The raw material of CH ₃ NH ₃ I is the methylamine ethanol solution that mass percent concentration is 33% and the hydrogen iodide solution that mass percent concentration is 57%, is the methylamine ethanol solution that mass percent concentration is 33% by volume ratio: mass percent The hydrogen iodide solution with a concentration of 57% = 2～3:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.5～2h at 0°C. After stirring, use a rotary evaporator to remove the solvent by rotary evaporation at 50°C, and wash the obtained white solid with ether three times. Dry diethyl ether to precipitate a precipitate. Repeat this process twice. Finally, put the obtained white solid into a vacuum drying oven and dry it at 60°C and a vacuum of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ I;

B-2. on the P-type thin-film crystalline silicon hole-transport layer on the transparent conductive substrate that the first step makes spin _- coating PbI thin film:

Dissolve PbI with a mass percent purity of 99.999% in N,N _- dimethylformamide with a mass percent purity of 99.9%, so that the concentration of the PbI solution is _0.5 to 1M, and stir at 70°C until a clear Bright yellow _PbI2 solution, before spin-coating, heat the temperature of the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step and the above-mentioned yellow _PbI2 solution to 60-65°C, and then Put the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step as a whole on a spin coater, wherein the P-type thin-film crystalline silicon hole-transport layer is on top, and take the required amount of the above to obtain The yellow PbI ₂ solution is spin-coated on the P-type thin-film crystalline silicon hole transport layer, the speed of the spin coater is accelerated to 3000rpm and the speed is maintained at this speed for 10-20s, and then dried for 10 minutes, on the transparent conductive substrate On the P-type thin film crystalline silicon hole transport layer, a spin-coated _PbI2 film is obtained, and the film thickness is 10-800nm;

B-3. The PbI ₂ film spin-coated on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate obtained in the above B-2 step becomes CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , Thin film formed by mixing CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ :

Dissolve the required amount of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I prepared by the above step B-1 in N,N-dimethylformamide with a mass percent purity of 99.9%, and the obtained CH The concentrations of ₃ NH ₃ Cl solution and CH ₃ NH ₃ I solution are both 1-10 mg/mL. According to the volume ratio, CH ₃ NH ₃ I solution: CH ₃ NH ₃ Cl solution = 1: 0.1-10 respectively take CH ₃ NH ₃ I solution and CH ₃ NH ₃ Cl solution are mixed to obtain a mixed solution of CH ₃ NH ₃ I and CH ₃ NH ₃ Cl. Preheat the _PbI2 thin film spin-coated on the transmission layer to 60°C, then fully immerse the _PbI2 thin film in the above mixed solution to react with it, and take it out after standing for 5-30min. The spin-coated PbI ₂ film on the P-type thin film crystalline silicon hole transport layer becomes a mixture of CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ formed film;

B-4. Heat treatment:

Spin-coat the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate obtained in step B-3 of the second step above with CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ The entire thin film formed by mixing NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ was placed in an oven for heat treatment. First, it was kept at 90°C for 1 hour, and then heated to 100°C and kept for 25 minutes. The perovskite light-absorbing layer is spin-coated on the thin-film crystalline silicon hole-transporting layer. The thickness of the perovskite light-absorbing layer is 0.05-30um, and the P-type thin-film crystalline The mineral light absorbing layer forms a thin-film crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

Place the entire product obtained in the second step above into a magnetron sputtering device, and prepare an electron transport layer composed of dense titanium dioxide on the perovskite light-absorbing layer by magnetron sputtering. The specific operation method is: target The material is a _TiO2 target with a purity mass percentage of 99.99%. The target diameter is 60 mm and the thickness is 5 mm. 4.0×10 ^-3 Pa, followed by argon and oxygen, the volume ratio of argon and oxygen is controlled to be 9:1 by adjusting the flow rate, the total pressure is kept at 2.0Pa, the sputtering power is 80W, and the sputtering time is 4h After the growth is completed, annealing at 70°C to 150°C is performed to prepare an electron transport layer composed of dense titanium dioxide on the perovskite light absorbing layer;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

Prepare the back electrode on the electron transport layer made of dense titanium dioxide prepared in the third step above, and the specific operation method is to adopt any one of the following two methods:

A. Magnetron sputtering method:

Place the whole of the product obtained in the third step above into an ultra-vacuum DC magnetron sputtering device, and coat the electron transport layer made of dense titanium dioxide prepared in the third step. The sputtering target adopts a mass percent purity >99.99 % aluminum, copper or silver, and Ar with a mass percent purity of 99.999% is passed into the sputtering chamber as a sputtering gas. The vacuum degree is 4.0×10 ^-4 Pa, the flow rate of argon gas is 20cm ³ /S, and the target substrate Under the conditions of distance of 10cm and working current of 1A, after sputtering for 60-90min, the third step is to prepare a thin-layer back electrode or grid line made of aluminum, copper or silver on the back electrode on the electron transport layer. back electrode;

B. Thermal evaporation method:

Put the whole product prepared in the third step above into a vacuum coating machine, coat the electron transport layer made of dense titanium dioxide prepared in the third step, and use a resistance wire to heat the vacuum coating machine at a voltage of 150-175V , at a vacuum of 1×10 ^-4 Pa to 8.0×10 ^-4 Pa and a temperature of room temperature to 150°C, use the method of evaporating aluminum, copper or silver for 2 to 60 seconds, that is, in the third A thin-layer back electrode made of aluminum, copper or silver is prepared on the electron transport layer made of dense titanium dioxide prepared in one step;

So far, a thin-film crystalline silicon perovskite heterojunction solar cell consisting of a transparent conductive substrate, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorbing layer, an electron transport layer made of dense titanium dioxide, and a back electrode has finally been obtained. Battery.

In the preparation method of the above-mentioned thin-film crystalline silicon perovskite heterojunction solar cell, the transparent conductive substrate is an AZO, ITO or FTO transparent oxide conductive layer based on glass.

The preparation method of the above-mentioned thin-film crystalline silicon perovskite heterojunction solar cell, the raw materials, equipment and process operation methods involved are all known.

The beneficial effects of the present invention are: compared with prior art, the outstanding substantive features of the present invention are as follows:

(1) Compared with the all-solid-state perovskite microcrystalline silicon composite solar cell and its preparation method disclosed in CN201410568822.X, the thin-film crystalline silicon perovskite heterojunction solar cell and its preparation method are substantially different technologies The feature is: CN201410568822.X adopts the microcrystalline silicon thin film layer as the hole transport layer, while the present invention adopts the crystal silicon thin film as the hole transport layer. Microcrystalline silicon is essentially a mixed phase of tiny silicon crystal particles and amorphous silicon. There are a large number of defects and dangling bonds on the surface of tiny silicon crystal particles, the grain boundaries between crystal grains, and amorphous silicon. Crystalline silicon is a crystal in which silicon atoms are regularly arranged and has a basically complete lattice structure, and there are basically no defects or grain boundaries inside. Because there are a large number of defects such as grain boundaries and dangling bonds in the microcrystalline silicon film that are much more than those in the crystalline silicon film, the carrier recombination in the microcrystalline silicon hole transport layer is significantly higher than that of the crystalline silicon material, so the performance of the CN201410568822.X battery It is weaker than the battery using thin-film crystalline silicon material as the hole transport layer of the present invention. The difficulty of using a thin-film crystalline silicon hole layer to replace a microcrystalline silicon hole layer is to design a thin-film crystalline silicon process that matches the process, performance, and cost of perovskite materials. First of all, the traditional crystalline silicon material converts the disordered arrangement of liquid silicon atoms into an ordered and regular arrangement through high-purity polysilicon raw materials at a high temperature of 1450 degrees Celsius, and the high temperature of 1450 degrees Celsius is much higher than the stable temperature of perovskite materials at about 200 degrees Celsius , hindering the introduction of crystalline silicon into perovskite cells. Second, the method of obtaining crystalline silicon thin films from mechanically cut monocrystalline silicon materials is limited by the brittleness of the silicon material itself and the strength of the corundum wire, and it is impossible to economically obtain crystalline silicon wafers with a thickness of less than 150 microns. Chips are used in the hole transport layer of perovskite cells, because the carrier transport distance in the silicon chip is too long and recombined in large quantities, so the performance of the device drops sharply and even the photoelectric conversion cannot be realized, and because the silicon material consumed is different from that of traditional crystalline silicon Batteries are so comparable that it doesn't have cost value. In order to overcome the defects of the technology of CN201410568822.X, the team of inventors of the present invention has done arduous research, careful design and a large number of experiments, and successfully obtained the technology matching with perovskite material, and the thickness of crystalline silicon is far less than 150um. Thin film crystalline silicon perovskite heterojunction solar cell with matching performance and cost and preparation method thereof. The above distinguishing technical features prove that the present invention has outstanding substantive features and significant progress compared with the prior art CN201410568822.X.

(2) The present invention is different from the existing planar perovskite solar cells and thin-film crystalline silicon solar cells in structure. The structure of the existing planar perovskite solar cells is: ① transparent conductive substrate, ② electron transport layer composed of dense titanium dioxide, ③ perovskite layer, ④ organic hole transport layer, ⑤ back electrode. These five parts are stacked together to form a perovskite solar cell; the structure of the existing crystalline silicon thin film solar cell: ①P-type crystalline silicon thin film layer, ②I-type (intrinsic layer) amorphous silicon thin film layer, ③N-type Amorphous silicon thin film layer, these three layers are stacked together, and after the conductive silver grid wire and the conductive substrate composed of thin films such as copper or aluminum are plated on both sides of the film, a crystalline silicon thin film solar cell is formed; the existing calcium The structure of titanium ore microcrystalline silicon solar cells is: ① transparent conductive substrate, ② electron transport layer composed of dense titanium dioxide, ③ perovskite layer, ④ microcrystalline silicon hole transport layer, ⑤ back electrode. These five parts are stacked together to form a perovskite microcrystalline silicon solar cell; and the structure of the thin-film crystalline silicon perovskite solar cell of the present invention is: ① transparent conductive substrate, ② P-type thin-film crystalline silicon hole transport layer , ③ perovskite light absorbing layer, ④ electron transport layer composed of dense titanium dioxide, ⑤ back electrode. These five parts are matched and compounded together, especially the perovskite light absorbing layer and the P-type thin film crystalline silicon hole transport layer are combined to form a thin film crystalline silicon perovskite heterojunction film, thus forming the thin film crystalline silicon of the present invention Perovskite heterojunction solar cells.

(3) Finding and developing a suitable material for the hole transport layer is an important step in the development of perovskite solar cells. The highest molecular occupied orbital (abbreviated as HOMO) and the lowest molecular unoccupied unoccupied orbital (abbreviated as LUMO) match the conduction band energy level position to realize carrier transport, and it also needs to have long-term stability in outdoor operation and low cost. At present, it is very difficult to prepare materials that meet this requirement. The present invention combines the perovskite light absorbing layer material and the P-type thin film crystalline silicon hole transport layer material to prepare a thin film crystalline silicon perovskite heterojunction film, which has the performance of energy level matching, and not only utilizes perovskite The low cost and excellent light absorption and photoelectric conversion performance of the light absorption layer, the low-cost light absorption layer is obtained, and the mature and stable characteristics of P-type thin film silicon are absorbed, which has the outstanding essence of developing low-cost and high-efficiency new solar cells for practical use sexual characteristics.

(4) In the prior art, the crystalline silicon thin film solar cell uses the crystalline silicon thin film as the light absorbing layer, and there is a contradiction between the thickness of the crystalline silicon thin film and the performance of the battery. Due to the low light absorption coefficient of crystalline silicon materials, when the thickness of crystalline silicon film is thin, the light absorption is insufficient; and when the thickness of crystalline silicon film is thick, the cost of crystalline silicon thin film solar cells is significantly lower than that of traditional single crystal silicon and solar cells. Polycrystalline silicon solar cells. In addition, crystalline silicon thin film solar cells use amorphous silicon thin film as the emitter of the cell, which further increases the overall manufacturing cost, and because there are a large number of dangling bonds and other defects in the amorphous silicon thin film, the photoelectric conversion performance of this cell is relatively low. Silicon cells are inferior. In the present invention, the perovskite material is used as the light-absorbing layer, and the light-absorbing function is realized by the perovskite material whose light-absorbing ability is tens of times that of the crystalline silicon material, and the crystalline silicon film only undertakes the function of isolating electrons and transporting holes, so The amount of crystalline silicon material used in the present invention is much lower than that of crystalline silicon thin film solar cells.

Compared with the prior art, the remarkable progress of the present invention lies in: the perovskite light absorbing layer material and the P-type thin film crystalline silicon material are matched and compounded, and the obtained thin film crystalline silicon perovskite solar cell overcomes the existing Perovskite-type solar cells have the disadvantages of poor stability and high price due to the use of organic hole transport materials, and overcome the disadvantages of low light absorption coefficient of thin-film crystalline silicon solar cells with crystalline silicon materials as the light-absorbing layer; at the same time, Compared with the perovskite microcrystalline silicon solar cell, the solar cell and its preparation technology of the present invention use thin-film crystalline silicon as the hole transport material in the cell, and its carrier recombination is significantly better than that of the microcrystalline silicon material, and because it is Thin-filmed crystalline silicon has the advantage of low cost, which is embodied as follows:

(1) The thin film crystalline silicon perovskite heterojunction solar cell of the present invention has good stability:

The highest efficiency perovskite solar cells reported so far are all based on organic hole transport materials. The mature and stable thin film crystalline silicon layer of the present invention is used to replace various organic hole transport materials currently reported, and its advantages are: the thin film crystalline silicon material is mature and stable, and has been successfully applied to thin film crystalline silicon solar cells, etc. Effects of organic oxidation, reduction and decomposition on the stable working life of perovskite solar cells. Therefore, one of the advantages of the thin film crystalline silicon perovskite microcrystalline silicon composite thin film solar cell and the preparation method thereof of the present invention is that the working life of the perovskite solar cell is prolonged and the efficiency attenuation of the cell is reduced.

(2) The preparation rate of the thin film crystalline silicon perovskite heterojunction solar cell of the present invention is high, and the preparation cost is low:

As mentioned in the background technology section above, the most important factor restricting thin-film crystalline silicon solar cells is the low light absorption coefficient of the crystalline silicon material used as the light-absorbing layer. In order to ensure light absorption, the thickness of thin-film crystalline silicon solar cells still needs to be within tens of Micron or more. However, the thin film crystalline silicon perovskite heterojunction solar cell of the present invention uses the perovskite layer as the light absorbing layer, and the thickness of the required thin film crystalline silicon hole transport layer is greatly reduced, which significantly reduces the amount of silicon material used; The crystalline silicon light absorbing layer material and the perovskite light absorbing layer are prepared by solution at low temperature, and the preparation speed is fast and the preparation cost is low. The thin-film crystalline silicon material used in the present invention is different from the 2,2',7,7'-tetrakis[N,N-bis(4-methoxy], which is more expensive than gold and platinum used in traditional perovskite solar cells. phenyl)amino]-9,9'-spirobifluorene (SpiroOMeTAD for short), polymerized 3-hexylthiophene (P3HT for short) and fullerene derivatives (PCBM for short) compared with several organic hole transport materials, which have Great cost advantage. Therefore, another advantage of the thin-film crystalline silicon perovskite heterojunction solar cell and the preparation method thereof of the present invention is that the preparation rate is high and the preparation cost is low.

(3) The photoelectric conversion performance of the thin film crystalline silicon perovskite heterojunction solar cell of the present invention is good:

The P-type thin film crystalline silicon in the thin film crystalline silicon perovskite heterojunction solar cell of the present invention has the energy level position (-5.43 electron volts) of the highest molecule occupied orbital and the lowest molecular unoccupied space of the perovskite light absorbing layer material. The energy level of the orbital (-3.93 eV) matches the position of the conduction band energy level (respectively -5.328 eV and -4.17 eV), to achieve carrier transport and final photoelectric conversion, and compared to the use of microcrystalline Silicon layer materials, crystalline silicon materials have less carrier recombination. Therefore, another advantage of the thin film crystalline silicon perovskite solar cell and its preparation method of the present invention is that it has good photoelectric conversion performance.

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is a schematic structural view of a thin film crystalline silicon perovskite solar cell of the present invention.

In the figure, 1. Transparent conductive substrate, 2. P-type thin film crystalline silicon hole transport layer, 3. Perovskite light absorption layer, 4. Electron transport layer made of dense titanium dioxide, 5. Back electrode.

detailed description

The embodiment shown in Figure 1 shows that the thin-film crystalline silicon perovskite heterojunction solar cell consists of a transparent conductive substrate 1, a P-type thin-film crystalline silicon hole transport layer 2, a perovskite light absorption layer 3, and a solar cell made of dense titanium dioxide. The electron transport layer 4 and the back electrode 5 constitute. The incident light enters the transparent conductive substrate 1, the P-type thin-film crystalline silicon hole transport layer 2, the perovskite light absorption layer 3 and the electron transport layer 4 composed of dense titanium dioxide in sequence to form a photocurrent, and the resulting current can be obtained from The back electrode 5 and the transparent conductive substrate 1 output.

Example 1

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

Use a P-type single crystal silicon wafer coated with a layer of corrosion-resistant metal on the back as the anode, and use platinum as the cathode. Anodic oxidation is carried out by an electric current, and the P _- type single crystal silicon wafer is corroded by an electrochemical method to form a porous silicon structure on the surface of the single crystal silicon wafer. ℃ annealing, during the annealing process, the pores of the small porosity layer on the surface of the single crystal silicon wafer will gradually close to form a quasi-single crystal layer as a template for epitaxial devices, and the quasi-single crystal layer is epitaxially formed on the quasi-single crystal layer to become P-type by low-pressure chemical vapor deposition. Thin-film crystalline silicon film, the formed P-type crystalline silicon film is transferred from a single crystal silicon wafer to a transparent conductive substrate composed of a glass-based AZO transparent oxide conductive layer, and thus prepared on a transparent conductive substrate P-type thin film crystalline silicon hole transport layer;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

A. Single spin coating method:

A-1. Preparation of CH ₃ NH ₃ Cl:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution = 2:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.5h at 0°C. After the stirring is completed, use a rotary evaporation The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with ether. The specific cleaning steps were as follows: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether to precipitate the precipitate. This process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl;

A-2. Preparation of perovskite precursor solution whose composition is CH ₃ NH ₃ PbCl ₃ :

Mix the molar ratio of PbCl ₂ with a mass percentage of 99.999%: CH ₃ NH ₃ Cl obtained in the above step A-1 = 1:3, and dissolve it in N,N-dimethylformaldehyde with a mass percentage of 99.9% purity A solution A-2 was obtained in the amide, wherein the concentration of PbCl ₂ was 0.5M, and the concentration of CH ₃ NH ₃ Cl was 1M. At room temperature, the above solution A-2 was stirred with a magnetic stirrer for 12h, and the obtained component was CH ₃ The perovskite precursor solution of NH ₃ PbCl ₃ , stand-by;

A-3. Wet film of spin-coated perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate:

Put the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step as a whole on a spin coater, wherein the P-type thin-film crystalline silicon hole-transport layer is on top, and take the required amount of the above-mentioned The perovskite precursor solution whose composition is CH ₃ NH ₃ PbCl ₃ prepared in step A-2 is spin-coated on the P-type thin-film crystalline silicon hole transport layer, and the speed of the spin coater is accelerated to 6000rpm and maintained at this speed for spin coating 10s, spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of AZO transparent oxide conductive layer based on glass;

A-4. Heat treatment:

Spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of the AZO transparent oxide conductive layer based on glass, which is obtained in the above A-3 step Put the whole into an oven for heat treatment, first heat treatment at 90°C for 0.5h, then heat to 100°C and keep it warm for 25min, so that the perovskite light absorbing layer is spin-coated on the P-type thin film crystalline silicon hole transport layer, The thickness of the perovskite light-absorbing layer is 10nm, and the P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer form a thin film Crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

Place the entire product obtained in the second step above into a magnetron sputtering device, and prepare an electron transport layer composed of dense titanium dioxide on the perovskite light-absorbing layer by magnetron sputtering. The specific operation method is: target The material is a _TiO2 target with a purity mass percentage of 99.99%. The target diameter is 60 mm and the thickness is 5 mm. 4.0×10 ^-3 Pa, followed by argon and oxygen, the volume ratio of argon and oxygen is controlled to be 9:1 by adjusting the flow rate, the total pressure is kept at 2.0Pa, the sputtering power is 80W, and the sputtering time is 4h After the growth is completed, annealing at 70°C is performed to prepare an electron transport layer composed of dense titanium dioxide on the perovskite light absorbing layer;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

Prepare the back electrode on the electron transport layer made of dense titanium dioxide prepared in the third step above, and the specific operation method is as follows:

A. Magnetron sputtering method:

Place the whole of the product obtained in the third step above into an ultra-vacuum DC magnetron sputtering device, without using a mask, and coat the electron transport layer made of dense titanium dioxide prepared in the third step. The sputtering target adopts Aluminum with a mass percentage purity >99.99%, and Ar with a mass percentage purity ^{of 99.999} % are passed into the sputtering chamber as a sputtering gas. Under the conditions of a base distance of 10 cm and an operating current of 1 A, after sputtering for 60 minutes, a thin-layer back electrode made of aluminum is prepared on the electron transport layer and on the back electrode in the third step;

So far, a transparent conductive substrate composed of a glass-based AZO transparent oxide conductive layer, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide and aluminum A thin-film crystalline silicon perovskite heterojunction solar cell composed of a thin-layer back electrode.

Example 2

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

With a P-type single crystal silicon wafer coated with a layer of corrosion-resistant metal on the back as the anode and platinum as the cathode, in a hydrofluoric acid ethanol solution with a volume ratio of hydrofluoric acid: absolute ethanol = 1:1, the size is 4.5 The current of A is used for anodic oxidation, and the P _- type single crystal silicon wafer is corroded by an electrochemical method to form a porous silicon structure on the surface of the single crystal silicon wafer. Annealing at 550°C. During the annealing process, the holes in the small porosity layer on the surface of the single crystal silicon wafer will gradually close to form a quasi-single crystal layer as a template for epitaxial devices. The quasi-single crystal layer is epitaxially formed on the quasi-single crystal layer to form P Type thin-film crystalline silicon film, the formed P-type crystalline silicon film is transferred from a single crystal silicon wafer to a transparent conductive substrate composed of a glass-based ITO transparent oxide conductive layer, thus being prepared on a transparent conductive substrate P-type thin film crystalline silicon hole transport layer;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of the glass-based ITO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

A. Single spin coating method:

A-1. Preparation of CH ₃ NH ₃ I:

The raw material for preparing CH ₃ NH ₃ I is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen iodide solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass The hydrogen iodide solution with a percentage concentration of 57% = 2.5: 1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.8h at 0°C, and the stirring is completed Finally, use a rotary evaporator to remove the solvent by rotary evaporation at 50°C, and wash the obtained white solid with ether three times. The specific cleaning steps are: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether. Precipitate was precipitated, and this process was repeated twice. Finally, the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ I;

A-2. Preparation of perovskite precursor solution whose composition is CH ₃ NH ₃ PbI ₃ :

Mix the molar ratio of PbI ₂ with a mass percentage of 99.999%: CH ₃ NH ₃ I obtained in the above step A-1 = 1:3, and dissolve it in N,N-dimethylformaldehyde with a mass percentage of 99.9% purity The solution A-2 was obtained in the amide, wherein the concentration of PbI ₂ was 0.8M, and the concentration of CH ₃ NH ₃ I was 1.8M. At room temperature, the above solution A-2 was stirred with a magnetic stirrer for 12h, and the obtained component was CH The perovskite precursor solution of ₃ NH ₃ PbI ₃ , stand-by;

A-3. Spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based ITO transparent oxide conductive layer:

Put the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based ITO transparent oxide conductive layer as a whole on the spin coater, wherein the P-type thin-film crystalline silicon holes On the hole transport layer, take the required amount of the perovskite precursor solution with the composition of CH ₃ NH ₃ PbI ₃ prepared in the above step A-2 and spin-coat it on the P-type thin film crystalline silicon hole transport layer. Accelerate the rotation speed of the coating instrument to 6000rpm and maintain this rotation speed for 15s, and spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate;

A-4. Heat treatment:

Spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of the ITO transparent oxide conductive layer based on the glass as the substrate in the above A-3 step Put the whole into an oven for heat treatment, first heat treatment at 90°C for 0.8h, then heat to 100°C and keep it warm for 25min, so that the perovskite light absorbing layer is spin-coated on the P-type thin film crystalline silicon hole transport layer, The thickness of the perovskite light-absorbing layer is 500nm, and the P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate made of glass-based ITO transparent oxide conductive layer form a thin film Crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

With embodiment 1;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

Prepare the back electrode on the electron transport layer made of dense titanium dioxide prepared in the third step above, and the specific operation method is as follows:

A. Magnetron sputtering method:

Place the whole of the product obtained in the third step above into an ultra-vacuum DC magnetron sputtering device, without using a mask, and coat the electron transport layer made of dense titanium dioxide prepared in the third step. The sputtering target adopts Copper with a mass percentage purity >99.99%, and Ar with a mass percentage purity ^{of 99.999} % are passed into the sputtering chamber as the sputtering gas. The target Under the condition that the base distance is 10cm and the working current is 1A, after sputtering for 75min, the thin-layer back electrode made of copper is prepared on the back electrode on the electron transport layer in the third step;

So far, a transparent conductive substrate composed of a glass-based ITO transparent oxide conductive layer, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide and copper A thin-film crystalline silicon perovskite heterojunction solar cell composed of a thin-layer back electrode.

Example 3

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

With a P-type single crystal silicon wafer coated with a layer of corrosion-resistant metal on the back as the anode, and platinum as the cathode, in a hydrofluoric acid ethanol solution with a volume ratio of hydrofluoric acid: absolute ethanol = 1:1, a size of 7.5 The current of A is used for anodic oxidation, and the P _- type single crystal silicon wafer is corroded by an electrochemical method to form a porous silicon structure on the surface of the single crystal silicon wafer. Annealing at 550°C. During the annealing process, the holes in the small porosity layer on the surface of the single crystal silicon wafer will gradually close to form a quasi-single crystal layer as a template for epitaxial devices. The quasi-single crystal layer is epitaxially formed on the quasi-single crystal layer to form P Type thin-film crystalline silicon film, the formed P-type crystalline silicon film is transferred from a single crystal silicon wafer to a transparent conductive substrate composed of a glass-based FTO transparent oxide conductive layer, thereby being prepared on a transparent conductive substrate P-type thin film crystalline silicon hole transport layer;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based FTO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

A. Single spin coating method:

A-1. Preparation of CH ₃ NH ₃ Cl:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution = 3:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously for 2 hours with a constant temperature magnetic stirrer at 0°C, and use a rotary evaporator after stirring The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with diethyl ether. The specific cleaning steps were: first redissolve all the white solid obtained above in ethanol, and then continuously add dry diethyl ether to precipitate the precipitate. The process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl;

A-2. Preparation of perovskite precursor solution whose composition is CH ₃ NH ₃ PbCl ₃ :

Mix the molar ratio of PbCl ₂ with a mass percentage of 99.999%: CH ₃ NH ₃ Cl obtained in the above step A-1 = 1:3, and dissolve it in N,N-dimethylformaldehyde with a mass percentage of 99.9% purity A solution A-2 was obtained in the amide, wherein the concentration of PbCl ₂ was 1M, and the concentration of CH ₃ NH ₃ Cl was 2.5M. At room temperature, the above solution A-2 was stirred with a magnetic stirrer for 12h, and the obtained component was CH ₃ The perovskite precursor solution of NH ₃ PbCl ₃ , stand-by;

A-3. Spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate composed of the glass-based FTO transparent oxide conductive layer:

Put the P-type thin-film crystalline silicon hole-transport layer on the transparent conductive substrate made of glass-based FTO transparent oxide conductive layer as a whole on the spin coater, wherein the P-type thin-film crystalline silicon holes On the hole transport layer, get the required amount of the perovskite precursor solution with the composition of CH ₃ NH ₃ PbCl ₃ prepared in the above step A-2 and spin-coat it on the P-type thin film crystalline silicon hole transport layer. Accelerate the rotation speed of the coating instrument to 6000rpm and maintain this rotation speed for 30s, and spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate;

A-4. Heat treatment:

Spin-coat the wet film of the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of the glass-based FTO transparent oxide conductive layer made in the above-mentioned A-3 step The whole is put into an oven for heat treatment, first heat treatment at 90 ° C for 1 h, then heat to 100 ° C and keep it warm for 25 min, so that the perovskite light absorption layer is spin-coated on the P-type thin film crystalline silicon hole transport layer, the The thickness of the perovskite light-absorbing layer is 1000nm, and the P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer form a thin-film crystal on a transparent conductive substrate composed of a glass-based FTO transparent oxide conductive layer. Silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

With embodiment 1;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

Prepare the back electrode on the electron transport layer made of dense titanium dioxide prepared in the third step above, and the specific operation method is as follows:

A. Magnetron sputtering method:

Put the whole product prepared in the third step above into the ultra-vacuum DC magnetron sputtering equipment, use a mask plate to coat the electron transport layer made of dense titanium dioxide prepared in the third step, and the sputtering target adopts quality Silver with a percentage purity >99.99% is fed into the sputtering chamber with Ar with a mass percentage purity ^{of 99.999} % as the sputtering gas. Under the condition that the distance is 10cm and the working current is 1A, after sputtering for 90min, the grid line back electrode made of silver is prepared on the back electrode prepared on the electron transport layer in the third step;

So far, a transparent conductive substrate composed of a glass-based FTO transparent oxide conductive layer, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide, and silver A thin film crystalline silicon perovskite heterojunction solar cell composed of a gate line back electrode.

Example 4

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

With embodiment 1;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

B. Spin coating + dipping method

B-1. Preparation of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution = 2:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.5h at 0°C. After the stirring is completed, use a rotary evaporation The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with ether. The specific cleaning steps were as follows: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether to precipitate the precipitate. This process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl; to prepare CH ₃ NH _3. The raw material of 1 is that the mass percent concentration is 33% methylamine ethanol solution and the mass percent concentration is the hydrogen iodide solution of 57%, and the mass percent concentration is 33% methylamine ethanol solution by volume ratio: the mass percent concentration is 57% % hydrogen iodide solution = 2: 1, put the two solutions into a 250mL round bottom flask after mixing, and stir for 1.5h with a constant temperature magnetic stirrer at 0°C, and use rotary evaporation after the stirring is completed The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with ether. The specific cleaning steps were as follows: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether to precipitate the precipitate. This process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ I;

B-2. spin-coat PbI on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on glass constitutes in the first step ₂ thin films:

Dissolve PbI with a mass percent purity of 99.999% in N,N _- dimethylformamide with a mass percent purity of 99.9% so that the concentration of the _PbI solution is 0.5M, and stir at 70°C until a clear and bright The yellow PbI ₂ solution, before spin-coating, the temperature of the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step and the above yellow PbI ₂ solution was heated to 60 ° C, and then the first The P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step is placed on a spin coater as a whole, wherein the P-type thin-film crystalline silicon hole-transport layer is on the top, and the required amount of the yellow PbI obtained above is taken. ₂ The solution is spin-coated on the P-type thin-film crystalline silicon hole transport layer, and the speed of the spin coater is accelerated to 3000rpm and maintained at this speed for 10s, and then dried for 10 minutes, and the glass-based AZO transparent oxide On the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the conductive layer constitutes, obtain spin-coated PbI ₂ thin film, this thin film thickness is 10nm;

B-3. with above-mentioned B- ₂ step gained in the PbI thin film that is spin-coated on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on the glass is formed becomes by CH Thin film formed by mixing ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ :

Dissolve the required amount of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I prepared by the above step B-1 in N,N-dimethylformamide with a mass percent purity of 99.9%, and the obtained CH ₃ NH ₃ Cl solution and CH ₃ NH ₃ I solution, the concentration of which is 1mg/mL, according to the volume ratio of CH ₃ NH ₃ I solution: CH ₃ NH ₃ Cl solution = 1: 0.1 respectively take CH ₃ NH ₃ I solution Mix with CH ₃ NH ₃ Cl solution to obtain a mixed solution of CH ₃ NH ₃ I and CH ₃ NH ₃ Cl, first spin the mixed solution and the P-type thin film crystalline silicon hole transport layer prepared by B-2 step Preheat the coated _PbI2 film to 60°C, and then fully immerse the _PbI2 film in the above mixed solution to react with it, and take it out after standing for 5 minutes. The spin-coated PbI ₂ thin film on the silicon hole transport layer becomes a thin film composed of CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ ;

B-4. Heat treatment:

Spin-coat CH ₃ NH ₃ on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer prepared in step B-3 of the second step above. The whole film composed of PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ is placed in an oven for heat treatment, firstly at 90°C for 1 hour, and then heated to 100°C and heat preservation for 25 minutes, thus spin-coating the perovskite light-absorbing layer on the P-type thin-film crystal silicon hole transport layer. The thickness of the perovskite light-absorbing layer is 10nm, and it is transparent The P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate composed of an oxide conductive layer form a thin-film crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

With embodiment 1;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

B. Thermal evaporation method:

Place the whole product obtained in the third step above into a vacuum coating machine, coat the electron transport layer made of dense titanium dioxide prepared in the third step, and use a resistance wire to heat the vacuum coating machine at a voltage of 150V. Under the conditions of a vacuum of 1×10 ^-4 Pa and a temperature of room temperature to 150°C, use the method of evaporative aluminum deposition for 2 seconds, that is, it is prepared on the electron transport layer composed of dense titanium dioxide prepared in the third step A thin layer back electrode made of aluminum;

So far, a transparent conductive substrate composed of a glass-based AZO transparent oxide conductive layer, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide and aluminum A thin-film crystalline silicon perovskite heterojunction solar cell composed of a thin-layer back electrode.

Example 5

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

With embodiment 1;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

B. Spin coating + dipping method

B-1. Preparation of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution = 2.5:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously with a constant temperature magnetic stirrer for 1.8h at 0°C. After the stirring is completed, use a rotary evaporation The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with ether. The specific cleaning steps were as follows: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether to precipitate the precipitate. This process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl; to prepare CH ₃ NH _3. The raw material of 1 is that the mass percent concentration is 33% methylamine ethanol solution and the mass percent concentration is the hydrogen iodide solution of 57%, and the mass percent concentration is 33% methylamine ethanol solution by volume ratio: the mass percent concentration is 57% % hydrogen iodide solution = 2.5:1, put the two solutions into a 250mL round-bottomed flask after mixing them, and stir them with a constant temperature magnetic stirrer for 1.8h at 0°C. After the stirring is completed, use a rotary evaporation The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with ether. The specific cleaning steps were as follows: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry ether to precipitate the precipitate. This process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ I;

B-2. spin-coat PbI on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on glass constitutes in the first step ₂ thin films:

Dissolve PbI with a mass percent purity of 99.999% in N,N _- dimethylformamide with a mass percent purity of 99.9% so that the concentration of the _PbI solution is 0.8M, and stir at 70°C until a clear and bright The yellow PbI ₂ solution, before spin-coating, the temperature of the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step and the above yellow PbI ₂ solution was heated to 62 ° C, and then the first The P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step is placed on a spin coater as a whole, wherein the P-type thin-film crystalline silicon hole-transport layer is on the top, and the required amount of the yellow PbI obtained above is taken. ₂ The solution is spin-coated on the P-type thin-film crystalline silicon hole transport layer, and the rotation speed of the spin-coater is accelerated to 3000rpm and maintained at this speed for 15 seconds, and then dried for 10 minutes, and the P-type thin-film crystal silicon on the transparent conductive substrate Obtain spin-coated PbI _on the silicon hole transport layer Thin film, this thin film thickness is 400nm;

B-3. with above-mentioned B- ₂ step gained in the PbI thin film that is spin-coated on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on the glass is formed becomes by CH Thin film formed by mixing ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ :

Dissolve the required amount of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I prepared by the above step B-1 in N,N-dimethylformamide with a mass percent purity of 99.9%, and the obtained CH ₃ NH ₃ Cl solution and CH ₃ NH ₃ I solution, both of which have a concentration of 5 mg/mL, according to the volume ratio of CH ₃ NH ₃ I solution: CH ₃ NH ₃ Cl solution = 1: 5, respectively take CH ₃ NH ₃ I solution Mix with CH ₃ NH ₃ Cl solution to obtain a mixed solution of CH ₃ NH ₃ I and CH ₃ NH ₃ Cl, first spin the mixed solution and the P-type thin film crystalline silicon hole transport layer prepared by B-2 step Preheat the coated _PbI2 film to 60°C, and then fully immerse the _PbI2 film in the above mixed solution to react with it, and take it out after standing for 16 minutes. The spin-coated PbI ₂ thin film on the silicon hole transport layer becomes a thin film composed of CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ ;

B-4. Heat treatment:

Spin-coat CH ₃ NH ₃ on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer prepared in step B-3 of the second step above. The whole film composed of PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ is placed in an oven for heat treatment, firstly at 90°C for 1 hour, and then heated to 100°C and heat preservation for 25 minutes, thus spin-coating the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer. The thickness of the perovskite light-absorbing layer is 500nm, and the AZO transparent The P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate composed of an oxide conductive layer form a thin-film crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

With embodiment 1;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

B. Thermal evaporation method:

Put the whole product obtained in the third step above into a vacuum coating machine, coat the electron transport layer made of dense titanium dioxide prepared in the third step, and use a resistance wire to heat the vacuum coating machine at a voltage of 165V. Under the conditions of a vacuum of 4.0×10 ^-4 Pa and a temperature of room temperature to 150°C, use the method of evaporative copper plating for 31 seconds, that is, it is prepared on the electron transport layer composed of dense titanium dioxide prepared in the third step. Thin layer back electrode made of copper;

So far, a transparent conductive substrate composed of a glass-based AZO transparent oxide conductive layer, a P-type thin-film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide, and copper A thin-film crystalline silicon perovskite heterojunction solar cell composed of a back electrode.

Example 6

The first step is to prepare a P-type thin film crystalline silicon hole transport layer on a transparent conductive substrate:

With embodiment 1;

The second step is to spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer:

Spin-coat the perovskite light-absorbing layer on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer formed in the first step above, and adopt the following steps:

B. Spin coating + dipping method

B-1. Preparation of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I:

The raw material for preparing CH ₃ NH ₃ Cl is that the mass percentage concentration is 33% methylamine ethanol solution and the mass percentage concentration is 57% hydrogen chloride solution, and the mass percentage concentration is 33% methylamine ethanol solution by volume ratio: mass percentage concentration 57% hydrogen chloride solution = 3:1, put the two solutions into a 250mL round-bottomed flask after mixing, and stir continuously for 2 hours with a constant temperature magnetic stirrer at 0°C, and use a rotary evaporator after stirring The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with diethyl ether. The specific cleaning steps were: first redissolve all the white solid obtained above in ethanol, and then continuously add dry diethyl ether to precipitate the precipitate. The process was repeated twice, and finally the obtained white solid was put into a vacuum drying oven, and dried at 60°C and a vacuum degree of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ Cl; to prepare CH ₃ NH ₃ The raw material of I is that the mass percent concentration is the methylamine ethanol solution of 33% and the mass percent concentration is the hydrogen iodide solution of 57%, is the mass percent concentration by volume ratio and is the methylamine ethanol solution of 33%: the mass percent concentration is 57% Hydrogen iodide solution=3:1, put these two solutions into a 250mL round bottom flask after mixing, and stir continuously for 2h with a constant temperature magnetic stirrer at 0°C, and use a rotary evaporator after stirring The solvent was removed by rotary evaporation at 50°C, and the obtained white solid was washed three times with diethyl ether. The specific cleaning steps were: first re-dissolve all the white solid obtained above in ethanol, and then continuously add dry diethyl ether to precipitate the precipitate. This process Repeat twice, and finally put the obtained white solid into a vacuum drying oven, and dry it at 60°C and a vacuum of 5×10 ⁴ Pa for 24 hours to obtain CH ₃ NH ₃ I;

B-2. spin-coat PbI on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on glass constitutes in the first step ₂ thin films:

Dissolve PbI with a mass percent purity of 99.999% in N,N _- dimethylformamide with a mass percent purity of 99.9%, so that the _PbI solution has a concentration of 1M, and stir at 70°C until a clear and bright Yellow _PbI2 solution, before spin-coating, heat the temperature of the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate prepared in the first step and the above yellow _PbI2 solution to 65 ° C, and then the first step The P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate is placed on a spin coater as a whole, wherein the P-type thin-film crystalline silicon hole-transport layer is _on top, and the yellow PbI obtained above is taken in a required amount. The solution is spin-coated on the P-type thin film crystalline silicon hole transport layer, and the rotation speed of the spin coater is accelerated to 3000rpm and maintained at this speed for 20 seconds, and then dried for 10 minutes, and the P-type thin film crystalline silicon on the transparent conductive substrate Obtain spin-coated PbI _on the hole transport layer Thin film, this thin film thickness is 800nm;

B-3. with above-mentioned B- ₂ step gained in the PbI thin film that is spin-coated on the P-type thin film crystalline silicon hole transport layer on the transparent conductive substrate that the AZO transparent oxide conductive layer that is based on the glass is formed becomes by CH Thin film formed by mixing ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ :

Dissolve the required amount of CH ₃ NH ₃ Cl and CH ₃ NH ₃ I prepared by the above step B-1 in N,N-dimethylformamide with a mass percent purity of 99.9%, and the obtained CH ₃ NH ₃ Cl solution and CH ₃ NH ₃ I solution, both of which have a concentration of 10 mg/mL, according to the volume ratio of CH ₃ NH ₃ I solution: CH ₃ NH ₃ Cl solution = 1: 10 respectively take CH ₃ NH ₃ I solution Mix with CH ₃ NH ₃ Cl solution to obtain a mixed solution of CH ₃ NH ₃ I and CH ₃ NH ₃ Cl, first spin the mixed solution and the P-type thin film crystalline silicon hole transport layer prepared by B-2 step Preheat the coated _PbI2 film to 60°C, then fully immerse the _PbI2 film in the above mixed solution to react with it, and take it out after standing for 30 minutes. The spin-coated PbI ₂ thin film on the silicon hole transport layer becomes a thin film composed of CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ ;

B-4. Heat treatment:

Spin-coat CH ₃ NH ₃ on the P-type thin-film crystalline silicon hole transport layer on the transparent conductive substrate made of glass-based AZO transparent oxide conductive layer prepared in step B-3 of the second step above. The whole film composed of PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₂ Cl and CH ₃ NH ₃ PbICl ₂ is placed in an oven for heat treatment, firstly at 90°C for 1 hour, and then heated to 100°C and keep it warm for 25 minutes, thus spin-coat the perovskite light absorbing layer on the P-type thin film crystalline silicon hole transport layer, the thickness of the perovskite light absorbing layer is 1000nm, and it is transparent The P-type thin-film crystalline silicon hole transport layer and the perovskite light-absorbing layer on the transparent conductive substrate composed of an oxide conductive layer form a thin-film crystalline silicon perovskite heterojunction;

The third step is to fabricate an electron transport layer made of dense titanium dioxide on the perovskite light absorbing layer:

With embodiment 1;

The fourth step is to prepare the back electrode on the electron transport layer composed of dense titanium dioxide:

B. Thermal evaporation method:

Place the whole product obtained in the third step above into a vacuum coating machine, coat the electron transport layer made of dense titanium dioxide prepared in the third step, and use a resistance wire to heat the vacuum coating machine at a voltage of 175V. Under the conditions of a vacuum of 8.0×10 ^-4 Pa and a temperature of room temperature to 150°C, by evaporating silver plating for 60 seconds, it is prepared on the electron transport layer composed of dense titanium dioxide prepared in the third step A thin-layer back electrode composed of silver;

So far, a transparent conductive substrate composed of AZO transparent oxide conductive layer based on glass, a P-type thin film crystalline silicon hole transport layer, a perovskite light absorption layer, an electron transport layer composed of dense titanium dioxide and silver A thin-film crystalline silicon perovskite heterojunction solar cell composed of a back electrode.

The raw materials, equipment and process operation methods involved in the above embodiments are all known.

Claims (6)

1. film crystal silicon perovskite heterojunction solar cell, it is characterized in that: be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode, wherein, perovskite light absorbing zone and P type film crystal silicon hole transmission layer possess the energy level matched; Its composition sequential system is: P type film crystal silicon hole transport is placed on electrically conducting transparent substrate, perovskite light absorbing zone is placed in above P type film crystal silicon hole transmission layer, perovskite light absorbing zone and P type film crystal silicon hole transmission layer form film crystal silicon perovskite heterojunction, the electric transmission be made up of compact titanium dioxide is placed on above perovskite light absorbing zone, back electrode is placed in by above the electron transfer layer that compact titanium dioxide is formed, above five functional layers superpose successively, form this film crystal silicon perovskite heterojunction solar cell.

2. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described perovskite light absorbing zone perovskite material used is CH ₃nH ₃pbX ₃, wherein X=Cl is or/and I, and thickness is 0.05 ~ 30um.

3. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.

4. film crystal silicon perovskite heterojunction solar cell according to claim 1, is characterized in that: described back electrode is the thin layer that forms of aluminium, silver or copper or grid line.

5. the preparation method of film crystal silicon perovskite heterojunction solar cell described in claim 1, its step is as follows:

The first step, is prepared in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:

The p type single crystal silicon sheet of one deck corrosion resistant metal is coated with as anode using the back side, using platinum as negative electrode, at volume ratio hydrofluoric acid: absolute ethyl alcohol=1: in the hydrofluoric acid ethanolic solution of 1, passing to size is that the electric current of 1A ~ 7.5A carries out anodic oxidation, by electrochemical process corrosion p type single crystal silicon sheet, monocrystalline silicon sheet surface formed Porous Silicon structures, then by the monocrystalline silicon piece of this formation Porous Silicon structures at H ₂lower 200 DEG C to the 550 DEG C annealing of atmosphere, in annealing process, the hole of this monocrystalline silicon piece top layer small porosity layer can close gradually and form the template of accurate single crystalline layer as epitaxial device, low-pressure chemical vapour deposition technique extension on this accurate single crystalline layer is utilized to become P type film polycrystal silicon film, formed P type polycrystal silicon film is transferred in electrically conducting transparent substrate from monocrystalline silicon piece, is prepared at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer thus;

Second step, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer:

At the spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the above-mentioned first step is obtained, adopt in following two kinds of methods any one:

A. single spin-coating method:

A-1.CH ₃nH ₃the preparation of X, wherein X=Cl or I (lower same):

Preparation CH ₃nH ₃the raw material of X to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen halide solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen halide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree ⁴dry 24h under the condition of Pa, obtained CH ₃nH ₃x, described hydrogen halide solution is hydrogen chloride solution or hydrogen iodide solution,

A-2. composition is CH ₃nH ₃pbX ₃the preparation of perovskite precursor aqueous solution:

To be mass percent by mol ratio be 99.999% PbX ₂: the CH that above-mentioned A-1 step is obtained ₃nH ₃x=1:3 mixes, and to be dissolved in mass percent purity be obtain solution A-2 in the DMF of 99.9%, wherein PbX ₂concentration be 0.5 ~ 1M, CH ₃nH ₃the concentration of X is 1 ~ 2.5M, and at room temperature, above-mentioned solution A-2 is used magnetic stirrer 12h, obtained composition is CH ₃nH ₃pbX ₃perovskite precursor aqueous solution, stand-by, above-mentioned PbX ₂in X=Cl or I, and and CH ₃nH ₃x in X is consistent;

A-3. the wet film of spin coating perovskite light absorbing zone on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer:

Be put on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, and the composition obtained by above-mentioned A-2 step getting aequum is CH ₃nH ₃pbX ₃perovskite precursor aqueous solution be spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 6000rpm and keeps such rotating speed spin coating 10 ~ 30s, the wet film of perovskite light absorbing zone in spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer;

A-4. heat treatment:

By obtained for above-mentioned A-3 step on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer in spin coating the entirety of the wet film of perovskite light absorbing zone put in baking oven and heat-treat, first heat treatment 0.5 ~ 1h at 90 DEG C, be heated to 100 DEG C again and be incubated 25min, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;

B. spin coating+infusion process

B-1.CH ₃nH ₃cl and CH ₃nH ₃the preparation of I:

Preparation CH ₃nH ₃the raw material of Cl to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be the hydrogen chloride solution of 57%, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen chloride solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree ⁴dry 24h under the condition of Pa, obtained CH ₃nH ₃cl, preparation CH ₃nH ₃the raw material of I to be mass percent concentration be 33% methylethylolamine solution and mass percent concentration be 57% hydrogen iodide solution, be methylethylolamine solution that mass percent concentration is 33% by volume: mass percent concentration is hydrogen iodide solution=2 ~ 3 of 57%: 1, to put in the round-bottomed flask of 250mL after these two kinds of solution mixing, at 0 DEG C, stirring 1.5 ~ 2h is not stopped by constant temperature blender with magnetic force, Rotary Evaporators is utilized to remove solvent by rotary evaporation after stirring at 50 DEG C, the white solid ether of acquisition is cleaned three times, concrete cleaning step is: first again all dissolved in ethanol by the white solid of aforementioned acquisition, constantly add dry diethyl ether again and separate out sediment, this process repeats twice, finally the white solid obtained is put in vacuum drying chamber, be 5 × 10 60 DEG C and vacuum degree ⁴dry 24h under the condition of Pa, obtained CH ₃nH ₃i,

B-2. at the spin coating PbI on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer that the first step is obtained ₂film:

Be 99.999%PbI by mass percent purity ₂being dissolved in mass percent purity is in the DMF of 99.9%, makes this PbI ₂the concentration of solution is 0.5 ~ 1M, and stirs at 70 DEG C so that form the bright yellow PbI of clarification ₂solution, before spin coating, by obtained for the first step at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and above-mentioned yellow PbI ₂heating temperatures to 60 ~ 65 DEG C of solution, be then placed on spin coating instrument by obtained for the first step in electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer entirety, wherein P type film crystal silicon hole transmission layer is upper, gets the obtained above yellow PbI of aequum ₂solution is spun on P type film crystal silicon hole transmission layer, spin coating instrument rotating speed is accelerated to 3000rpm and keeps such rotating speed spin coating 10 ~ 20s, then drying process 10 minutes, and electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtains spin coating PbI ₂film, this film thickness is 10 ~ 800nm;

B-3. above-mentioned B-2 is walked the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer ₂film becomes by CH ₃nH ₃pbI ₃, CH ₃nH ₃pbCl ₃, CH ₃nH ₃pbI ₂cl and CH ₃nH ₃pbICl ₂the film that mixing is formed:

By the CH obtained through above-mentioned B-1 step of aequum ₃nH ₃cl and CH ₃nH ₃it is in the DMF of 99.9% that I is dissolved in mass percent purity respectively, the CH obtained respectively ₃nH ₃cl solution and CH ₃nH ₃i solution, its concentration is 1 ~ 10mg/mL, is CH according to volume ratio ₃nH ₃i Rong Ye ︰ CH ₃nH ₃cl solution=1 ︰ 0.1 ~ 10 gets CH respectively ₃nH ₃i solution and CH ₃nH ₃cl solution is mixed to get CH ₃nH ₃i and CH ₃nH ₃the mixed solution of Cl, first by this mixed solution and the PbI being walked obtained spin coating on P type film crystal silicon hole transmission layer by B-2 ₂film is preheated to 60 DEG C, then by this PbI ₂film immerses fully in above-mentioned mixed solution and reacts with it, takes out after leaving standstill 5 ~ 30min, and above-mentioned B-2 walks the PbI of gained spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer ₂film becomes by CH ₃nH ₃pbI ₃, CH ₃nH ₃pbCl ₃, CH ₃nH ₃pbI ₂cl and CH ₃nH ₃pbICl ₂the film that mixing is formed;

B-4. heat treatment:

Spin coating on electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer obtained by being walked by the B-3 of above-mentioned second step has CH ₃nH ₃pbI _3-ycl _ythe entirety of film is put in baking oven and is heat-treated, first at 90 DEG C, be incubated 1 hour, be heated to 100 DEG C again and be incubated 25 minutes, spin coating perovskite light absorbing zone on P type film crystal silicon hole transmission layer thus, the thickness of this perovskite light absorbing zone is 0.05 ~ 30um, and forms film crystal silicon perovskite heterojunction at electrically conducting transparent suprabasil P type film crystal silicon hole transmission layer and perovskite light absorbing zone;

3rd step, perovskite light absorbing zone makes the electron transfer layer be made up of compact titanium dioxide:

The entirety of goods obtained by above-mentioned second step is placed in magnetron sputtering apparatus, on perovskite light absorbing zone, prepared the electron transfer layer be made up of compact titanium dioxide by magnetron sputtering method, concrete operation method is: target is the TiO of purity Coriolis mass percentage 99.99% ₂target, target diameter is 60mm, and thickness is 5mm, before sputtering, carries out 5min cleaning, then vacuumize with high-purity argon gas to magnetron sputtering apparatus cavity, and base vacuum is 4.0 × 10 ^-3pa, pass into argon gas and oxygen successively subsequently, the volume ratio being controlled argon gas and oxygen by adjust flux is 9: 1, total pressure remains 2.0Pa, sputtering power is 80W, sputtering time is 4h, again through the annealing in process of 70 DEG C to 150 DEG C after growth terminates, and the obtained electron transfer layer be made up of compact titanium dioxide on perovskite light absorbing zone thus;

4th step, preparing back electrode by the electron transfer layer that compact titanium dioxide is formed:

What be prepared in above-mentioned 3rd step prepares back electrode by the electron transfer layer that compact titanium dioxide is formed, concrete operation method be adopt in the following two kinds method any one:

A. magnetically controlled sputter method:

The entirety of goods obtained by above-mentioned 3rd step is placed in ultravacuum DC magnetron sputtering device, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, sputtering target adopts the aluminium of mass percent purity >99.99%, copper or silver, using mass percent purity be 99.999% Ar pass in sputtering chamber as sputter gas, be 4.0 × 10 in vacuum degree ^-4pa, argon flow amount are 20cm ³/ S, target-substrate distance are 10cm and operating current is under the condition of 1A, after sputtering 60 ~ 90min, is namely prepared into prepared by electron transfer layer in the 3rd step and back electrode is prepared into the thin layer back electrode or grid line back electrode that aluminium, copper or silver forms;

B. hot evaporation coating method:

The entirety of goods obtained by above-mentioned 3rd step is placed in vacuum coating equipment, plated film is carried out to the electron transfer layer be made up of compact titanium dioxide that the 3rd step is prepared into, under the voltage of 150 ~ 175V, use Resistant heating vacuum coating equipment, be 1 × 10 in vacuum degree ^-4pa ~ 8.0 × 10 ^-4pa and temperature are under room temperature to 150 DEG C condition, by the method for evaporation plating aluminium, copper or silver, evaporation 2 ~ 60 seconds, namely the 3rd step be prepared into by the thin layer back electrode electron transfer layer that compact titanium dioxide is formed being prepared into aluminium, copper or silver and forming;

So far, the final obtained film crystal silicon perovskite heterojunction solar cell be made up of electrically conducting transparent substrate, P type film crystal silicon hole transmission layer, perovskite light absorbing zone, the electron transfer layer be made up of compact titanium dioxide and back electrode.

6. the preparation method of film crystal silicon perovskite heterojunction solar cell according to claim 5, is characterized in that: described electrically conducting transparent substrate is take glass as AZO, ITO or FTO transparent oxide conductive layer of substrate.