CN113782679A - Preparation method of all-inorganic semitransparent perovskite solar cell - Google Patents
Preparation method of all-inorganic semitransparent perovskite solar cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 15
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical group [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007733 ion plating Methods 0.000 claims abstract description 11
- 230000005525 hole transport Effects 0.000 claims abstract description 10
- 230000031700 light absorption Effects 0.000 claims abstract description 9
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000000224 chemical solution deposition Methods 0.000 claims abstract description 3
- 238000005516 engineering process Methods 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 3
- 239000000075 oxide glass Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 15
- 230000008020 evaporation Effects 0.000 description 15
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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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
- H10K30/10—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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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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
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- 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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- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a preparation method of an all-inorganic semitransparent perovskite solar cell, which comprises the following steps: (1) preparing an electron transport layer on a conductive glass substrate by adopting a chemical bath deposition method; (2) sequentially depositing a perovskite light absorption layer and a hole transport layer by adopting a thermal evaporation method; (3) preparing a top electrode by utilizing a hollow cathode ion plating technology; the perovskite in the step (2) is an inorganic CsPbBr3 perovskite, and the thickness is 600 nm; the hole transport layer is copper phthalocyanine and has a thickness of 20-80 nm. The invention optimizes the photoelectric property of the semitransparent perovskite solar cell by regulating and controlling the thickness of copper phthalocyanine so as to obtain a high-transmittance and high-efficiency cell device.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a preparation method of an all-inorganic semitransparent perovskite solar cell.
Background
The building integration of photovoltaic has become an important direction of solar energy application, and not only can the building energy efficiency be improved on the premise of not occupying space, but also the application range of photovoltaic devices can be expanded. The semitransparent photovoltaic device can absorb partial wavelength sunlight to generate electricity for a building, can also absorb partial sunlight to generate heat radiation, and the rest sunlight can penetrate through a room to illuminate. In order to meet different practical construction scenes and requirements, the transmittance of the device and the photoelectric conversion efficiency are often balanced. The novel thin film battery taking the perovskite type material as the light absorption layer can easily adjust the band gap of the light absorption layer through component regulation and control so as to meet the requirements of different practical conditions.
In order to realize practical application of perovskite solar cells in building integration photovoltaics, the devices themselves must have excellent stability. Most of the existing semitransparent batteries are based on organic-inorganic hybrid perovskite, and most of devices adopting inorganic light absorption layers also adopt organic materials as hole transmission layers, so that the existing semitransparent batteries cannot adapt to severe environment change in practical use.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of an all-inorganic semi-transparent perovskite solar cell.
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of an all-inorganic semi-transparent perovskite solar cell comprises the following steps:
(1) preparing an electron transport layer on a conductive glass substrate by adopting a chemical bath deposition method;
(2) sequentially depositing a perovskite light absorption layer and a hole transport layer by adopting a thermal evaporation method;
(3) the top electrode is prepared by utilizing a hollow cathode ion plating technology.
As a further improvement of the invention, the conductive glass substrate in the step (1) is fluorine-doped tin oxide glass; the electron transport layer is TiO2。
As a further improvement of the invention, the perovskite in the step (2) is inorganic CsPbBr3Perovskite with thickness of 600 nm; the hole transport layer is copper phthalocyanine and has a thickness of 20-80 nm.
As a further improvement of the invention, the top electrode in the step (3) is a tungsten-doped tin oxide transparent conductive film with the thickness of 80 nm.
The invention has the advantages of
Compared with the prior art, the invention has the advantages that:
the invention optimizes the photoelectric property of the semitransparent perovskite solar cell by regulating and controlling the thickness of copper phthalocyanine so as to obtain a high-transmittance and high-efficiency cell device.
Drawings
FIG. 1: examples 1-3 visible light transmission patterns for perovskite solar cells prepared;
FIG. 2: examples 1-3 comparative J-V curves for perovskite solar cells prepared;
FIG. 3: examples 1-3 comparative IPCE plots for perovskite solar cells prepared.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1
(1) Fully mixing 388mL of ultrapure water and 112mL of titanium tetrachloride raw stock in a magnetic stirrer placed in an ice bath environment to prepare 2mol/L mother liquor; the cleaned FTO glass is placed in a plasma cleaning machine for treatment for 15min, and simultaneously 5mL of titanium tetrachloride mother liquor and 195mL of pure water are mixed into a titanium tetrachloride water solution with the concentration of 0.025 mol/L. Immersing the treated FTO glass in the solution, ensuring that the conductive surface faces upwards, soaking the FTO glass in a constant-temperature environment at 70 ℃ for 30min, and cleaning and drying the residual solution on the surface of the glass after the soaking is finished. After repeating the above process twice, the FTO glass is placed on a hot bench, and the temperature is raised from room temperature to 450 ℃ and kept for 30min, so as to prepare the titanium dioxide electron transport layer.
(2) The perovskite light absorption layer is prepared by adopting a thermal evaporation method, and evaporation parameters are set as follows: the deposition thickness of CsBr is 260nm, and the deposition rate is
PbBr2The thickness of the evaporation coating is 330nm, and the evaporation coating rate is
After the FTO glass deposited with the titanium dioxide electron transport layer in the step (1) is cooled to room temperature, the FTO glass is put into a plasma cleaning machine for treatment for 15min, and CsBr and PbBr are evaporated in sequence according to the parameters after the treatment2To the glass substrate. After the completion, the wafer was taken out and transferred to a muffle furnace to be heated from room temperature to 300 ℃ for reaction sintering for 20 min.
(3) After the reaction is finished, preparing the copper phthalocyanine hole transport layer by adopting a thermal evaporation method, wherein the evaporation thickness is 20nm, and the evaporation rate is
(4) Depositing an IWO transparent conductive film on the surface of the hole transport layer by adopting a hollow cathode ion plating method to be used as an electrode, wherein the ion plating working current is 40A, the deposition time is 180s, 100 standard milliliters of argon per minute is introduced in the process, and after the completion, the battery is placed on a 200 ℃ hot bench for annealing for 10 min.
Example 2
(1) Fully mixing 388mL of ultrapure water and 112mL of titanium tetrachloride raw stock in a magnetic stirrer placed in an ice bath environment to prepare 2mol/L mother liquor; the cleaned FTO glass is placed in a plasma cleaning machine for treatment for 15min, and simultaneously 5mL of titanium tetrachloride mother liquor and 195mL of pure water are mixed into a titanium tetrachloride water solution with the concentration of 0.025 mol/L. Immersing the treated FTO glass in the solution, ensuring that the conductive surface faces upwards, soaking the FTO glass in a constant-temperature environment at 70 ℃ for 30min, and cleaning and drying the residual solution on the surface of the glass after the soaking is finished. After repeating the above process twice, the FTO glass is placed on a hot bench, and the temperature is raised from room temperature to 450 ℃ and kept for 30min, so as to prepare the titanium dioxide electron transport layer.
(2) The perovskite light absorption layer is prepared by adopting a thermal evaporation method, and evaporation parameters are set as follows: the deposition thickness of CsBr is 260nm, and the deposition rate is
PbBr2The thickness of the evaporation coating is 330nm, and the evaporation coating rate is
After the FTO glass deposited with the titanium dioxide electron transport layer in the step (1) is cooled to room temperature, the FTO glass is put into a plasma cleaning machine for treatment for 15min, and CsBr and PbBr are evaporated in sequence according to the parameters after the treatment2To the glass substrate. After the completion, the wafer was taken out and transferred to a muffle furnace to be heated from room temperature to 300 ℃ for reaction sintering for 20 min.
(3) After the reaction is finished, preparing a copper phthalocyanine hole transport layer and a silver barrier layer by adopting a thermal evaporation method, wherein the evaporation thickness of the copper phthalocyanine is 50nm, and the evaporation rate is
(4) And depositing an IWO transparent conductive film on the surface of the silver barrier layer by adopting a hollow cathode ion plating method to serve as an electrode, wherein the ion plating working current is 40A, the deposition time is 180s, 100 standard milliliters of argon per minute are introduced in the process, and after the completion of the ion plating, the battery is placed on a 200 ℃ hot bench for annealing for 10 min.
Example 3
(1) Fully mixing 388mL of ultrapure water and 112mL of titanium tetrachloride raw stock in a magnetic stirrer placed in an ice bath environment to prepare 2mol/L mother liquor; the cleaned FTO glass is placed in a plasma cleaning machine for treatment for 15min, and simultaneously 5mL of titanium tetrachloride mother liquor and 195mL of pure water are mixed into a titanium tetrachloride water solution with the concentration of 0.025 mol/L. Immersing the treated FTO glass in the solution, ensuring that the conductive surface faces upwards, soaking the FTO glass in a constant-temperature environment at 70 ℃ for 30min, and cleaning and drying the residual solution on the surface of the glass after the soaking is finished. After repeating the above process twice, the FTO glass is placed on a hot bench, and the temperature is raised from room temperature to 450 ℃ and kept for 30min, so as to prepare the titanium dioxide electron transport layer.
(2) The perovskite light absorption layer is prepared by adopting a thermal evaporation method, and evaporation parameters are set as follows: the deposition thickness of CsBr is 260nm, and the deposition rate is
PbBr2The thickness of the evaporation coating is 330nm, and the evaporation coating rate is
After the FTO glass deposited with the titanium dioxide electron transport layer in the step (1) is cooled to room temperature, the FTO glass is put into a plasma cleaning machine for treatment for 15min, and CsBr and PbBr are evaporated in sequence according to the parameters after the treatment2To the glass substrate. After the completion, the wafer was taken out and transferred to a muffle furnace to be heated from room temperature to 300 ℃ for reaction sintering for 20 min.
(3) The copper phthalocyanine hole transport layer and the silver barrier layer are prepared by a thermal evaporation method, the evaporation thickness of the copper phthalocyanine is 80nm, and the evaporation rate is
(4) And depositing an IWO transparent conductive film on the surface of the silver barrier layer by adopting a hollow cathode ion plating method to serve as an electrode, wherein the ion plating working current is 40A, the deposition time is 180s, 100 standard milliliters of argon per minute are introduced in the process, and after the completion of the ion plating, the battery is placed on a 200 ℃ hot bench for annealing for 10 min.
The implementation effect is as follows: the visible light transmittance test was performed on the battery devices prepared in examples 1 to 3, and the results are shown in fig. 3. The device transmission is gradually reduced along with the increase of the thickness of the copper phthalocyanine, and the values are 32.9%, 31.9% and 31.5% in average, and the numerical values are not greatly different. Since CsPbBr3 perovskite does not absorb visible light with a wavelength of less than 540nm, the average transmission of the device is not high. The photoelectric conversion efficiency of the battery devices prepared in examples 1 to 3 was measured, and the results are shown in fig. 2. The open-circuit voltage of a 20nm device is 1.258V, the short-circuit current density is 5.78mA/cm2, the filling factor is lower and is only 0.5, and the efficiency is only 3.64%; the 50nm device has the highest efficiency of 5.87 percent, wherein the open-circuit voltage is 1.359V, the short-circuit current density is 6.42mA/cm2, and the filling factor is 0.673; the open-circuit voltage of the 80nm device is 1.309V, the short-circuit current density is 6.37mA/cm2, and the filling factor is 0.605. When the thickness of copper phthalocyanine is only 20nm, the copper phthalocyanine is not enough to cover the perovskite thin film compactly, so that the electric leakage of a device is caused; copper phthalocyanine is thicker (80nm) compared to 50nm current, but the voltage and fill factor are significantly reduced. Thus, example 2 is the preferred embodiment.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (3)
1. A preparation method of an all-inorganic semitransparent perovskite solar cell is characterized by comprising the following steps:
(1) preparing an electron transport layer on a conductive glass substrate by adopting a chemical bath deposition method;
(2) sequentially depositing a perovskite light absorption layer and a hole transport layer by adopting a thermal evaporation method;
(3) preparing a top electrode by utilizing a hollow cathode ion plating technology;
the perovskite in the step (2) is inorganic CsPbBr3Perovskite with thickness of 600 nm; the hole transport layer is copper phthalocyanine and has a thickness of 20-80 nm.
2. The perovskite solar cell according to claim 1, characterized in that the electrically conductive glass substrate of step (1) is a fluorine-doped tin oxide glass; the electron transport layer is TiO2。
3. The perovskite solar cell according to claim 1, characterized in that the top electrode of step (3) is a tungsten doped tin oxide transparent conductive thin film with a thickness of 80 nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102982861A (en) * | 2012-11-27 | 2013-03-20 | 无锡力合光电石墨烯应用研发中心有限公司 | Transparent conductive film layer for capacitive touch screen |
| CN106953014A (en) * | 2017-03-31 | 2017-07-14 | 周德明 | A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer |
| CN106953015A (en) * | 2017-04-01 | 2017-07-14 | 武汉理工大学 | A kind of preparation method of high efficiency large area perovskite solar cell |
| CN107993848A (en) * | 2017-11-08 | 2018-05-04 | 华中科技大学 | Based on titania-doped perovskite solar cell of nickel and preparation method thereof |
| CN109273612A (en) * | 2018-11-10 | 2019-01-25 | 济南大学 | CsPbBr3The continuous gas-phase deposition process for preparing of perovskite battery |
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- 2021-07-26 CN CN202110842751.8A patent/CN113782679A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102982861A (en) * | 2012-11-27 | 2013-03-20 | 无锡力合光电石墨烯应用研发中心有限公司 | Transparent conductive film layer for capacitive touch screen |
| CN106953014A (en) * | 2017-03-31 | 2017-07-14 | 周德明 | A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer |
| CN106953015A (en) * | 2017-04-01 | 2017-07-14 | 武汉理工大学 | A kind of preparation method of high efficiency large area perovskite solar cell |
| CN107993848A (en) * | 2017-11-08 | 2018-05-04 | 华中科技大学 | Based on titania-doped perovskite solar cell of nickel and preparation method thereof |
| CN109273612A (en) * | 2018-11-10 | 2019-01-25 | 济南大学 | CsPbBr3The continuous gas-phase deposition process for preparing of perovskite battery |
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