CN104269452A - Perovskite solar battery made of silicon-based thin-film materials and manufacturing method thereof - Google Patents

Abstract

A silicon-based thin film material perovskite solar cell and a preparation method thereof, wherein the silicon-based thin film material perovskite solar cell structure includes: a conductive glass; an n-type electron transport layer made on the conductive glass; A perovskite photosensitive layer, which is fabricated on the n-type electron transport layer; a p-type hole transport layer, which is fabricated on the perovskite photosensitive layer; a metal counter electrode, which is fabricated on the p-type hole transport layer . The invention has the advantages of using low-cost and easy-to-synthesize p-type silicon-based film material as the hole transport layer to replace the expensive spiro-OMeTAD organic material, and improving the long-wave response and battery efficiency of silicon solar cells.

Description

Perovskite solar cell of silicon-based thin film material and preparation method thereof

technical field

The invention relates to the technical field of solar cells, in particular to a silicon-based thin-film material perovskite solar cell and a preparation method thereof.

Background technique

The current thin-film batteries are mainly represented by cadmium telluride (CdTe) and copper indium gallium selenide solar (CIGS) batteries. The conversion efficiency of small-area batteries reported in the world has reached 19.6% and 19.8% respectively. However, the above-mentioned thin-film battery preparation materials involve expensive rare elements tellurium, indium, gallium, and cadmium elements that have great pollution to the human body and the environment, so the development of these thin-film batteries at the level of total installed capacity of terawatts in the future will be greatly restricted. .

Recently, new perovskite-structured thin-film solar cells, which are an "upgraded version" of dye-sensitized cells, have attracted great interest in the photovoltaic cell community. In just four years, the efficiency of solar cells based on perovskite-structured organic-inorganic hybrid methylamine lead-iodide materials has improved by leaps and bounds. The battery preparation materials are all elements with abundant reserves in the earth's crust, the preparation method is simple, and the whole process is low temperature, so it has very broad industrialization prospects. This perovskite structure lead halide photosensitive material has typical semiconductor material characteristics and a suitable band gap. The absorption efficiency of sunlight with a wavelength of less than 800nm can reach more than 95%, and the carrier has a high mobility. and diffusion length, especially suitable for photovoltaic applications.

However, the existing high-efficiency perovskite cells with an efficiency exceeding 15% all use the organic compound spiro-OMeTAD as the p-type hole transport layer (HTM) without exception, and its price is ten times that of gold. More than twice (4000RMB/g), which greatly limits the industrial application process of perovskite batteries, the search for a more suitable and easy-to-synthesize p-type hole transport layer has become an important driving force to promote the development of devices. The material used as the p-type hole transport layer must form a typical hole-selective, electron-repulsive heterojunction contact at the interface with the perovskite layer, that is, it is required to have a suitable band gap width, electron affinity and band gap. edge position, and has good photoconductivity and mobility. In order to meet the above requirements, the p-type silicon-based thin film material can be doped with appropriate nitrogen, carbon or oxygen elements, thereby significantly changing the energy band structure of the p-type silicon-based thin film material. The invention proposes to use the p-type silicon-based thin film material with adjustable band gap, variable doping type, and certain excellent characteristics such as absorption of sunlight to realize the replacement of spiro-OMeTAD organic materials, thereby greatly promoting the development of the amorphous silicon industry and An organic combination of perovskite cells.

Contents of the invention

The purpose of the present invention is to provide a perovskite solar cell structure of a silicon-based thin film material and a preparation method thereof, which has a low cost and easy-to-synthesize p-type silicon-based thin film material as a hole transport layer to replace the expensive spiro - OMeTAD organic material, the advantage of improving the long-wave response and cell efficiency of silicon solar cells.

In order to achieve the above object, the present invention proposes a perovskite solar cell structure of a silicon-based thin film material, including:

a conductive glass;

An n-type electron transport layer made on conductive glass;

A perovskite photosensitive layer fabricated on the n-type electron transport layer;

A p-type hole transport layer, which is fabricated on the perovskite photosensitive layer;

A metal counter electrode is fabricated on the p-type hole transport layer.

The present invention also provides a perovskite solar cell structure of a silicon-based thin film material, comprising:

a conductive glass;

A p-type hole transport layer made on conductive glass;

A perovskite photosensitive layer fabricated on the p-type electron transport layer;

An n-type electron transport layer fabricated on the perovskite photosensitive layer;

A metal counter electrode is fabricated on the n-type hole transport layer.

The present invention provides a kind of preparation method of the perovskite solar cell of silicon base film material again, comprises the steps:

Step 1: Take a conductive glass;

Step 2: Wash and dry;

Step 3: sequentially depositing an n-type electron transport layer, a perovskite photosensitive layer, a p-type hole transport layer and a metal counter electrode on the conductive glass to complete the preparation.

The present invention provides a kind of preparation method of the perovskite solar cell of silicon base film material again, comprises the steps:

Step 1: Take a conductive glass;

Step 2: Wash and dry;

Step 3: sequentially depositing a p-type hole transport layer, a perovskite photosensitive layer, an n-type electron transport layer and a metal counter electrode on the conductive glass to complete the preparation.

The present invention has the following beneficial effects:

1. Utilizing the present invention, it can ensure that the carriers excited by long-wavelength light are separated at the nearest silicon-based film/perovskite heterojunction, and an additional heterojunction potential is added to the device, which significantly improves the short-circuit current and open circuit voltage.

2. Compared with other p-type hole-selective layer materials, amorphous silicon has an adjustable band gap, especially the characteristics of low cost and easy manufacture, which can greatly reduce the production cost of perovskite solar cells and accelerate the promotion of perovskite solar cells .

3. Utilizing the present invention, the vacuum deposition process of the whole process of the battery can be realized, the technology of preparing the p-type hole transport layer by the solution method is avoided, and it is completely compatible with the existing amorphous silicon battery production technology, thus facilitating large-scale production.

Description of drawings

In order to further illustrate the technical content of the present invention, the following detailed description is as follows in conjunction with the embodiments and accompanying drawings, wherein:

Figure 1 is a schematic diagram of the energy band structure of a perovskite/silicon-based film stack;

Fig. 2 is the structural representation of the first embodiment of the present invention;

Fig. 3 is the structural representation of the second embodiment of the present invention;

Fig. 4 is the preparation flowchart of the first embodiment of the present invention;

Fig. 5 is a preparation flow chart of the second embodiment of the present invention.

Detailed ways

Please refer to shown in Fig. 1, the working principle of the perovskite solar cell that the present invention provides silicon-based thin film material is briefly described as follows:

For perovskite solar cells with NIP structure, the bottom of the conduction band of the perovskite material is -3.93eV (relative to the vacuum energy level), the top of the valence band is -5.43eV, and the p-type amorphous film passes carbon, nitrogen, oxygen Doping with other alloys, the conduction band edge and valence band edge can be adjusted to be higher than the corresponding band edge of the perovskite I layer, and the formed discrete energy band structure is shown in Figure 1(a). As shown in Figure 1(b), the Fermi level reaches unity at this time. The heterostructure formed after connection is suitable for transporting holes from the perovskite I layer to the P-type layer, but the electrons are blocked by the conduction band, that is, it has obvious hole carrier collection ability. In the PIN structure, the energy band of the perovskite I layer tilts under the penetration of the heterojunction self-built field on both sides, which will accelerate the flow of photogenerated electrons to the N region, and the flow of photogenerated holes to the P region, resulting in a significant field-assisted collection effect of photogenerated carriers.

Please refer to Fig. 2, the present invention provides a perovskite solar cell structure of a silicon-based thin film material, including:

A conductive glass 1, the material of the conductive glass 1 can be FTO glass, ITO glass, AZO glass or IZO glass, and the sheet resistance of the glass is 5-30Ω/□;

An n-type electron transport layer 2, which is made on the conductive glass 1, the n-type electron transport layer 2 is an n-type zinc oxide film, an n-type titanium oxide film or an n-type silicon-based film, and the film thickness is 5nm-50nm;

A perovskite photosensitive layer 3, which is fabricated on the n-type electron transport layer 2, the perovskite photosensitive layer 3 is CH ₃ NH ₃ PbI ₃ or CH ₃ NH ₃ PbI _3-x Cl _x , with a thickness of 50nm- 2000nm;

A p-type hole transport layer 4, which is made on the perovskite photosensitive layer 3, the p-type hole transport layer 4 is a p-type silicon-based film, including a silicon-based alloy film, such as microcrystalline silicon-carbon alloy, microcrystalline One or a combination of crystalline silicon-nitrogen alloys, microcrystalline silicon-oxygen alloys, amorphous silicon-carbon alloys, amorphous silicon-nitrogen alloys or amorphous silicon-oxygen alloys. The deposition method is plasma enhanced chemical vapor deposition, the thickness is 10nm-100nm, the atomic fraction of carbon is 10%-30%, the atomic fraction of nitrogen is 10%-30%, and the atomic fraction of oxygen is 10%-30 %;

A metal counter electrode 5 is fabricated on the p-type hole transport layer 4, and the metal counter electrode 5 is one of gold, silver, copper or aluminum or a combination thereof.

Please refer to Fig. 3, the present invention additionally provides a perovskite solar cell structure of a silicon-based thin film material, including:

A conductive glass 1, the material of the conductive glass 1 can be FTO glass, ITO glass, AZO glass or IZO glass, and the sheet resistance of the glass is 5-30Ω/□;

A p-type hole transport layer 4, which is made on the conductive glass 1, the p-type hole transport layer 4 is a p-type silicon-based film, including a silicon-based alloy film, such as microcrystalline silicon-carbon alloy, microcrystalline silicon nitrogen alloy, microcrystalline silicon-oxygen alloy, amorphous silicon-carbon alloy, amorphous silicon-nitrogen alloy, or amorphous silicon-oxygen alloy, or a combination thereof. The deposition method is plasma enhanced chemical vapor deposition, the thickness is 10nm-100nm, the atomic fraction of carbon is 10%-30%, the atomic fraction of nitrogen is 10%-30%, and the atomic fraction of oxygen is 10%-30 %;

A perovskite photosensitive layer 3, which is fabricated on the p-type electron transport layer 4, the perovskite photosensitive layer 3 is CH ₃ NH ₃ PbI ₃ or CH ₃ NH ₃ PbI _3-x Cl _x , with a thickness of 50nm- 2000nm;

An n-type electron transport layer 2, which is made on the perovskite photosensitive layer 3, the n-type electron transport layer 2 is an n-type zinc oxide film, an n-type titanium oxide film or an n-type silicon-based film, and the film thickness is 5nm -50nm;

A metal counter electrode 5, which is fabricated on the n-type electron transport layer 2, and the metal counter electrode 5 is one of gold, silver, copper or aluminum or a combination thereof.

Please refer to FIG. 4, and refer to FIG. 2 in conjunction with a method for preparing a perovskite solar cell made of a silicon-based thin film material, including the following steps:

Step 1: Take a conductive glass 1 . The material of the conductive glass 1 can be FTO glass, ITO glass, AZO glass or IZO glass, and the sheet resistance of the glass is 5-30Ω/□, which plays the role of support and conduction of the subsequent coating layer.

Step 2: Rinse and blow dry. After cleaning with an ultrasonic organic solvent, blow dry with nitrogen. Local corrosion or masking is carried out on the conductive layer to avoid short-circuiting of the upper and lower electrodes during subsequent coating.

Step 3: Depositing an n-type electron transport layer 2, a perovskite photosensitive layer 3, a p-type hole transport layer 4 and a metal counter electrode 5 sequentially on the conductive glass 1 to complete the preparation. The n-type electron transport layer 2 is a thin film of zinc oxide or titanium oxide, with a film thickness of 5nm-50nm, deposited by magnetron sputtering, or an n-type silicon-based thin film, including hydrogen diluted or undiluted n Type microcrystalline silicon or n-type amorphous silicon, the film thickness is 5-50nm, and the deposition method is chemical vapor deposition. Before depositing the n-type electron transport layer 2, the glass conductive layer can be etched with an acid solution to define the pattern of the active region, and the surface can be cleaned with oxygen or nitrogen plasma. The perovskite photosensitive layer 3 is CH ₃ NH ₃ PbI ₃ or CH ₃ NH ₃ PbI _3-x Cl _x , the deposition method is organic-inorganic dual-source co-evaporation method or spin coating method, the thickness is 50nm-2000nm, and the deposition method is After the annealing step, a stable perovskite photosensitive layer is formed. The annealing method includes hot plate annealing, oven annealing, furnace tube annealing or sintering furnace annealing. The annealing temperature is 70-200°C and the time is 10min-100min. The p-type hole transport layer 4 is a p-type silicon-based alloy thin film, including microcrystalline silicon-carbon alloy, microcrystalline silicon-nitrogen alloy, microcrystalline silicon-oxygen alloy, amorphous silicon-carbon alloy, amorphous silicon-nitrogen alloy or non-microcrystalline One or a combination of crystalline silicon-oxygen alloys. The deposition method is chemical vapor deposition, including plasma chemical vapor deposition, hot wire chemical vapor deposition, light-induced chemical vapor deposition, the thickness is 10nm-100nm, the atomic fraction of carbon is 10%-30%, and the atomic fraction of nitrogen is in 10%-30%, the atomic fraction of oxygen is 10%-30%. The metal counter electrode 5 is one or a combination of gold, silver, copper or aluminum, and the deposition method includes electron beam evaporation or resistance thermal evaporation.

Please refer to Fig. 5, and refer to Fig. 3 in conjunction with Fig. 3, another method for preparing a perovskite solar cell made of a silicon-based thin film material, including the following steps:

Step 1: Take a conductive glass 1 . The material of the conductive glass 1 can be FTO glass, ITO glass, AZO glass or IZO glass, and the sheet resistance of the glass is 5-30Ω/□, which plays the role of support and conduction of the subsequent coating layer.

Step 2: Rinse and blow dry. After cleaning with an ultrasonic organic solvent, blow dry with nitrogen. Local corrosion or masking is carried out on the conductive layer to avoid short-circuiting of the upper and lower electrodes during subsequent coating.

Step 3: sequentially depositing a p-type hole transport layer 4, a perovskite photosensitive layer 3, an n-type electron transport layer 2 and a metal counter electrode 5 on the conductive glass 1 to complete the preparation. The p-type hole transport layer 4 is a p-type silicon-based alloy thin film, including microcrystalline silicon-carbon alloy, microcrystalline silicon-nitrogen alloy, microcrystalline silicon-oxygen alloy, amorphous silicon-carbon alloy, amorphous silicon-nitrogen alloy or non-microcrystalline One or a combination of crystalline silicon-oxygen alloys. The deposition method is chemical vapor deposition, including plasma chemical vapor deposition, hot wire chemical vapor deposition, light-induced chemical vapor deposition, the thickness is 10nm-100nm, the atomic fraction of carbon is 10%-30%, and the atomic fraction of nitrogen is in 10%-30%, the atomic fraction of oxygen is 10%-30%. The perovskite photosensitive layer 3 is CH ₃ NH ₃ PbI ₃ or CH ₃ NH ₃ PbI _3-x Cl _x , the deposition method is organic-inorganic dual-source co-evaporation method or spin coating method, the thickness is 50nm-2000nm, and the deposition method is After the annealing step, a stable perovskite photosensitive layer is formed. The annealing method includes hot plate annealing, oven annealing, furnace tube annealing or sintering furnace annealing. The annealing temperature is 70-200°C and the time is 10min-100min. The n-type electron transport layer 2 is a thin film of zinc oxide or titanium oxide, with a film thickness of 5nm-50nm, deposited by magnetron sputtering, or an n-type silicon-based thin film, including hydrogen diluted or undiluted n Type microcrystalline silicon or n-type amorphous silicon, the film thickness is 5-50nm, and the deposition method is chemical vapor deposition. Before depositing the n-type electron transport layer 2, the glass conductive layer can be etched with an acid solution to define the pattern of the active region, and the surface can be cleaned with oxygen or nitrogen plasma. The metal counter electrode 5 is one or a combination of gold, silver, copper or aluminum, and the deposition method includes electron beam evaporation or resistance thermal evaporation.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and do not limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. a perovskite solar battery structure for silica-base film material, comprising:

One electro-conductive glass;

One N-shaped electron transfer layer, it is produced on electro-conductive glass;

One perovskite photosensitive layer, it is produced on N-shaped electron transfer layer;

One p-type hole transmission layer, it is produced on perovskite photosensitive layer;

One metal counter electrode, it is produced on p-type hole transmission layer.

2. a perovskite solar battery structure for silica-base film material, comprising:

One electro-conductive glass;

One p-type hole transmission layer, it is produced on electro-conductive glass;

One perovskite photosensitive layer, it is produced on p-type electron transfer layer;

One N-shaped electron transfer layer, it is produced on perovskite photosensitive layer;

One metal counter electrode, it is produced on N-shaped hole transmission layer.

3. the perovskite solar battery structure of silica-base film material according to claim 1 and 2, the material of wherein said N-shaped electron transfer layer is N-shaped zinc-oxide film, N-shaped thin film of titanium oxide or N-shaped silica-base film, and thickness is 5nm-50nm.

4. the perovskite solar battery structure of silica-base film material according to claim 1 and 2, the material of wherein said perovskite photosensitive layer is CH ₃nH ₃pbI ₃or CH ₃nH ₃pbI _3-xcl _x, thickness is 50nm-2000nm.

5. the perovskite solar battery structure of silica-base film material according to claim 1 and 2, the material of wherein said p-type hole transmission layer is p-type silica-base film, this p-type silica-base film comprises silicon-base alloy film, and the material of this p-type silica-base film is one in microcrystal silicon carbon alloy, microcrystal silicon nitrogen alloy, microcrystal silicon oxygen alloy, non-crystal silicon carbon alloy, amorphous silicon nitrogen alloy or non-crystalline/micro-crystalline silicon oxygen alloy or its combination; The thickness of this p-type silica-base film is 10nm-100nm.

6. a preparation method for the perovskite solar cell of silica-base film material, comprises the steps:

Step 1: get an electro-conductive glass;

Step 2: clean, dry up;

Step 3: depositing n-type electron transfer layer, perovskite photosensitive layer, p-type hole transmission layer and metal counter electrode successively on electro-conductive glass, complete preparation.

7. a preparation method for the perovskite solar cell of silica-base film material, comprises the steps:

Step 1: get an electro-conductive glass;

Step 2: clean, dry up;

Step 3: depositing p-type hole transmission layer, perovskite photosensitive layer, N-shaped electron transfer layer and metal counter electrode successively on electro-conductive glass, complete preparation.

8. the preparation method of the perovskite solar cell of the silica-base film material according to claim 6 or 7, the material of wherein said N-shaped electron transfer layer is zinc oxide or thin film of titanium oxide, thickness is 5nm-50nm, deposition process is magnetron sputtering method, or the material of N-shaped electron transfer layer is N-shaped silica-base film, thickness is 5-50nm, and deposition process is chemical vapour deposition technique.

9. the preparation method of the perovskite solar cell of the silica-base film material according to claim 6 or 7, the material of wherein said perovskite photosensitive layer is CH ₃nH ₃pbI ₃or CH ₃nH ₃pbI _3-xcl _x, thickness is 50nm-2000nm, and deposition process is organic and inorganic double source coevaporation method or spin-coating method.

10. the preparation method of the perovskite solar cell of the silica-base film material according to claim 6 or 7, the material of wherein said p-type hole transmission layer is p-type silicon-base alloy film, comprise one in microcrystal silicon carbon alloy, microcrystal silicon nitrogen alloy, microcrystal silicon oxygen alloy, non-crystal silicon carbon alloy, amorphous silicon nitrogen alloy or non-crystalline/micro-crystalline silicon oxygen alloy or and combination, deposition process is chemical vapour deposition (CVD), deposit thickness is 10nm-100nm, the atomic fraction of carbon containing is at 10%-30%, nitrogenous atomic fraction is at 10%-30%, and oxygen containing atomic fraction is at 10%-30%.