CN111477747A - Perovskite solar cell with zirconium oxide passivated tin oxide as electron transport layer and method - Google Patents
Perovskite solar cell with zirconium oxide passivated tin oxide as electron transport layer and method Download PDFInfo
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- CN111477747A CN111477747A CN202010364564.9A CN202010364564A CN111477747A CN 111477747 A CN111477747 A CN 111477747A CN 202010364564 A CN202010364564 A CN 202010364564A CN 111477747 A CN111477747 A CN 111477747A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 45
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000005525 hole transport Effects 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000002161 passivation Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 239000012296 anti-solvent Substances 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- 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
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a perovskite solar cell taking zirconium oxide passivated tin oxide as an electron transmission layer, which comprises a transparent conductive substrate, an electron transmission layer, a perovskite layer and an electrode; or a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer, and an electrode; the electronic transmission layer is tin oxide passivated by zirconium oxide, and a zirconium oxide passivation layer is grown on the surface of a tin oxide film in situ by adopting a low-temperature solution method. The electron transport layer ensures the extraction of electrons in the perovskite layer, simultaneously avoids the problem of high recombination of current carriers at certain sites caused by overhigh oxygen vacancies, and lays a good foundation for improving the efficiency and stability of devices. Meanwhile, the preparation method by adopting the low-temperature solution method has the advantages of simple preparation, economy, practicability and convenience for large-area production.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
With the increasing use of fossil energy, the problems of energy exhaustion and environmental pollution are becoming more serious. Therefore, the development and utilization of clean energy is a trend in the future. The energy of the clean energy source of solar energy is far more than the sum of all other energy sources, so that the solar energy source has an important development prospect for the utilization of solar energy. Among them, the direct conversion of solar energy into electrical energy by means of photovoltaic devices is one of the most directly effective ways. Solar cell development has gone through three generations to date: the first generation is a crystalline silicon solar cell, the second generation is a thin film solar cell, and the third generation is a new solar cell into which nanotechnology is introduced. The third generation solar cells include dye-sensitized solar cells, organic-inorganic hybrid Perovskite Solar Cells (PSC). Among them, organic-inorganic hybrid perovskite batteries have attracted much attention and have been developed rapidly because of their high photoelectric conversion efficiency (highest authentication efficiency: 25.2%) and the advantages of solution-soluble preparation.
The quality of the electron transport layer has an important effect on the performance of the perovskite device. At the beginning of perovskite cell research, ZnO, a material was used as an electron transport layer. However, during the heating process, ZnO catalyzes the decomposition of perovskite, which leads to a great reduction in the photoelectric conversion efficiency and stability of the device. Followed by TiO2Has been widely used, but TiO2The conductivity of the layer is poor and the diffusion length of the carriers is small due to the wide forbidden band width. And under the action of ultraviolet light, the layer can catalyze the decomposition of perovskite. Thus, SnO with better conductive properties is now available2Entering the field of vision of people. The Yongjing Bian adopts tin oxide as an electron transport layer to prepare a perovskite solar cell device, and the domestic highest authentication efficiency of 23.7 percent is obtained. But due to SnO during preparation2The uncontrollable property of the middle oxygen vacancy ensures that the content of the oxygen vacancy is uncertain at different positions of the film, so that the blocking effect on holes is greatly reduced at certain positions due to the overhigh content of the oxygen vacancy, and the carrier recombination is serious. EDTA and SnO are adopted by Liu Sheng Zhongzhi subject group of Shanxi university2The complex compound is used as an electron transport layer, and the improvement of the device performance is obtained by modifying tin oxide, so that the international certification efficiency of 21.5 percent is obtained. However, EDTA has the advantagesThe organic matter can be degraded in the long-term use process, and the long-term effective protection effect can not be provided for industrial products. Therefore, it is of far-reaching importance to find a suitable method for improving the current problems.
Disclosure of Invention
The invention aims to provide a perovskite solar cell with zirconium oxide passivated tin oxide as an electron transport layer and a method thereof. The method has the advantages of simple and easy operation, low cost, convenient large-area production and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a perovskite solar cell with tin oxide passivated by zirconium oxide as an electron transport layer comprises a transparent conductive substrate, the electron transport layer, a perovskite layer and an electrode; or a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer, and an electrode; the method is characterized in that the electron transport layer is tin oxide passivated by zirconium oxide, and the zirconium oxide layer is grown on the surface of the tin oxide film in situ by adopting a low-temperature solution method.
Furthermore, the thickness of the tin oxide layer in the zirconium oxide passivation tin oxide layer is 20-50 nm.
Furthermore, the thickness of the zirconia layer in the zirconia passivation tin oxide layer is 1-5 nm.
Further, the preparation method of the zirconium oxide passivated tin oxide layer comprises the following steps:
(1) immersing the conductive glass sheet into stannous chloride aqueous solution with the concentration of 0.02-0.1 mol/L;
(2) hydrolyzing at 60-120 deg.C for 30-120 min;
(3) taking out the sample, and immersing the sample into a ZrOCl2 solution with the concentration of 0.01-0.1 mol/L;
(4) hydrolyzing at 80-200 deg.C for 10-30 min;
(5) after the sample is taken out, the sample is thermally treated for 60-120min at the temperature of 150-.
Further, the SnCl2Passing an aqueous solution through SnCl2.6H2Mixing O with water or acid or hydrolysis inhibitor; ZrOCl2The aqueous solution is prepared by ZrOCl2·8H2Mixing O with water or acid or hydrolysis inhibitor;
further, the preparation method of the titanium ore solar cell comprises the following steps:
(1) preparing a zirconium oxide passivated tin oxide layer on a transparent conductive substrate by adopting a low-temperature hydrolysis method;
(2) preparing a perovskite film on the substrate by adopting an air extraction method or an anti-solvent method;
(3) for a device containing a hole transport layer, spin coating and natural drying to prepare the layer;
(4) preparing an electrode by adopting a vacuum evaporation method for a metal electrode; for the carbon electrode, the carbon paste is coated on the perovskite or the hole transport layer by adopting a screen printing and scraping method, and then is heated, cured and dried at 80-120 ℃.
Further, the metal electrode comprises Au, Ag, Al and Cu; the carbon electrode raw material-carbon slurry is low-temperature slurry prepared by mixing a conductive material, a solvent and a binder.
Compared with the prior art, the invention has the beneficial effects that:
the zirconium oxide passivation tin oxide adopted by the invention is prepared by preparing a tin oxide layer as a main material of an electron transmission layer, and then growing an ultrathin zirconium oxide layer on a tin oxide film in situ. On one hand, the electron transmission layer ensures proper conductivity of the whole electron transmission layer, and obtains longer carrier diffusion length of carriers in the electron transmission layer; meanwhile, the problem of serious carrier recombination caused by more oxygen vacancies of tin oxide at certain sites is avoided by the ultrathin zirconium oxide layer, and a good foundation is laid for preparing high-performance devices.
Compared with the passivation of organic matters, the metal oxide such as zirconium oxide is adopted as the passivation layer, so that the passivation layer has excellent long-term stability, and the stable and continuous passivation effect of the layer is met in the long-term service process of the device.
Compared with A L D sol-gel method of high temperature and high pressure, the method has low cost and simple preparation process, and is very suitable for large-area industrial production.
Drawings
FIG. 1 is a schematic structural view of a zirconium oxide passivated tin oxide layer provided by the present invention;
FIG. 2(a) is a schematic diagram of a comparative example cell with a cross-section enlarged by 50000 times, and FIG. 2(b) is a schematic diagram of a comparative example cell with a cross-section enlarged by 100000 times; FIG. 2(c) is a graph of battery J-V performance;
FIG. 3(a) is a schematic diagram of the cell of example 1 with a cross section enlarged by 100000 times, and FIG. 3(b) is a J-V performance diagram of the cell;
fig. 4 and 5 are J-V performance plots for the batteries of examples 2 and 3, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples.
Comparative example
1. Spin coating stannous chloride aqueous solution with concentration of 0.05 mol/L on FTO conductive glass sheet, and hydrolyzing at 90 deg.C for 60min to form SnO2The electron transport layer is thermally treated at 180 ℃ for 60min to obtain SnO2A film.
2. At SnO2Spin-on MAPbI3Drying the precursor and an anti-solvent, and carrying out heat treatment at 100 ℃ for 10min to form a perovskite thin film;
3. spin-coating Spiro-OMeTAD on the perovskite thin film as a hole transport layer;
4. and (4) evaporating Au on the hole transport layer in vacuum to form an electrode, thus obtaining the perovskite solar cell.
The cross-sectional morphology of the cell was tested and recorded, as shown in FIGS. 2(a) and (b), it can be seen that SnO2The thickness of the layer is about 30 nm; and the devices were tested for their optoelectronic properties as shown in fig. 2 (c).
Example 1
1. Immersing the FTO conductive glass sheet into the solution with the concentration of 0.05mol/L in aqueous stannous chloride solution and hydrolyzing at 90 deg.C for 60min to form SnO2An electron transport layer;
2. the sample was then placed in ZrOCl at a concentration of 0.02 mol/L2Hydrolyzing in the solution at 150 ℃ for 15min, and carrying out heat treatment at 180 ℃ for 60min to obtain a zirconium oxide passivated tin oxide electron transport layer;
3. spin coating MAPbI on zirconia passivated tin oxide layer3Drying the precursor and an anti-solvent, and carrying out heat treatment at 100 ℃ for 10min to form a perovskite thin film;
3. spin-coating Spiro-OMeTAD on the perovskite thin film as a hole transport layer;
4. and (4) evaporating Au on the hole transport layer in vacuum to form an electrode, thus obtaining the perovskite solar cell.
The cross-sectional morphology of the cell was tested and recorded, as shown in FIG. 3(a), it can be seen that SnO2The thickness of the layer is about 40 nm; and the photoelectric performance of the device was tested, as shown in fig. 3(b), the photoelectric conversion efficiency was stabilized at 17.1% or more.
Example 2
1. The FTO conductive glass sheet is immersed into stannous chloride aqueous solution with the concentration of 0.03 mol/L and hydrolyzed for 70 minutes at 100 ℃ to form SnO2An electron transport layer;
2. the sample was then placed in ZrOCl at a concentration of 0.01 mol/L2Hydrolyzing in the solution at 180 ℃ for 20min, and carrying out heat treatment at 150 ℃ for 90min to obtain a zirconium oxide passivated tin oxide electron transport layer;
3. spin coating MAPbI on zirconia passivated tin oxide layer3Drying the precursor and an anti-solvent, and carrying out heat treatment at 100 ℃ for 10min to form a perovskite thin film;
3. spin-coating Spiro-OMeTAD on the perovskite thin film as a hole transport layer;
4. and (4) evaporating Au on the hole transport layer in vacuum to form an electrode, thus obtaining the perovskite solar cell.
The J-V efficiency of the cell is tested, and as shown in FIG. 4, the cell has good performance and the photoelectric conversion efficiency is stabilized to be more than 16.6%.
Example 3
1. The FTO conductive glass sheet is immersed into stannous chloride aqueous solution with the concentration of 0.08 mol/L and hydrolyzed for 90 minutes at 60 ℃ to form SnO2An electron transport layer;
2. then putting the sample into a ZrOCl2 solution with the concentration of 0.08 mol/L, hydrolyzing for 10min at 90 ℃, and carrying out heat treatment for 120min at 120 ℃ to obtain a zirconium oxide passivated tin oxide electron transport layer;
3. spin-coating MAPbI3 precursor on the tin oxide layer passivated by zirconia, drying by antisolvent, and carrying out heat treatment at 100 ℃ for 10min to form a perovskite thin film;
3. spin-coating Spiro-OMeTAD on the perovskite thin film as a hole transport layer;
4. and (4) evaporating Au on the hole transport layer in vacuum to form an electrode, thus obtaining the perovskite solar cell.
The photoelectric performance of the device is tested, and as shown in fig. 5, the cell has good performance and the photoelectric conversion efficiency is stabilized to be more than 16.7%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiments according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer is characterized in that the zirconium oxide passivated tin oxide is adopted as the electron transport layer of the perovskite solar cell.
2. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer according to claim 1 is characterized by comprising a transparent conductive substrate, the electron transport layer, a perovskite layer and an electrode which are arranged in sequence; or a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode which are arranged in sequence.
3. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer according to claim 1, wherein the electron transport layer is prepared by growing a zirconium oxide passivation layer on the surface of a tin oxide thin film in situ by a low-temperature solution method.
4. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer according to claim 1, wherein the thickness of the tin oxide layer in the zirconium oxide passivated tin oxide layer is 20-50 nm.
5. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer according to claim 1, wherein the thickness of the zirconium oxide layer in the zirconium oxide passivated tin oxide layer is 1-5 nm.
6. The perovskite solar cell with the zirconium oxide passivated tin oxide as the electron transport layer according to claim 1, wherein the preparation method of the zirconium oxide passivated tin oxide comprises the following steps:
step 1, immersing a conductive glass sheet into a stannous chloride aqueous solution with the concentration of 0.02-0.1 mol/L, and hydrolyzing for 30-120min at the temperature of 60-120 ℃;
step 2, taking out the sample, and immersing the sample in ZrOCl with the concentration of 0.01-0.1 mol/L2Hydrolyzing in water solution at 80-200 deg.C for 10-30 min;
and 3, after taking out the sample, carrying out heat treatment at the temperature of 150-.
7. A preparation method of a perovskite solar cell with zirconium oxide passivated tin oxide as an electron transport layer is characterized by comprising the following steps:
step 1), preparing a zirconium oxide passivated tin oxide layer on a transparent conductive substrate by adopting a low-temperature hydrolysis method;
step 2), preparing a perovskite film on the zirconium oxide passivated tin oxide layer by adopting an air extraction method or an anti-solvent method;
step 3), spin coating and naturally drying a device containing the hole transport layer to prepare the hole transport layer; step 4) of development without hole transport layer
Step 4), preparing the electrode by adopting a vacuum evaporation method for the metal electrode; and for the carbon electrode, coating carbon paste on the perovskite or hole transport layer by adopting a screen printing or scraper method, and then heating, curing and drying at 80-120 ℃ to obtain the perovskite solar cell taking the zirconium oxide passivated tin oxide as an electron transport layer.
8. The method for preparing a perovskite solar cell with zirconium oxide passivated tin oxide as an electron transport layer according to claim 7, wherein the step 1 specifically comprises:
step 1, immersing a conductive glass sheet into a stannous chloride aqueous solution with the concentration of 0.02-0.1 mol/L, and hydrolyzing for 30-120min at the temperature of 60-120 ℃;
step 2, taking out the sample, and immersing the sample in ZrOCl with the concentration of 0.01-0.1 mol/L2Hydrolyzing in water solution at 80-200 deg.C for 10-30 min;
and 3, after taking out the sample, carrying out heat treatment at the temperature of 150-.
9. The method according to claim 7, wherein the metal electrode is selected from Au, Ag, Al and Cu; the raw material of the carbon electrode, namely carbon slurry, is low-temperature slurry prepared by mixing a conductive material, a solvent and a binder.
10. The method for preparing a perovskite solar cell with zirconium oxide passivated tin oxide as an electron transport layer according to claim 8, characterized in that stannous chloride aqueous solution is passed through SnCl2 .6H2Mixing O with water or acid or hydrolysis inhibitor; ZrOCl2The aqueous solution is prepared by ZrOCl2·8H2O and water or acid or hydrolysis inhibitor.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505409A (en) * | 2014-12-24 | 2015-04-08 | 武汉大学 | SnO2 porous structure perovskite photovoltaic cell and preparation method thereof |
| CN106158997A (en) * | 2016-10-09 | 2016-11-23 | 天津市职业大学 | A kind of preparation method of doped tin oxide transparent conductive film |
| CN106784329A (en) * | 2017-01-12 | 2017-05-31 | 武汉大学 | A kind of SnO2Quantum dot electron transfer layer perovskite solar cell and preparation method thereof |
| CN109326721A (en) * | 2018-10-12 | 2019-02-12 | 河南理工大学 | A kind of the perovskite solar battery and its liquid phase preparation process of high stability |
| CN109980126A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Carrier transmission material, carrier transport film and its preparation method and application |
| CN110350089A (en) * | 2019-06-18 | 2019-10-18 | 华南理工大学 | Bi2O2S modifies SnO2The perovskite solar battery and preparation method of electron transfer layer |
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2020
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505409A (en) * | 2014-12-24 | 2015-04-08 | 武汉大学 | SnO2 porous structure perovskite photovoltaic cell and preparation method thereof |
| CN106158997A (en) * | 2016-10-09 | 2016-11-23 | 天津市职业大学 | A kind of preparation method of doped tin oxide transparent conductive film |
| CN106784329A (en) * | 2017-01-12 | 2017-05-31 | 武汉大学 | A kind of SnO2Quantum dot electron transfer layer perovskite solar cell and preparation method thereof |
| CN109980126A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Carrier transmission material, carrier transport film and its preparation method and application |
| CN109326721A (en) * | 2018-10-12 | 2019-02-12 | 河南理工大学 | A kind of the perovskite solar battery and its liquid phase preparation process of high stability |
| CN110350089A (en) * | 2019-06-18 | 2019-10-18 | 华南理工大学 | Bi2O2S modifies SnO2The perovskite solar battery and preparation method of electron transfer layer |
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