CN115295658A - Solvation-free all-inorganic perovskite solar cell and preparation method thereof - Google Patents
Solvation-free all-inorganic perovskite solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN115295658A CN115295658A CN202211026414.2A CN202211026414A CN115295658A CN 115295658 A CN115295658 A CN 115295658A CN 202211026414 A CN202211026414 A CN 202211026414A CN 115295658 A CN115295658 A CN 115295658A
- Authority
- CN
- China
- Prior art keywords
- target material
- layer
- solar cell
- target
- batio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 30
- -1 Bismuth iron chromium oxygen Chemical compound 0.000 claims abstract description 24
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001451 molecular beam epitaxy Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000013077 target material Substances 0.000 claims description 50
- 239000010408 film Substances 0.000 claims description 33
- 230000031700 light absorption Effects 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 16
- 230000005525 hole transport Effects 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 5
- 238000000926 separation method Methods 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
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 8
- 102100036822 Ankyrin repeat and KH domain-containing protein 1 Human genes 0.000 description 6
- 101000928335 Homo sapiens Ankyrin repeat and KH domain-containing protein 1 Proteins 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- JOOXLBAUOYFAPZ-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2].[Bi+3].[O-2].[O-2].[O-2] Chemical compound [O-2].[Cr+3].[Fe+2].[Bi+3].[O-2].[O-2].[O-2] JOOXLBAUOYFAPZ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a solvation-free all-inorganic perovskite solar cell and a preparation method thereof, which are based on NiO/BaTiO 3 Bismuth iron chromium oxygen/SnO 2 The heterostructure of the material is realized, proper energy level matching is realized among layers, and the built-in electric field of the heterojunction and the polarization electric field of the ferroelectric perovskite have a superposition effect, so that the electric field of a junction region is enhanced, the separation of electron-hole pairs is promoted, the recombination of the electron-hole pairs is reduced, the transport efficiency of current carriers is improved, and the battery has excellent performance. The all-inorganic perovskite solar cell is prepared by in-situ deposition through a laser molecular beam epitaxy technology, has strong controllability of growth conditions, small influence of external environmental factors in the preparation process, strong repeatability and simple method, and has important significance for application of inorganic photo-ferroelectric perovskite materials.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a solventless all-inorganic perovskite solar cell and a preparation method thereof.
Background
Governments around the world have adopted various policies and measures for the vigorous development of the solar energy industry, such as the european union's formulation of a "million roof solar energy plan", germany' a hundred thousand roof solar energy plan ", japan 'a new sunlight plan", and the united states california's release of a "million solar roof act". China puts forward large-scale development and high-quality development of comprehensively promoting wind power and solar power generation. This indicates that the development of the field of solar cells is of great interest, wherein the use of new materials is favored by researchers worldwide.
Currently, silicon solar cells have achieved 26.3% conversion efficiency, perovskite solar cells have achieved 25.7% photoelectric conversion efficiency, and the efficiency of full perovskite stacks has also entered 28% efficiency racetracks. However, the perovskite solar cell is expensive in raw material price, the light absorption layer has great instability, and the traditional solution spin coating method has low repeatability in device preparation due to factors such as environmental conditions. Currently, research on perovskite solar cells focuses on three aspects of reducing cost, improving efficiency and enhancing stability, and the main measures taken are as follows: attempts to add passivation layers between the transmission layer and the light-absorbing layer, optimization of doping of the light-absorbing layer, replacement of the light-absorbing layer material, preparation of the stack structure, and improvement in the manufacturing process. It can be seen that new perovskite solar cells are playing a great role in this field of application due to their unique advantages and potential for development.
Therefore, finding a perovskite light absorption layer material with high stability and a preparation process with controllable conditions and high effect repeatability is necessary for promoting the commercialization process of the perovskite light absorption layer material. Photo-ferroelectric perovskite solar cells are thus present in the field of view of researchers. Most of ferroelectric materials are inorganic materials with wider forbidden bands, and the charge mobility is lower, so that the photovoltaic efficiency is often very low, and the application in the aspect of energy is greatly limited. However, the band gap of the polyoxide solar cell can be tuned by adjusting the growth conditions and the element doping ratio. At present, the photo-ferroelectric perovskite material is used as a relatively stable inorganic substance, and has great development potential in the field of novel solar cell materials.
Disclosure of Invention
The invention aims to provide a solvent-free all-inorganic perovskite solar cell which is simple in preparation method, strong in growth condition controllability and excellent in performance.
The invention adopts the following technical scheme for realizing the purpose:
the invention firstly provides a solventless all-inorganic perovskite solar cell which is characterized in that: the solar cell takes FTO conductive glass as a substrate, and a material growth area and an anode connection area are arranged on a conductive layer of the FTO conductive glass at intervals; a NiO hole transport layer and BaTiO are sequentially deposited in the material growth zone from bottom to top 3 Auxiliary light absorption layer (BTO for short), bismuth iron chromium oxygen light absorption layer (BFCO for short), snO 2 An electron transport layer and an Ag electrode as a positive electrode; and taking the conductive layer of the FTO conductive glass as an anode layer of a battery, and depositing an Ag electrode as a negative electrode on the anode connecting area.
Further, the thickness of the NiO hole transport layer is 15-30nm, and the BaTiO is 3 The auxiliary light absorption layer has a thickness of 80-120nm, the bismuth iron chromium oxygen light absorption layer has a thickness of 180-220nm, and the SnO is 2 The thickness of the electron transmission layer is 8-15nm, and the thickness of the Ag electrode used as the anode and the thickness of the Ag electrode used as the cathode are both 50-80nm.
Existing perovskite battery devices or components generally employ a sandwich structure, i.e., a perovskite light absorbing material is sandwiched between a battery anode and a battery cathode. Wherein, the positive electrode or the negative electrode adopts a transparent electrode, so that illumination can be absorbed by the perovskite material through the electrode. However, the light transmittance of the current transparent electrode is generally less than 90%, so that the light absorption efficiency of the perovskite solar cell has a loss of more than 10%. The back contact type solar cell adopts the distribution mode of different electrodes and perovskite light absorption materials, namely, the positive electrode and the negative electrode are positioned on one side of perovskite, so that 100% of the perovskite light absorption materials can receive illumination from the other side. Considering the device manufacturing process and the utilization efficiency comprehensively, as shown in fig. 1, the device of the present invention finally receives light from the FTO glass side.
Further, the component of the BFCO light absorption layer is Bi 2 FeCrO 6 . After the bismuth, iron, chromium and oxygen are optimized by element proportion, the forbidden band width is greatly reduced, but the light is absorbedThe wave band is still limited, so BaTiO is added 3 The film is used as an auxiliary light absorption layer to improve ferroelectric property. BaTiO 2 3 The forbidden band width exceeds 3eV, so that a small part of visible light can be absorbed, and the forbidden band width is complementary with the bismuth iron chromium oxygen light absorption wave band, thereby improving the utilization efficiency of each wave band.
Further, the NiO hole transport layer and the BaTiO 3 Auxiliary light absorption layer, bismuth iron chromium oxygen light absorption layer and SnO 2 The electron transport layer is obtained by in-situ deposition by adopting a laser molecular beam epitaxy (L-MBE) technology.
The invention also discloses a preparation method of the solvent-free all-inorganic perovskite solar cell, which comprises the following steps:
(a) Fixing the cleaned FTO conductive glass on a sample holder, and then transmitting the FTO conductive glass into a sample table of a deposition chamber in a laser molecular beam epitaxy system for later use;
(b) Preparing NiO target and BaTiO 3 The target material fixing device comprises a target material fixing device, a target material support and a target material conveying device, wherein the target material fixing device is used for fixing two target materials on the target material support and then conveying the target materials into a target material table of a deposition chamber for later use;
(c) Bombarding the NiO target by laser to sputter so as to deposit a layer of NiO film on the material growth area of the substrate;
(d) Bombardment of BaTiO with laser 3 Sputtering the target to deposit a layer of BaTiO on the NiO film 3 A film;
(e) Preparing bismuth iron chromium oxygen target material and SnO 2 The target material fixing device comprises a target material fixing device, a target material support and a target material conveying device, wherein the target material fixing device is used for fixing two target materials on the target material support and then conveying the target materials into a target material table of a deposition chamber for later use;
(f) Bombarding the bismuth iron chromium oxygen target material by laser to enable BaTiO 3 Depositing a bismuth iron chromium oxide film on the film;
(g) Bombardment of SnO with laser 2 Target material, depositing a layer of SnO on the bismuth-iron-chromium-oxygen film 2 Thin films, i.e. formed on the basis of NiO/BaTiO 3 Bismuth iron chromium oxygen/SnO 2 A heterostructure of materials;
(h) At SnO 2 And simultaneously evaporating and plating the film and the anode connecting area of the FTO conductive glass to be used as an anode and an Ag electrode as a cathode, thus obtaining the solvent-free all-inorganic perovskite solar cell.
Compared with the prior art, the invention has the beneficial effects that:
1. the all-inorganic perovskite solar cell is based on NiO/BaTiO 3 Bismuth iron chromium oxygen/SnO 2 The material has a heterostructure, proper energy level matching is realized among layers, and NiO and SnO can be fully exerted 2 The advantages of the material in the aspect of carrier transmission are fully utilized by BaTiO 3 The spontaneous polarization mechanism of the bismuth iron chromium oxygen ferroelectric property and the superposition of the heterojunction built-in electric field and the ferroelectric perovskite polarization electric field enhance the junction electric field, promote the separation of electron-hole pairs, reduce the recombination of the electron-hole pairs, improve the transport efficiency of current carriers and enable the battery to have excellent performance.
2. The all-inorganic perovskite solar cell is prepared by in-situ deposition through a laser molecular beam epitaxy technology, the growth condition is high in controllability, the thickness of the film is accurate and controllable, the obtained film is high in compactness, each layer of film is good in contact, the preparation process is slightly influenced by external environment factors, the repeatability is high, the method is simple, and the all-inorganic perovskite solar cell has important significance for application of inorganic photo-ferroelectric perovskite materials.
Drawings
Fig. 1 is a schematic structural diagram of a solar cell according to the present invention.
FIG. 2 is a schematic diagram of the separation of the conductive layer of the FTO conductive glass into a material growth area and an anode connection area by using a mask.
Fig. 3 is a schematic diagram showing relative positions of energy band structures of layers of the solar cell according to the present invention.
Fig. 4 is a schematic view of the internal carrier transport direction of the solar cell according to the present invention.
Fig. 5 is a graph of atomic force microscopy test data for BFCO films prepared in example 1 of the present invention.
FIG. 6 is a diagram of a reticle used to plate an electrode.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1
As shown in fig. 1, the solvation-free all-inorganic perovskite solar cell of the embodiment uses FTO conductive glass as a substrate, and a material growth region and an anode connection region are arranged on a conductive surface of the FTO conductive glass at intervals; a NiO hole transport layer and BaTiO are deposited in the material growth zone from bottom to top in sequence 3 Auxiliary light absorption layer (BTO for short), bismuth iron chromium oxygen light absorption layer (BFCO for short), snO 2 An electron transport layer and an Ag electrode as a positive electrode; and taking a conductive layer of FTO conductive glass as an anode layer of the battery, and depositing an Ag electrode as a negative electrode on the anode connecting area. The preparation method comprises the following steps:
1. putting FTO conductive glass (square resistance is 15 omega) with the size of 10 multiplied by 1.6mm into a polytetrafluoroethylene cleaning frame, integrally putting into a beaker, adding acetone until the substrate is just completely submerged, and cleaning for 15min in an ion cleaning machine; after the instrument is stopped, taking out the beaker for replacing, adding ethanol until the substrate is just completely submerged, and cleaning for 15min in an ion cleaning machine; after the instrument is stopped, taking out the replacement beaker, adding deionized water until the substrate is just completely submerged, and cleaning for 15min in an ion cleaning machine; and blowing off the residual solution of the substrate by using a nitrogen gun after the three steps of cleaning.
2. And fixing the cleaned FTO conductive glass substrate on a sample holder, and then conveying the FTO conductive glass substrate into a sample stage of a deposition chamber for later use.
3. Preparing NiO target and BaTiO 3 Target materials (all specifications are
99.99%) and then the two targets are fixed on a target holder and then are conveyed into a target table of a deposition chamber for standby.
4. And (3) carrying out heating pretreatment on the substrate, starting a heating system, and heating to 280 ℃. Preheating at 280 deg.C for 10min, starting laser, setting dotting frequency to 1Hz, and adjusting laser energy density to 1.5J/cm 2 (ii) a Starting an oxygen pressure system while preheating the substrate, and adjusting the oxygen pressure to 1.3Pa; bombarding NiO target material with laser, starting dotting deposition, and finishing deposition after 18minDepositing to obtain a NiO film with the thickness of about 20nm on the substrate; and (4) closing the oxygen pressure system, annealing at the constant temperature of 300 ℃ for 40min, then closing the heating system, and naturally cooling to room temperature.
5. Starting a heating system, adjusting the temperature to 600 ℃, and preheating for 10min; the laser is started, the dotting frequency is set to be 4Hz, and the laser energy density is still set to be 1.5J/cm 2 Bombardment of BaTiO with laser 3 Sputtering the target to deposit a layer of BaTiO on the NiO film 3 Film, finishing deposition after 20min to obtain BaTiO 3 The thickness of the film is about 100 nm. And (4) closing the oxygen pressure system, annealing at the constant temperature of 600 ℃ for 40min, then closing the heating system, and naturally cooling to room temperature.
6. Preparation of Bi 2 FeCrO 6 Target material and SnO 2 Target materials (all specifications are
99.99%) and then the two targets are fixed on a target holder and then are conveyed into a target table of a deposition chamber for standby.
Starting a heating system, adjusting the temperature to 600 ℃, and preheating for 10min; starting a laser, setting the dotting frequency to be 4Hz and the laser energy density to be 2J/cm 2 While preheating the substrate, starting an oxygen pressure system, adjusting the oxygen pressure to 0.2Pa, and bombarding Bi by laser 2 FeCrO 6 Sputtering the target material to ensure that BaTiO 3 Depositing a layer of Bi on the film 2 FeCrO 6 Film, finishing deposition after 60min to obtain Bi 2 FeCrO 6 The thickness of the film is about 200 nm. And closing the oxygen pressure system, annealing at the constant temperature of 600 ℃ for forty minutes, closing the heating system, and naturally cooling to room temperature.
7. Starting a heating system, adjusting the temperature to 280 ℃, and preheating for 10min; starting the laser, setting the dotting frequency to be 1Hz, and setting the laser energy density to be 2J/cm 2 Bombardment of SnO with laser 2 Target material of Bi 2 FeCrO 6 Depositing a layer of SnO on the film 2 Film, deposition is finished after 15min, snO 2 The thickness of the film is about 10 nm. And closing the heating system, and naturally cooling to room temperature. Finally obtaining the productBased on NiO/BaTiO 3 Bismuth iron chromium oxygen/SnO 2 Heterostructures of materials.
8. And (3) putting the sample prepared in the step (7) on a mask with a designed electrode pattern, putting the mask into a film plating machine for electrode evaporation, selecting a silver (Ag) metal material, controlling the film plating rate in a current adding mode, controlling the final electrode thickness to be about 75nm, and taking 90min for the whole electrode plating operation.
Specifically, the method comprises the following steps:
the specific steps for turning on the heating system for steps 4, 5, 6, 7 are: starting a circulating water system, and focusing whether the heating light spot and the temperature control sensing point are in the central area of the sample holder or not; starting the heating system, adjusting the current to 8A, adjusting the temperature control system to be in a PID mode after the temperature reaches 160 ℃, setting the temperature, and increasing the temperature to the target temperature at the speed of 50 ℃/min.
The specific steps for turning off the heating system for steps 4, 5, 6, 7 are: adjusting the temperature control system to be in a Manual mode, and adjusting the current to be 5.9A at the lowest value; after the reading is reduced to 160 ℃, closing the heating system; closing the circulating water system; and waiting for the sample in the main cavity to naturally cool to the room temperature.
The specific steps for starting the oxygen pressure system in the steps 4 and 6 are as follows: closing the vacuum silicon in the main cavity and the main valve of the molecular pump, and adjusting the rotating Speed of the molecular pump to be in a Low Speed mode after the display is stable; opening an oxygen valve to enable a pointer of a pressure gauge in an oxygen passage to be displayed near 0.1 Pa; the micro-leakage valve is rotated anticlockwise to slowly adjust the oxygen pressure until the indication of the oxygen pressure in the main cavity reaches the required oxygen pressure condition.
The specific steps for turning off the oxygen pressure system in steps 4 and 6 are as follows: slowly rotating the micro-leakage valve clockwise until the micro-leakage valve is parallel to the lower datum line; closing the oxygen valve; and regulating the rotating speed of the molecular pump to be in a normal mode, and opening a main valve of the molecular pump.
For the relevant data set when material deposition is performed: the sample table is not rotated; the autorotation speed of the target holder is 20r/min; when the material grows each time, firstly, a baffle between the target material and the sample is opened, the target material is bombarded by laser to carry out pre-sputtering for 3min, then the baffle is returned, and the material sputtering growth is continued.
Control of the material growth area: because two sets of MASK combined type shielding growth multi-element combined films are arranged in a main cavity of a Laser molecular beam epitaxy system (Laser-MBE), only one set of MASK combined type shielding growth multi-element combined film is needed in the experiment. The control motor before heating drives the MASK1 edge to move to be flush with one side of the sample, the position (x) mm of the MASK1 at this time is recorded, and then the MASK1 is retracted. When deposition is started, MASK1 is driven to shield, and the shielding position value is (x + 4) mm. After the material deposition was complete, no material was grown in the left 4 × 10mm area of the sample, exposing the FTO surface for subsequent connection to the other side electrode.
Fig. 1 is a schematic structural diagram of a solar cell according to the present invention, in which a back electrode structure is adopted, light is incident from one side of FTO conductive glass, an electron-hole pair separation is excited in a light-absorbing layer material, and electrons are transmitted to an external circuit through an electrode via a tin dioxide electron transport layer, so as to generate a current, thereby realizing the function of the solar cell.
FIG. 2 is a schematic diagram of using MASK1 to control the material growth region, wherein MASK1 is located between the target and the sample, and the target cannot be sputtered in the covered region by aligning and shielding, thereby exposing the FTO conductive glass substrate.
Fig. 3 and fig. 4 are mechanism supports of the cell structure of the present invention, and it can be seen that the nickel oxide, barium titanate, bismuth iron chromium oxygen, and tin dioxide are energy level matched between layers, which is suitable for carrier transport, and can perform related functions as a solar cell. Barium titanate is used as an auxiliary light absorption layer and is cooperated with bismuth, iron, chromium and oxygen of a main light absorption layer, a spontaneous polarization mechanism of ferroelectric properties of two materials is fully utilized, and a built-in electric field of a multilayer heterostructure and a ferroelectric perovskite polarization electric field are superposed to enhance a junction electric field, promote separation of electron-hole pairs, reduce recombination of the electron-hole pairs and improve the transport efficiency of current carriers.
Fig. 5 is a graph of atomic force microscopy test data for the BFCO thin film prepared in example 1.
FIG. 6 is a mask for vapor deposition of an electrode, in which a prepared sample is placed in a tank and integrally fixed in a coater to perform an electrode plating operation. The cell prepared as shown in the figure has a common negative electrode, and 3 counter electrodes are positive electrodes.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A solventless all inorganic perovskite solar cell characterized by: the solar cell takes FTO conductive glass as a substrate, and a material growth area and an anode connection area are arranged on a conductive layer of the FTO conductive glass at intervals; a NiO hole transport layer and BaTiO are deposited in the material growth zone from bottom to top in sequence 3 Auxiliary light absorption layer, bismuth iron chromium oxygen light absorption layer, snO 2 An electron transport layer and an Ag electrode as a positive electrode; and taking the conductive layer of the FTO conductive glass as an anode layer of a battery, and depositing an Ag electrode as a negative electrode on the anode connecting area.
2. The solventless, all-inorganic perovskite solar cell of claim 1, wherein: the thickness of the NiO hole transport layer is 15-30nm, and the BaTiO layer 3 The auxiliary light absorption layer has a thickness of 80-120nm, the bismuth iron chromium oxygen light absorption layer has a thickness of 180-220nm, and the SnO 2 The thickness of the electron transmission layer is 8-15nm, and the thickness of the Ag electrode used as the anode and the Ag electrode used as the cathode are both 50-80nm.
3. The solventless, all-inorganic perovskite solar cell of claim 1, wherein: the NiO hole transport layer and the BaTiO 3 Auxiliary light absorption layer, bismuth iron chromium oxygen light absorption layer and SnO 2 The electron transport layer is obtained by in-situ deposition by adopting a laser molecular beam epitaxy technology.
4. The solventless, all-inorganic perovskite solar cell of claim 1, wherein: the component of the bismuth iron chromium oxygen light absorption layer is Bi 2 FeCrO 6 。
5. A method for preparing the unsolvated all-inorganic perovskite solar cell according to any one of claims 1 to 4, characterized by comprising the following steps:
(a) Fixing the cleaned FTO conductive glass on a sample holder, and then transmitting the FTO conductive glass into a sample table of a deposition chamber in a laser molecular beam epitaxy system for later use;
(b) Preparing NiO target and BaTiO 3 The target material fixing device comprises a target material fixing device, a target material support and a target material conveying device, wherein the target material fixing device is used for fixing two target materials on the target material support and then conveying the target materials into a target material table of a deposition chamber for later use;
(c) Bombarding the NiO target by laser to sputter so as to deposit a layer of NiO film on the material growth area of the substrate;
(d) Bombardment of BaTiO with laser 3 Sputtering the target to deposit a layer of BaTiO on the NiO film 3 A film;
(e) Preparing bismuth iron chromium oxygen target material and SnO 2 The target material fixing device comprises a target material fixing device, a target material support and a target material conveying device, wherein the target material fixing device is used for fixing two target materials on the target material support and then conveying the target materials into a target material table of a deposition chamber for later use;
(f) Bombarding bismuth iron chromium oxygen target material by laser to enable BaTiO 3 Depositing a bismuth-iron-chromium-oxygen film on the film;
(g) Bombardment of SnO with laser 2 Target material, depositing a layer of SnO on the bismuth-iron-chromium-oxygen film 2 Thin films, i.e. formed on the basis of NiO/BaTiO 3 Bismuth iron chromium oxygen/SnO 2 A heterostructure of materials;
(h) At SnO 2 And simultaneously evaporating Ag electrodes serving as a positive electrode and a negative electrode on the film and an anode connecting area of the FTO conductive glass, thus obtaining the solvent-free all-inorganic perovskite solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211026414.2A CN115295658A (en) | 2022-08-25 | 2022-08-25 | Solvation-free all-inorganic perovskite solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211026414.2A CN115295658A (en) | 2022-08-25 | 2022-08-25 | Solvation-free all-inorganic perovskite solar cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115295658A true CN115295658A (en) | 2022-11-04 |
Family
ID=83832119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211026414.2A Pending CN115295658A (en) | 2022-08-25 | 2022-08-25 | Solvation-free all-inorganic perovskite solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115295658A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116322083A (en) * | 2023-05-16 | 2023-06-23 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
-
2022
- 2022-08-25 CN CN202211026414.2A patent/CN115295658A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116322083A (en) * | 2023-05-16 | 2023-06-23 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
| CN116322083B (en) * | 2023-05-16 | 2023-11-24 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20020063065A1 (en) | Method of forming zinc oxide film and process for producing photovoltaic device using it | |
| US20130045563A1 (en) | Method and device for producing a semiconductor layer | |
| EP2876696B1 (en) | Method for preparing copper indium gallium selenide film solar cell | |
| Heo et al. | Fabrication of titanium-doped indium oxide films for dye-sensitized solar cell application using reactive RF magnetron sputter method | |
| CN115295658A (en) | Solvation-free all-inorganic perovskite solar cell and preparation method thereof | |
| CN109309136B (en) | Ultra-thin MgO layer modified Cu2O-plane heterojunction solar cell | |
| CN102312201B (en) | Preparation method of Al-doped zinc oxide transparent conductive thin film | |
| US20230387342A1 (en) | Method for preparing electrode film layer on surface of solar cell substrate | |
| CN102956722B (en) | Thin-film solar cell | |
| CN112951933A (en) | Method for preparing copper-zinc-tin-sulfur/bismuth sulfide film heterojunction by room temperature pulse laser deposition method | |
| CN111668340A (en) | Cd (cadmium)3Cl2O2Thin film, preparation method thereof and thin film solar cell | |
| KR20100085769A (en) | Cds/cdte thin film solar cells and manufacturing method thereof | |
| KR100936487B1 (en) | Manufacturing method of cds/cdte thin film solar cells | |
| CN101980368A (en) | Copper indium gallium selenide film battery and preparation method thereof | |
| CN114583064A (en) | Preparation method of photovoltaic device based on magnetron sputtering perovskite light absorption layer | |
| CN101101931A (en) | Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method | |
| CN109037390A (en) | A kind of cadmium stannate base transparent conductive film, its production technology and solar battery | |
| CN107293605A (en) | Back electrode of solar cell and solar cell and preparation method thereof | |
| CN106098858A (en) | A kind of cadmium telluride preparation method of solar battery | |
| CN112331729A (en) | Light absorption layer of CIGS thin-film solar cell and forming method thereof | |
| CN205205219U (en) | Evaporate device that sputter mixes | |
| CN110071218B (en) | Method for preparing lead-free perovskite film through electrodeposition | |
| CN117098437A (en) | Perovskite/crystalline silicon laminated solar cell and preparation method thereof | |
| CN221777986U (en) | Coating equipment | |
| CN113193122B (en) | Perovskite thin film based on PbCl2 buffer layer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |