CN111540831B - Titanium ore solar cell and preparation method thereof - Google Patents
Titanium ore solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010936 titanium Substances 0.000 title abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052719 titanium Inorganic materials 0.000 title abstract description 16
- 239000010410 layer Substances 0.000 claims abstract description 121
- 239000011241 protective layer Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 23
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 32
- 238000000137 annealing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 230000005525 hole transport Effects 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011265 semifinished product Substances 0.000 claims description 8
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910005855 NiOx Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- -1 methyl amine halide Chemical class 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 6
- 239000003518 caustics Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000004528 spin coating Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 230000000513 bioprotective effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The application discloses a titanium ore solar cell and a preparation method thereof, and belongs to the field of new photovoltaic energy. The titanium ore solar cell comprises a glass substrate, a front electrode, a hole transmission layer, a perovskite absorption layer, an electron transmission layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protective layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film. The back electrode protective layer is a zinc oxide or indium oxide conductive film doped with boron and high in environmental stability, and a layer of zinc oxide or indium oxide protective layer doped with boron is added on the surface of the metal back electrode, so that the metal electrode can be protected from oxidation and sulfuration corrosion, and meanwhile, the perovskite layer can be further isolated from contacting water, oxygen and corrosive substances, and the environmental stability of the perovskite solar cell is improved. The back electrode protective layer is in a transparent state, so that the light transmittance of the battery can be improved, and the battery is more suitable for being applied to buildings such as glass curtain walls and the like.
Description
Technical Field
The application relates to the field of new photovoltaic energy, in particular to a titanium ore solar cell and a preparation method thereof.
Background
The solar cell has the advantages of green environmental protection, rich energy storage and the like, and is honored as the most promising green energy source. In recent years, organic-inorganic hybrid perovskite solar cells are developed very rapidly, the photoelectric conversion efficiency of the organic-inorganic hybrid perovskite solar cells reaches about 25%, and the perovskite solar cells are rich in raw material sources, simple in process and low in cost, can be prepared into flexible cells, and receive wide attention in academia and industry.
The main reason for limiting commercialization of perovskite solar cells is that they are poor in environmental stability and are vulnerable to water, oxygen and corrosive substances in the environment, so that improving the environmental stability is a key problem to be solved at present.
In addition, the back electrode of the perovskite battery is a metal layer and is easy to be corroded by oxygen, sulfur and the like. The traditional film battery back electrode protective layer is titanium, is easy to be corroded by acidic substances in the air, is opaque, and limits the application of the battery in construction.
Therefore, the development of a novel back electrode protection layer which can improve the light transmittance and prevent the back electrode from being corroded by oxidation has important significance.
Disclosure of Invention
In order to make up for the defects of the prior art, the application provides a titanium ore solar cell and a preparation method thereof. The preparation method of the titanium ore solar cell is simple, and the back electrode protective layer of the titanium ore solar cell can protect the metal back electrode from oxidation or vulcanization and can further isolate the perovskite layer from contacting water, oxygen and corrosive substances; the back electrode protective layer is transparent, so that the light transmittance of the battery can be improved, and the battery is more suitable for being applied to a glass curtain wall.
The technical scheme of the application is as follows:
a titanium ore solar cell comprises a glass substrate, a front electrode, a hole transmission layer, a perovskite absorption layer, an electron transmission layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protective layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film.
Preferably, the thickness of the back electrode protection layer is 10-100 nm.
Preferably, the thickness of the hole transport layer is 5-30 nm, the thickness of the perovskite absorption layer is 400-500 nm, the thickness of the electron transport layer is 50-80 nm, the thickness of the buffer layer is 10-15 nm, and the thickness of the metal back electrode layer is 70-200 nm.
The preparation method of the titanium ore solar cell comprises the following steps:
1) Processing of a glass conductive substrate: carrying out ultraviolet ozone treatment on the glass conductive substrate for standby;
2) Preparation of hole transport layer: adding NiOx nano particles into a solvent for ultrasonic dispersion to prepare NiOx suspension serving as a first precursor liquid; coating the first precursor liquid on the conductive surface of the conductive glass upwards, and carrying out heating annealing treatment after the coating is finished, and naturally cooling to room temperature to form a hole transport layer;
3) Preparation of perovskite absorption layer: dissolving lead halide and methyl amine halide in an organic solvent according to a certain proportion to prepare a second precursor solution, stirring and dissolving to obtain a perovskite precursor solution, coating the perovskite precursor solution on a hole transport layer, and annealing on a heating plate to obtain a perovskite absorption layer;
4) Preparation of an electron transport layer: dissolving fullerene derivative in chlorobenzene, heating and stirring to obtain a third precursor solution, coating the third precursor solution on a perovskite absorption layer, and annealing on a heating plate to obtain an electron transport layer;
5) Preparation of a buffer layer: adding BCP into methanol to obtain supersaturated solution, coating the supersaturated solution onto an electron transport layer, and then annealing the supersaturated solution on a heating plate;
6) Preparation of a metal back electrode layer: placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 multiplied by 10 -4 Evaporating Au, ag or Al on the surface of the buffer layer to form a metal back electrode layer;
7) Preparing a back electrode protection layer: placing the semi-finished product of the battery obtained in the step 6) into a magnetron sputtering coating chamber, wherein the vacuum degree reaches 5 multiplied by 10 -4 And sputtering a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film on the metal back electrode layer at Pa or above.
Preferably, in the step 7), the sputtering source of the magnetron sputtering is argon, and the oxygen flow is 10 to the whole20cm 3 Per min, the temperature of the substrate is 80-120 ℃, and the background vacuum degree is 10 -4 Pa, the target base distance is 6cm, the sputtering time is 1-10 min, the working pressure is 1-2 Pa, and the sputtering power is 100-200W. Under the technological parameters, the back electrode protective layer sputtered on the surface of the metal back electrode is compact and uniform.
In the step 7), the target material used for sputtering the protective layer of the back electrode of the zinc oxide transparent conductive film doped with boron is ZnO with the mass ratio of B 2 O 3 Ceramic target with 98-99:1-2; the target material used for sputtering the boron doped indium oxide transparent conductive film back electrode protection layer is In with the mass ratio 2 O 3 :B 2 O 3 Ceramic targets=97-99:1-3.
As a preferable scheme:
in the step 1), the time of the ultraviolet ozone treatment is 5-30 min;
in the step 2), the solvent is deionized water, ethanol or n-butanol; the heating annealing temperature is 100-200 ℃ and the time is 10-30 min
In the step 3), the organic solvent is DMF and/or DMSO; the temperature of the heating plate is controlled to be 100-120 ℃, and the annealing time is controlled to be 10-30 min;
in the step 4), the dissolution temperature is controlled to be 40-50 ℃, the temperature of a heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min;
in the step 5), the temperature of the heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min.
Preferably, in step 3), the lead halide is PbCl 2 、PbBr 2 Or PbI 2 One or two of the following components; the halomethylamine being CH 3 NH 3 Cl、CH 3 NH 3 Br or CH 3 NH 3 One of I; the molar ratio of the lead halide to the methyl amine halide is 1:1-3:1.
Preferably, in the step 3), the molar concentration of lead ions in the second precursor solution is 0.5-2 mol/L; in the step 4), the mass volume concentration of the fullerene derivative in the third precursor solution is 10-20 mg/mL.
As a preferred embodimentIn step 4), the fullerene derivative is PC 61 BM、PC 71 BM, ICBA or bis-PC 61 BM。
The beneficial effects of the application are as follows:
1. the back electrode protective layer is creatively arranged to be a conductive film of zinc oxide or indium oxide doped with boron, which has high environmental stability, and the dense and uniform back electrode protective layer is obtained through proper technological parameters.
2. The surface of the metal back electrode is added with a zinc oxide and indium oxide protective layer doped with boron, so that the metal electrode can be protected from oxidation, sulfuration and corrosion, and meanwhile, the perovskite layer can be further isolated from contacting water, oxygen and corrosive substances, so that the environmental stability of the perovskite solar cell is improved, and the attenuation of the photoelectric efficiency of the perovskite solar cell is obviously reduced.
3. The back electrode protective layer is in a transparent state, so that the light transmittance of the battery can be improved, and the battery is more suitable for being applied to buildings such as glass curtain walls and the like.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic diagram of the structure of a titanium-ore solar cell of the present application;
in the drawings, the list of components represented by the various numbers is as follows:
1. glass substrate, 2, front electrode, 3, hole transport layer, 4, perovskite absorption layer, 5, electron transport layer, 6, buffer layer, 7, metal back electrode layer, 8, back electrode protective layer.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
Example 1
As shown in fig. 1, a titanium-ore solar cell comprises a glass substrate 1, a front electrode 2, a hole-transporting layer 3, a perovskite absorbing layer 4, an electron-transporting layer 5, a buffer layer 6, a metal back electrode layer 7 and a back electrode protective layer 8 which are sequentially laminated from bottom to top; the back electrode protection layer 8 is a boron-doped zinc oxide transparent conductive film.
The preparation method of the titanium ore solar cell comprises the following steps:
1) Processing of a glass conductive substrate: the substrate is selected from common glass substrate, the sheet resistance of the front electrode layer is 5-40 omega, the transmittance is 75-90%, and after the conductive substrate is cleaned, the glass conductive substrate is treated by ultraviolet ozone for 25min for standby;
2) Preparation of hole transport layer: adding 3mg of nickel oxide nano particles into 1mL of deionized water, and performing ultrasonic dispersion for 24 hours to prepare uniform suspension serving as a first precursor liquid;
placing the conductive glass surface on a table top of a spin coater at a speed of 2000rpm, dripping a first precursor solution, spin-coating for 30s, heating and annealing at 100-200 ℃ for 10-20 min after coating, and naturally cooling to room temperature to obtain a compact nickel oxide hole transport layer;
3) Perovskite absorption layer (CH) 3 NH 3 Preparation of PbX, x=cl, br, I): CH with the molar ratio of 1:1-3:1 is used for preparing the catalyst 3 NH 3 X and PbX 2 Dissolving in DMF or DMSO or a mixed solution of the two to prepare a second precursor solution with the molar concentration of 0.5-2 mol/L, and stirring and dissolving for 4 hours to form a perovskite precursor solution. Spin-coating the perovskite precursor solution on NiO x On the hole transmission layer, spin coating speed is 6000rpm for 30s, and then annealing is carried out for 10-30 min at 80-100 ℃ to form a perovskite absorption layer with 400-500 nm;
4) Preparation of an electron transport layer: PC is put into 61 BM is dissolved in anhydrous chlorobenzene to prepare 10-20 mg/mL third precursor liquid, and the third precursor liquid is stirred and dissolved for 3-4 h at 40-50 ℃. The PC is put into 61 The chlorobenzene solution of BM is spin-coated on the perovskite absorption layer, the spin-coating speed is 1500rpm, the time is 30s, annealing is carried out for 10min at 70 ℃, and PC with the thickness of 50-80 nm is formed 61 A BM electron transport layer;
5) Preparation of a buffer layer: spin-coating a methanol saturated solution of BCP on the electron transport layer, and annealing for 10min at 70 ℃ to form a BCP buffer layer with the film thickness of 10-15 nm;
6) Preparation of a metal electrode layer: placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 multiplied by 10 -4 Evaporating 100nm Ag above Pa to form Ag electrode;
7) Preparing a back electrode protection layer: placing the semi-finished product of the battery obtained in the step 6) into a magnetron sputtering coating chamber, wherein the oxygen flow is 15cm 3 Per min, the vacuum degree reaches 10 -4 And sputtering a BZO protective layer on the metal back electrode layer at Pa or above. The target material is ZnO with mass ratio of B 2 O 3 The ceramic target with the ratio of (99:1) is subjected to magnetron sputtering, wherein a sputtering source is argon, the substrate temperature is 100 ℃, the target base distance is 6cm, the sputtering time is 2min, the working pressure is 1Pa, the sputtering power is 180W, and the BZO protective layer with the film thickness of 15nm is formed.
Example 2
As shown in fig. 1, a titanium-ore solar cell comprises a glass substrate 1, a front electrode 2, a hole-transporting layer 3, a perovskite absorbing layer 4, an electron-transporting layer 5, a buffer layer 6, a metal back electrode layer 7 and a back electrode protective layer 8 which are sequentially laminated from bottom to top; the back electrode protection layer 8 is a boron-doped zinc oxide transparent conductive film.
The preparation method of the titanium ore solar cell comprises the following steps:
1) Processing of a glass conductive substrate: the substrate is selected from common glass substrate, the sheet resistance of the front electrode layer is 5-40 omega, the transmittance is 75-90%, and after the conductive substrate is cleaned, the glass conductive substrate is treated by ultraviolet ozone for 25min for standby;
2) Preparation of hole transport layer: adding 3mg of nickel oxide nano particles into 1mL of deionized water, and performing ultrasonic dispersion for 24 hours to prepare uniform suspension serving as a first precursor liquid;
placing the conductive glass surface on a table top of a spin coater at a speed of 2000rpm, dripping a first precursor solution, spin-coating for 30s, heating and annealing at 100-200 ℃ for 10-20 min after coating, and naturally cooling to room temperature to obtain a compact nickel oxide hole transport layer;
3) Perovskite absorption layer (CH) 3 NH 3 Preparation of PbX, x=cl, br, I): CH with the molar ratio of 1:1-3:1 is used for preparing the catalyst 3 NH 3 X and PbX 2 Dissolving in DMF or DMSO or a mixed solution of the two to prepare a second precursor solution with the molar concentration of 0.5-2 mol/L, and stirring and dissolving for 4 hours to form a perovskite precursor solution. Spin-coating the perovskite precursor solution on NiO x On the hole transmission layer, spin coating speed is 6000rpm for 30s, and then annealing is carried out for 10-30 min at 80-100 ℃ to form a perovskite absorption layer with 400-500 nm;
4) Preparation of an electron transport layer: PC is put into 61 BM is dissolved in anhydrous chlorobenzene to prepare 10-20 mg/mL third precursor liquid, and the third precursor liquid is stirred and dissolved for 3-4 h at 40-50 ℃. The PC is put into 61 The chlorobenzene solution of BM is spin-coated on the perovskite absorption layer, the spin-coating speed is 1500rpm, the time is 30s, annealing is carried out for 10min at 70 ℃, and PC with the thickness of 50-80 nm is formed 61 A BM electron transport layer;
5) Preparation of a buffer layer: spin-coating a methanol saturated solution of BCP on the electron transport layer, and annealing for 10min at 70 ℃ to form a BCP buffer layer with the film thickness of 10-15 nm;
6) Preparation of a metal electrode layer: placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 multiplied by 10 -4 Evaporating 100nm Ag above Pa to form Ag electrode;
7) Preparing a back electrode protection layer: placing the semi-finished product of the battery obtained in the step 6) into a magnetron sputtering coating chamber, wherein the oxygen flow is 15cm 3 Per min, the vacuum degree reaches 10 -4 And sputtering a BIO protective layer on the metal back electrode layer at Pa or above. The target material is mass ratio InO to B 2 O 3 ＝982, the sputtering source of the magnetron sputtering is argon, the substrate temperature is 135 ℃, the target base distance is 6cm, the sputtering time is 2min, the working pressure is 1Pa, the sputtering power is 120W, and the BIO protective layer with the film thickness of 18nm is formed.
In other embodiments, the thickness of the back electrode protection layer may also be greater.
Comparative example 1
Step 7) was omitted compared to example 1, i.e., the titanium ore solar cell of comparative example 1 did not include the back electrode protective layer.
Comparative example 2
Compared with example 1, the back electrode protection layer is Ti in the prior art.
20 titanium-ore solar cells were respectively fabricated according to example 1, example 2, comparative example 1, comparative example 2; namely four groups of titanium ore solar cells, 20 in each group; in the preparation process of 20 batteries in each group, the process parameters are adjusted within the range described in the embodiment, and specific corresponding process parameters are not repeated. After all perovskite solar energy test data prepared in example 1, example 2, comparative example 1 and comparative example 2 were simultaneously subjected to an outdoor exposure test for 1000 hours, the electrical property data after exposure was tested, and then the average value was calculated, and the results are shown in table 1.
Table 1 electrical data of perovskite solar cell of each example and comparative example before and after exposure to sun
As can be seen from table 1, the electric properties before exposure of the back electrode protection layer were substantially the same for the batteries of titanium (Ti), BZO and BIO, respectively, which were slightly higher than the battery power generation Efficiency (EFF) without the back electrode protection layer, after 1000 hours of outdoor exposure, the battery attenuation rate of the back electrode protection layer was significantly reduced, and the battery attenuation rate of the back electrode protection layer of BZO or BIO was significantly reduced as compared with the case where the back electrode protection layer was Ti.
Claims (9)
1. A titanium-ore solar cell, characterized in that: the device comprises a glass substrate, a front electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protective layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film;
the back electrode protective layer is obtained by adopting a magnetron sputtering method, and the target material used for sputtering the boron-doped zinc oxide transparent conductive film back electrode protective layer is ZnO with the mass ratio of B 2 O 3 Ceramic target with 98-99:1-2; the target material used for sputtering the boron doped indium oxide transparent conductive film back electrode protection layer is In with the mass ratio 2 O 3 :B 2 O 3 Ceramic targets=97-99:1-3.
2. The titanium-ore solar cell of claim 1, wherein: the thickness of the back electrode protective layer is 10-100 nm.
3. The titanium-ore solar cell according to claim 1 or 2, characterized in that: the thickness of the hole transmission layer is 5-30 nm, the thickness of the perovskite absorption layer is 400-500 nm, the thickness of the electron transmission layer is 50-80 nm, the thickness of the buffer layer is 10-15 nm, and the thickness of the metal back electrode layer is 70-200 nm.
4. The method for manufacturing a titanium-ore solar cell according to claim 1, comprising the steps of:
1) Processing of a glass conductive substrate: carrying out ultraviolet ozone treatment on the glass conductive substrate for standby;
2) Preparation of hole transport layer: adding NiOx nano particles into a solvent for ultrasonic dispersion to prepare NiOx suspension serving as a first precursor liquid; coating the first precursor liquid on the conductive surface of the conductive glass upwards, and carrying out heating annealing treatment after the coating is finished, and naturally cooling to room temperature to form a hole transport layer;
3) Preparation of perovskite absorption layer: dissolving lead halide and methyl amine halide in an organic solvent according to a certain proportion to prepare a second precursor solution, stirring and dissolving to obtain a perovskite precursor solution, coating the perovskite precursor solution on a hole transport layer, and annealing on a heating plate to obtain a perovskite absorption layer;
4) Preparation of an electron transport layer: dissolving fullerene derivative in chlorobenzene, heating and stirring to obtain a third precursor solution, coating the third precursor solution on a perovskite absorption layer, and annealing on a heating plate to obtain an electron transport layer;
5) Preparation of a buffer layer: adding BCP into methanol to obtain supersaturated solution, coating the supersaturated solution onto an electron transport layer, and then annealing the supersaturated solution on a heating plate;
6) Preparation of a metal back electrode layer: placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 multiplied by 10 -4 Evaporating Au, ag or Al on the surface of the buffer layer to form a metal back electrode layer;
7) Preparing a back electrode protection layer: placing the semi-finished product of the battery obtained in the step 6) into a magnetron sputtering coating chamber, wherein the vacuum degree reaches 5 multiplied by 10 -4 And sputtering a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film on the metal back electrode layer at Pa or above.
5. The method for manufacturing a titanium-ore solar cell according to claim 4, wherein: in the step 7), the sputtering source of the magnetron sputtering is argon, and the oxygen flow is 10 cm to 20cm 3 Per min, the temperature of the substrate is 80-120 ℃, and the background vacuum degree is 10 -4 Pa, the target base distance is 6cm, the sputtering time is 1-10 min, the working pressure is 1-2 Pa, and the sputtering power is 100-200W.
6. The method for manufacturing a titanium-ore solar cell according to claim 4, wherein:
in the step 1), the time of the ultraviolet ozone treatment is 5-30 min;
in the step 2), the solvent is deionized water, ethanol or n-butanol; the heating annealing temperature is 100-200 ℃ and the time is 10-30 min
In the step 3), the organic solvent is DMF and/or DMSO; the temperature of the heating plate is controlled to be 100-120 ℃, and the annealing time is controlled to be 10-30 min;
in the step 4), the dissolution temperature is controlled to be 40-50 ℃, the temperature of a heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min;
in the step 5), the temperature of the heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min.
7. The method for manufacturing a titanium-ore solar cell according to claim 4, wherein: in step 3), the lead halide is PbCl 2 、PbBr 2 Or PbI 2 One or two of the following components; the halomethylamine being CH 3 NH 3 Cl、CH 3 NH 3 Br or CH 3 NH 3 One of I; the molar ratio of the lead halide to the methyl amine halide is 1:1-3:1.
8. The method for manufacturing a titanium-ore solar cell according to claim 4, wherein: in the step 3), the molar concentration of lead ions in the second precursor solution is 0.5-2 mol/L; in the step 4), the mass volume concentration of the fullerene derivative in the third precursor solution is 10-20 mg/mL.
9. The method for manufacturing a titanium-ore solar cell according to claim 4, wherein: in step 4), the fullerene derivative is PC 61 BM、PC 71 BM, ICBA or bis-PC 61 BM。
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