CN116171053B - Full perovskite laminated solar cell and preparation method thereof - Google Patents
Full perovskite laminated solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN116171053B CN116171053B CN202310276686.6A CN202310276686A CN116171053B CN 116171053 B CN116171053 B CN 116171053B CN 202310276686 A CN202310276686 A CN 202310276686A CN 116171053 B CN116171053 B CN 116171053B
- Authority
- CN
- China
- Prior art keywords
- transport layer
- hole transport
- perovskite
- solar cell
- layer
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000005525 hole transport Effects 0.000 claims description 74
- 238000004528 spin coating Methods 0.000 claims description 68
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 38
- 238000000137 annealing Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- 238000010521 absorption reaction Methods 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 25
- 230000004888 barrier function Effects 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 230000005540 biological transmission Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid Chemical compound 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims 1
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 238000004544 sputter deposition Methods 0.000 description 20
- 239000012296 anti-solvent Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 238000002207 thermal evaporation Methods 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000003949 trap density measurement Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Photovoltaic Devices (AREA)
Abstract
The application discloses a full perovskite laminated solar cell and a preparation method thereof, and belongs to the technical field of solar cells. The full perovskite laminated solar cell can effectively solve the problems of complex preparation process, high cost, serious interface non-radiative recombination and the like of the traditional laminated solar cell.
Description
Technical Field
The application belongs to the technical field of solar cells, and particularly relates to a full perovskite laminated solar cell and a preparation method thereof.
Background
Solar cells are an important place in the existing energy structures as a device that can directly convert solar energy into electrical energy. Among them, perovskite solar cells have received attention because of their outstanding photoelectric properties and simple production processes. Currently, the authentication efficiency of single junction perovskite solar cells has broken through 25.7%, but the improvement of the efficiency is limited by the Shore-Kui-Ever (S-Q) limit (-33%). In order to fully utilize solar spectrum and reduce heat dissipation of the battery, the S-Q limit of a single junction device is broken through, and the multi-junction laminated perovskite solar battery is developed.
The two-terminal perovskite-perovskite (full perovskite) stacked solar cell is generally composed of a wide bandgap (1.7-1.9 eV) top cell and a narrow bandgap (1.0-1.3 eV) bottom cell. While the efficiency of all perovskite stacked solar cells has exceeded that of single junction perovskite solar cells, severe interfacial non-radiative recombination has limited further improvement in their performance. To reduce such losses and manufacturing costs, it is important to select an appropriate hole transport material. The hole transport layer materials with wide band gap and narrow band gap in the full perovskite laminated solar cell disclosed in the prior art are usually PTAA and PEDOT respectively, namely, different hole transport layer materials are respectively adopted in two sub-cells in the full perovskite laminated solar cell in the prior art, so that the preparation process of the cell is more complex, the production cost is increased, and the requirements on equipment and environment are higher; in addition, the PEDOT in the prior art has stronger parasitic absorption to near infrared light by the PSS hole transport layer, and the acidity of the PSS hole transport layer can cause degradation of a perovskite film with a narrow band gap, which is not beneficial to the stability of a laminated device; furthermore, the hole transport layer/perovskite thin film interface has serious interface non-radiative recombination problems.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides a full perovskite laminated solar cell and a preparation method thereof, and the full perovskite laminated solar cell can effectively solve the problems of complex preparation process, high cost and serious interface non-radiation recombination existing in the conventional laminated solar cell.
In order to achieve the above purpose, the technical scheme adopted by the application for solving the technical problems is as follows:
a hole transport layer material in a wide bandgap top cell is the same as a hole transport layer material in a narrow bandgap bottom cell.
Further, the hole transport layer material is a material having self-assembly characteristics.
Further, the material having self-assembly properties is a phosphate-terminated SAM material, a carboxylic acid-terminated SAM material, a sulfuric acid-terminated SAM material, or an isocyanate-terminated SAM material.
Further, the hole transport layer material is 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid.
Further, the thickness of the hole transport layer in the wide bandgap top cell and the hole transport layer in the narrow bandgap bottom cell are both 3-15nm.
The preparation method of the full perovskite laminated solar cell comprises the following steps:
(1) Dissolving a hole transport layer material in a solvent to prepare a hole transport layer precursor solution;
(2) Spin-coating the hole transport layer precursor solution in the step (1) on ITO transparent conductive glass, and carrying out annealing treatment to obtain a hole transport layer of the wide-bandgap top battery;
(3) Sequentially depositing a wide band gap perovskite absorption layer, an electron transport layer and an intermediate connection layer on the hole transport layer of the wide band gap top cell in the step (2);
(4) Spin-coating the hole transport layer precursor solution in the step (1) on the intermediate connecting layer in the step (3), and carrying out annealing treatment to obtain a hole transport layer of the narrow band gap bottom cell;
(5) And (3) sequentially depositing a narrow band gap perovskite absorption layer, an electron transmission layer and a metal electrode on the hole transmission layer of the narrow band gap bottom cell in the step (4) to prepare the full perovskite laminated solar cell.
The deposition modes such as the wide band gap perovskite absorption layer, the electron transport layer, the intermediate connection layer, the narrow band gap perovskite absorption layer, the metal electrode and the like in the application can be carried out according to the conventional method in the field unless the deposition modes are specifically described, and the components or the raw materials in the field can be selected if the components or the raw materials are not specifically limited or specifically described.
Further, in the step (1), the solvent is toluene, ethanol, isopropanol, deionized water or diethyl ether, and the concentration of the hole transport layer precursor solution is 0.3-0.8mg/mL.
Further, the spin-coating parameters in the step (2) and the step (4) are the same, specifically: the spin coating speed is 3000-5000rpm, and the spin coating time is 20-40s.
Further, the annealing parameters in the step (2) and the step (4) are the same, specifically: the annealing temperature is 80-130 ℃, and the annealing time is 5-20min.
Further, the electron transport layer in step (3) is composed of C 60 Or C 70 A transport layer and a tin dioxide barrier layer, wherein in the step (5), the electron transport layer consists of C 60 Or C 70 A transport layer and a tin dioxide barrier layer, or C 60 Or C 70 A transport layer and a BCP barrier layer.
Further, in the step (3), the intermediate connection layer is made of IZO (zinc indium oxide) or ITO (indium tin oxide) or AZO (zinc aluminum oxide) or Au, and in the step (5), the metal electrode is made of Cu or Ag.
The beneficial effects of the application are as follows:
1. the application applies the same hole transport layer material to the two sub-cells with wide and narrow band gaps at the same time, simplifies the preparation process of the laminated solar cell, reduces the requirements on production equipment and preparation technology, has more obvious advantages especially when preparing large-area devices or components by roll-to-roll and slit coating, greatly reduces the investment of manpower, material resources and financial resources, and has great significance for reducing the preparation cost of the laminated devices and accelerating the mass production.
2. In the application, materials with self-assembly characteristics such as donor-acceptor P type molecules and the like are adopted to replace PTAA materials in a wide bandgap sub-cell and PEDOT/PSS materials in a narrow bandgap sub-cell in a laminated perovskite solar cell as hole transport layers in a laminated device, and the main working principle is as follows: firstly, the self-assembled hole transport layer has good hole extraction performance, so that effective transfer and extraction of holes are ensured; secondly, because the thickness of the self-assembled hole transport layer is extremely thin, after being deposited on the ITO surface, the self-assembled hole transport layer has better light transmittance than PTAA and PEDOT: PSS, and can improve the effective utilization of the perovskite film to sunlight; third, in a wide bandgap top cell, compared to the HOMO level of PTAA,the HOMO energy level of the self-assembled material is more matched with the valence band of the wide bandgap perovskite, which is beneficial to reducing the interface energy level barrier of hole transmission, accelerating the extraction of holes and reducing energy loss; in the narrow bandgap bottom cell, the self-assembled hole transport layer not only can reduce non-radiative recombination at the interface, but also can react with Sn 2+ The strong interaction between the tin and lead narrow-band gap perovskite thin film and the preparation method improves the crystallization kinetics of the tin and lead narrow-band gap perovskite thin film by delaying the crystallization speed of the tin and lead narrow-band gap perovskite, so that the high-quality tin and lead narrow-band gap perovskite thin film with higher crystallinity and lower defect state density is prepared. In conclusion, the hole transport layer greatly improves the photoelectric conversion efficiency of the two sub-cells, so that a laminated perovskite solar cell with higher efficiency and stability can be prepared.
3. The hole transmission layer in the application effectively improves the problems of low near infrared light transmittance of the intermediate connection layer and easy degradation and oxidation of the perovskite film in the all-perovskite laminated solar cell, mainly because the self-assembled hole transmission layer used in the application has extremely thin thickness of 3-15nm, the absorption and emission of sunlight can be reduced, thereby reducing the loss of sunlight, being beneficial to more sunlight irradiation to the surface of the perovskite film, enhancing the full utilization of sunlight by two sub-cells, particularly reducing the parasitic absorption of near infrared light by the intermediate connection layer, improving the quality of the narrow-band-gap perovskite film, and enhancing the stability of the device while improving the photoelectric conversion efficiency of the device.
In addition, the hole transport layer is extremely thin and has high tolerance to uneven film thickness, the hole transport layer material is more orderly arranged after being anchored on the ITO surface through the anchoring group, and the arrangement orientation is more parallel to the ITO, so that the extraction and transfer rate of holes can be effectively improved. In the prior art, the conventional hole transport layers such as PTAA, PEDOT, PSS and the like are arranged on the ITO surface in a disordered manner, and the hole extraction and transfer capability is poor.
Drawings
FIG. 1 is a schematic diagram of a prior art all perovskite stacked solar cell structure;
FIG. 2 is a schematic diagram of a full perovskite stacked solar cell structure according to the present application;
FIG. 3 is a graph showing the ultraviolet-visible transmission spectrum of the wide bandgap top cell of example 3 and comparative example 1;
FIG. 4 is a graph showing the ultraviolet-visible transmission spectrum of the narrow bandgap bottom cell of example 3 and comparative example 1;
FIG. 5 is a J-V plot of the all perovskite stacked solar cell of comparative example 1;
fig. 6 is a J-V plot of the all perovskite stacked solar cell in example 3.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the application, i.e., the embodiments described are merely some, but not all, of the embodiments of the application.
Thus, the following detailed description of the embodiments of the application, as provided, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application.
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The features and capabilities of the present application are described in further detail below with reference to the examples and figures.
Example 1
The preparation method of the all-perovskite laminated solar cell comprises the following steps:
(1) Dissolving 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid material in toluene to prepare a hole transport layer precursor solution having a concentration of 0.3 mg/mL;
(2) Spin-coating the hole transport layer precursor solution in the step (1) on the cleaned ITO transparent conductive glass, wherein the spin-coating speed is 4000rpm, the spin-coating time is 40s, and then annealing treatment is carried out, wherein the annealing temperature is 80 ℃, and the annealing time is 20min, so that the hole transport layer with the thickness of 6nm is prepared;
(3) Adopting an anti-solvent method to drop a widened band gap perovskite precursor solution on the hole transport layer prepared in the step (2) for spin coating, carrying out low-speed spin coating at 300rpm for 10s, high-speed spin coating at 2000rpm for 60s, dropping anti-solvent diethyl ether at 30 seconds during the high-speed spin coating, and then annealing at 50 ℃ for 8min and at 90 ℃ for 17min in sequence to prepare a wide band gap perovskite absorption layer;
(4) Depositing C with the thickness of 20nm on the wide-bandgap perovskite absorption layer prepared in the step (3) by adopting a thermal evaporation method 60 The transmission layer comprises the following specific operations: turning on power supply to slowly heat C 60 To a temperature above 530 ℃ to make the evaporation rate atUntil the deposition thickness reaches 20nm; then deposit on C by atomic layer 60 The electron transport layer is deposited with a tin dioxide barrier layer with the thickness of 20nm, and the specific operation is as follows: setting the temperature of the deposition chamber to 90 ℃, the pulse time of a tin source to 100ms, the cleaning time to 30s, and the pulse time of a water sourceThe time is 100ms, and the cleaning time is 30s;
(5) Sputtering an IZO film with the thickness of 120nm on the tin dioxide barrier layer prepared in the step (4) by adopting a radio frequency magnetron sputtering method, wherein the specific parameters are as follows: the sputtering power is 70W, the sputtering air pressure is 0.5Pa, the argon flow is 30sccm, and the sputtering time is controlled to adjust the sputtering thickness;
(6) Spin-coating the IZO film prepared in the step (5) with a hole transport layer precursor solution in the step (1) at a spin-coating speed of 4000rpm for 40s, and then annealing at 80 ℃ for 20min to obtain a hole transport layer with a thickness of 6 nm;
(7) Spin-coating a narrow band gap perovskite absorption layer on the hole transport layer prepared in the step (6) by adopting an anti-solvent method, wherein the spin-coating time is 20s, the spin-coating time is 4000rpm, the spin-coating time is 60s, anti-solvent chlorobenzene is dripped in 15 seconds during the high-speed spin-coating, and then annealing is carried out for 20min at 80 ℃ and 20min at 50 ℃ in sequence to prepare the narrow band gap perovskite absorption layer;
(8) Depositing C with the thickness of 20nm on the narrow-band gap perovskite absorption layer prepared in the step (7) by adopting a thermal evaporation method 60 A transport layer and a 20nm thick tin dioxide barrier layer;
(9) And (3) depositing a copper electrode with the thickness of 100nm on the tin dioxide barrier layer prepared in the step (8) by adopting a thermal evaporation method to prepare the full perovskite laminated solar cell.
Example 2
The preparation method of the all-perovskite laminated solar cell comprises the following steps:
(1) Dissolving 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid material in toluene to prepare a hole transport layer precursor solution at a concentration of 0.8 mg/mL;
(2) Spin-coating the hole transport layer precursor solution in the step (1) on the cleaned ITO transparent conductive glass, wherein the spin-coating speed is 5000rpm, the spin-coating time is 20s, and then annealing treatment is carried out, wherein the annealing temperature is 130 ℃, and the annealing time is 5min, so that the hole transport layer with the thickness of 15nm is prepared;
(3) Adopting an anti-solvent method to drop a widened band gap perovskite precursor solution on the hole transport layer prepared in the step (2) for spin coating, spin coating at a low speed of 800rpm for 2s, spin coating at a high speed of 4000rpm for 30s, dropping anti-solvent diethyl ether at the 30 th second during the high speed spin coating, and then annealing at 70 ℃ for 2min and 130 ℃ for 8min in sequence to prepare a wide band gap perovskite absorption layer;
(4) Depositing C with the thickness of 20nm on the wide-bandgap perovskite absorption layer prepared in the step (3) by adopting a thermal evaporation method 70 The transmission layer comprises the following specific operations: turning on power supply to slowly heat C 70 To a temperature above 530 ℃ to make the evaporation rate atUntil the deposition thickness reaches 20nm; then deposit on C by atomic layer 70 The electron transport layer is deposited with a tin dioxide barrier layer with the thickness of 20nm, and the specific operation is as follows: setting the temperature of a deposition chamber to 90 ℃, the pulse time of a tin source to be 100ms, the cleaning time to be 30s, the pulse time of a water source to be 100ms and the cleaning time to be 30s;
(5) Sputtering an IZO film with the thickness of 120nm on the tin dioxide barrier layer prepared in the step (4) by adopting a radio frequency magnetron sputtering method, wherein the specific parameters are as follows: the sputtering power is 70W, the sputtering air pressure is 0.5Pa, the argon flow is 30sccm, and the sputtering time is controlled to adjust the sputtering thickness;
(6) Spin-coating the IZO film prepared in the step (5) with a hole transport layer precursor solution in the step (1) at a spin-coating speed of 5000rpm for 20s, and then annealing at 130 ℃ for 5min to obtain a hole transport layer 15min thick;
(7) Spin-coating a narrow band gap perovskite absorption layer on the hole transport layer prepared in the step (6) by adopting an anti-solvent method, wherein the spin-coating time is 8s, the spin-coating time is 7000rpm, the spin-coating time is 30s, anti-solvent chlorobenzene is dripped in 15 seconds during the high-speed spin-coating, and then annealing is carried out for 10min at 120 ℃ and 10min at 60 ℃ in sequence to prepare the narrow band gap perovskite absorption layer;
(8) In step (7) by thermal evaporationC with the thickness of 20nm is sequentially deposited on the prepared narrow-band gap perovskite absorption layer 60 A transport layer and a 20nm thick BCP barrier layer;
(9) And (3) depositing a copper electrode with the thickness of 100nm on the tin dioxide barrier layer prepared in the step (8) by adopting a thermal evaporation method to prepare the full perovskite laminated solar cell.
Example 3
The preparation method of the all-perovskite laminated solar cell comprises the following steps:
(1) Dissolving 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid material in toluene to prepare a hole transport layer precursor solution at a concentration of 0.5 mg/mL;
(2) Spin-coating the hole transport layer precursor solution in the step (1) on the cleaned ITO transparent conductive glass, wherein the spin-coating speed is 4000rpm, the spin-coating time is 30s, and then annealing treatment is carried out, wherein the annealing temperature is 110 ℃, and the annealing time is 10min, so that the hole transport layer with the thickness of 10nm is prepared;
(3) Adopting an anti-solvent method to drop and widen the band gap perovskite precursor solution on the hole transport layer prepared in the step (2) for spin coating, spin coating at a low speed of 500rpm for 7s, spin coating at a high speed of 3000rpm for 50s, dropping anti-solvent diethyl ether at 20 seconds during the high speed spin coating, and then annealing at 60 ℃ for 5min and 110 ℃ for 12min in sequence to prepare a wide band gap perovskite absorption layer;
(4) Depositing C with the thickness of 20nm on the wide-bandgap perovskite absorption layer prepared in the step (3) by adopting a thermal evaporation method 60 The transmission layer comprises the following specific operations: turning on power supply to slowly heat C 60 To a temperature above 530 ℃ to make the evaporation rate atUntil the deposition thickness reaches 20nm; then deposit on C by atomic layer 60 The electron transport layer is deposited with a tin dioxide barrier layer with the thickness of 20nm, and the specific operation is as follows: setting the temperature of a deposition chamber to 90 ℃, the pulse time of a tin source to be 100ms, the cleaning time to be 30s, the pulse time of a water source to be 100ms and the cleaning time to be 30s;
(5) Sputtering an IZO film with the thickness of 120nm on the tin dioxide barrier layer prepared in the step (4) by adopting a radio frequency magnetron sputtering method, wherein the specific parameters are as follows: the sputtering power is 30W, the sputtering air pressure is 0.3Pa, the argon flow is 23sccm, and the sputtering time is controlled to adjust the sputtering thickness;
(6) Spin-coating the IZO film prepared in the step (5) with a hole transport layer precursor solution in the step (1) at a spin-coating speed of 4000rpm for 30s, and then annealing at 110 ℃ for 15min to obtain an 8-min thick hole transport layer;
(7) Spin-coating a narrow band gap perovskite absorption layer on the hole transport layer prepared in the step (6) by adopting an anti-solvent method, wherein the spin-coating time is 10s, the spin-coating time is 6000rpm, the spin-coating time is 50s, anti-solvent chlorobenzene is dripped in 15 seconds during the high-speed spin-coating, and then annealing is carried out for 15 minutes at 100 ℃ and for 15 minutes at 55 ℃ in sequence to prepare the narrow band gap perovskite absorption layer;
(8) Depositing C with the thickness of 20nm on the narrow-band gap perovskite absorption layer prepared in the step (7) by adopting a thermal evaporation method 60 A transport layer and a 20nm thick tin dioxide barrier layer;
(9) And (3) depositing a copper electrode with the thickness of 100nm on the tin dioxide barrier layer prepared in the step (8) by adopting a thermal evaporation method to prepare the full perovskite laminated solar cell.
Comparative example 1
The preparation method of the all-perovskite laminated solar cell comprises the following steps:
(1) Respectively preparing PTAA hole transport layer precursor solution and PEDOT/PSS hole transport layer precursor solution;
(2) Spin-coating the PTAA hole transport layer precursor solution on the cleaned ITO transparent conductive glass, wherein the spin-coating speed is 4000rpm, the spin-coating time is 30s, and then annealing treatment is carried out, wherein the annealing temperature is 110 ℃, and the annealing time is 10min, so that the hole transport layer with the thickness of 10nm is prepared;
(3) Adopting an anti-solvent method to drop and widen the band gap perovskite precursor solution on the hole transport layer prepared in the step (2) for spin coating, spin coating at a low speed of 500rpm for 7s, spin coating at a high speed of 3000rpm for 50s, dropping anti-solvent diethyl ether at 20 seconds during the high speed spin coating, and then annealing at 60 ℃ for 5min and 110 ℃ for 12min in sequence to prepare a wide band gap perovskite absorption layer;
(4) Depositing C with the thickness of 20nm on the wide-bandgap perovskite absorption layer prepared in the step (3) by adopting a thermal evaporation method 60 The electron transport layer comprises the following specific operations: turning on power supply to slowly heat C 60 To a temperature above 530 ℃ to make the evaporation rate atUntil the deposition thickness reaches 20nm; then deposit on C by atomic layer 60 The electron transport layer is deposited with a tin dioxide electron transport layer with the thickness of 20nm, and the specific operation is as follows: setting the temperature of a deposition chamber to 90 ℃, the pulse time of a tin source to be 100ms, the cleaning time to be 30s, the pulse time of a water source to be 100ms and the cleaning time to be 30s;
(5) Sputtering an IZO film with the thickness of 120nm on the tin dioxide barrier layer prepared in the step (4) by adopting a radio frequency magnetron sputtering method, wherein the specific parameters are as follows: the sputtering power is 70W, the sputtering air pressure is 0.5Pa, the argon flow is 30sccm, and the sputtering time is controlled to adjust the sputtering thickness;
(6) Spin-coating the precursor solution of the IZO film prepared in the step (5) by a spin-coating method, wherein the spin-coating speed is 4000rpm, the spin-coating time is 30s, and then annealing is performed at 110 ℃ for 15min to prepare an 8 nm-thick hole transport layer;
(7) Spin-coating a narrow band gap perovskite absorption layer on the hole transport layer prepared in the step (6) by adopting an anti-solvent method, wherein the spin-coating time is 10s, the spin-coating time is 6000rpm, the spin-coating time is 50s, anti-solvent chlorobenzene is dripped in 15 seconds during the high-speed spin-coating, and then annealing is carried out for 15 minutes at 100 ℃ and for 15 minutes at 55 ℃ in sequence to prepare the narrow band gap perovskite absorption layer;
(8) Depositing C with the thickness of 20nm on the narrow-band gap perovskite absorption layer prepared in the step (7) by adopting a thermal evaporation method 60 An electron transport layer and a 20nm thick tin dioxide barrier layer;
(9) And (3) depositing a copper electrode with the thickness of 100nm on the tin dioxide electron transport layer prepared in the step (8) by adopting a thermal evaporation method to prepare the full perovskite laminated solar cell.
Test examples
The performance of the all-perovskite stacked solar cell in example 3 and comparative example 1 was tested using the all-perovskite stacked solar cell in example 3 as an example, and the specific results are shown in fig. 3 to 6.
As can be seen from fig. 3, the SAM has higher light transmittance in the 300-450nm wavelength band, so that more sunlight with a short wavelength band irradiates the surface of the wide-bandgap perovskite thin film, and the wide-bandgap perovskite thin film just mainly absorbs the sunlight with a short wavelength, which can certainly enable the wide-bandgap perovskite absorbing layer to absorb more photons, thereby improving the output current of the wide-bandgap top cell.
As can be seen from fig. 4, the SAM has higher light transmittance in the 700-1200nm wavelength band, so that more long-wavelength-band sunlight irradiates the surface of the narrow-band-gap perovskite thin film, and the narrow-band-gap perovskite thin film just mainly absorbs the long-wavelength-band sunlight, which can certainly enable the narrow-band-gap perovskite absorption layer to absorb more photons, thereby improving the output current of the narrow-band-gap bottom cell.
Comparing FIGS. 5 and 6, it can be seen that V OC The improvement of (c) is mainly based on the obvious reduction of SAM/perovskite interface non-radiative recombination, mainly: in the wide bandgap top cell, compared with the HOMO level of PTAA, the HOMO level of the SAM material is more matched with the valence band of the wide bandgap perovskite, which is favorable for reducing the interface level barrier of hole transport, accelerating the extraction of holes and reducing energy loss; in the narrow bandgap bottom cell, the self-assembled hole transport layer not only can reduce non-radiative recombination at the interface, but also can react with Sn 2+ The strong interaction between the tin and lead narrow-band gap perovskite can improve the crystallization kinetics by delaying the crystallization speed of the tin and lead narrow-band gap perovskite, thereby preparing the titanium alloy with higher crystallinity and more defectsA high quality tin-lead narrow bandgap perovskite film with trap density. In conclusion, the hole transport layer greatly improves the photoelectric conversion efficiency of the two sub-cells, so that a laminated perovskite solar cell with higher efficiency and stability can be prepared.
J SC The improvement of the solar energy is mainly based on the improvement of solar light transmittance of two wave bands in the figures 3 and 4, so that the wide and narrow band gap perovskite thin film can absorb more photons, and the other reason is that the quality of the narrow band gap perovskite thin film is improved, so that the output current of the bottom cell is higher, and the output current of the bottom cell is more matched with the current of the top cell; the improvement of FF is mainly due to the enhancement of hole transmission and extraction capacity of SAM/perovskite interface, and is mainly due to the material characteristics of the SAM/perovskite interface and the more orderly arrangement of self-assembled materials after the self-assembled materials are anchored on the ITO surface through anchoring groups, and the arrangement orientation is more parallel to the ITO, so that the hole extraction and transfer efficiency can be effectively improved. And the traditional hole transport layers such as PTAA, PEDOT, PSS and the like are arranged on the ITO surface in a disordered manner, so that the hole extraction and transfer capability is poor. Based on this, the laminated device with the novel structure has higher photoelectric conversion efficiency.
Claims (8)
1. The full perovskite laminated solar cell is characterized in that a hole transport layer material in a wide-bandgap top cell is the same as a hole transport layer material in a narrow-bandgap bottom cell, and the hole transport layer material is 4- (7- (4- (bis (4-methoxyphenyl) amino) -2, 5-difluorophenyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) benzoic acid.
2. The all perovskite-stacked solar cell of claim 1 wherein the hole transport layer in the wide bandgap top cell and the hole transport layer in the narrow bandgap bottom cell each have a thickness of 3-15nm.
3. A method of producing a full perovskite stacked solar cell as claimed in claim 1 or 2 comprising the steps of:
(1) Dissolving a hole transport layer material in a solvent to prepare a hole transport layer precursor solution;
(2) Spin-coating the hole transport layer precursor solution in the step (1) on ITO transparent conductive glass, and carrying out annealing treatment to obtain a hole transport layer of the wide-bandgap top battery;
(3) Sequentially depositing a wide band gap perovskite absorption layer, an electron transport layer and an intermediate connection layer on the hole transport layer of the wide band gap top cell in the step (2);
(4) Spin-coating the hole transport layer precursor solution in the step (1) on the intermediate connecting layer in the step (3), and carrying out annealing treatment to obtain a hole transport layer of the narrow band gap bottom cell;
(5) And (3) sequentially depositing a narrow band gap perovskite absorption layer, an electron transmission layer and a metal electrode on the hole transmission layer of the narrow band gap bottom cell in the step (4) to prepare the full perovskite laminated solar cell.
4. The method of producing a full perovskite stacked solar cell according to claim 3, wherein the solvent in the step (1) is toluene, ethanol, isopropanol, deionized water or diethyl ether, and the concentration of the hole transporting layer precursor solution is 0.3 to 0.8mg/mL.
5. The method for manufacturing a full perovskite stacked solar cell according to claim 3, wherein the spin-coating parameters in step (2) and step (4) are the same, specifically: the spin coating speed is 3000-5000rpm, and the spin coating time is 20-40s.
6. The method for manufacturing a full perovskite stacked solar cell according to claim 3, wherein the annealing parameters in step (2) and step (4) are the same, specifically: the annealing temperature is 80-130 ℃, and the annealing time is 5-20min.
7. A method of fabricating a full perovskite stacked solar cell as claimed in claim 3 wherein in step (3) the electron transport layer consists of C 60 Or C 70 A transport layer and a tin dioxide barrier layer, wherein in the step (5), the electron transport layer consists of C 60 Or C 70 A transport layer and a tin dioxide barrier layer, or C 60 Or C 70 A transport layer and a BCP barrier layer.
8. The method of manufacturing a full perovskite stacked solar cell according to claim 3, wherein the intermediate connection layer material in step (3) is IZO, ITO, AZO or Au, and the metal electrode material in step (5) is Cu or Ag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310276686.6A CN116171053B (en) | 2023-03-21 | 2023-03-21 | Full perovskite laminated solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310276686.6A CN116171053B (en) | 2023-03-21 | 2023-03-21 | Full perovskite laminated solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116171053A CN116171053A (en) | 2023-05-26 |
| CN116171053B true CN116171053B (en) | 2023-11-21 |
Family
ID=86422008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310276686.6A Active CN116171053B (en) | 2023-03-21 | 2023-03-21 | Full perovskite laminated solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116171053B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116887652B (en) * | 2023-09-07 | 2023-11-24 | 南开大学 | Perovskite organic laminated solar cell at two ends and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311042A (en) * | 2019-05-31 | 2019-10-08 | 南京邮电大学 | A kind of preparation method and perovskite solar battery of self assembled monolayer and perovskite solar battery |
| CN110600612A (en) * | 2019-06-11 | 2019-12-20 | 华东理工大学 | P-i-n type perovskite battery hole transport layer based on self-assembly engineering |
| CN113892192A (en) * | 2019-05-23 | 2022-01-04 | 瑞士电子显微技术研究与开发中心股份有限公司 | Method for manufacturing photovoltaic cell |
| CN114512613A (en) * | 2022-02-21 | 2022-05-17 | 四川大学 | Intermediate connecting layer structure of perovskite/perovskite two-end laminated solar cell and preparation method and application thereof |
| CN114824094A (en) * | 2022-05-06 | 2022-07-29 | 天合光能股份有限公司 | Charge transmission layer structure of perovskite/crystalline silicon laminated solar cell and perovskite/crystalline silicon laminated solar cell |
| CN115215901A (en) * | 2022-08-03 | 2022-10-21 | 厦门大学 | Self-assembly hole transport material based on 7H-dibenzocarbazole and synthetic method |
| CN115440891A (en) * | 2022-09-29 | 2022-12-06 | 南开大学 | Perovskite base solar cell |
-
2023
- 2023-03-21 CN CN202310276686.6A patent/CN116171053B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113892192A (en) * | 2019-05-23 | 2022-01-04 | 瑞士电子显微技术研究与开发中心股份有限公司 | Method for manufacturing photovoltaic cell |
| CN110311042A (en) * | 2019-05-31 | 2019-10-08 | 南京邮电大学 | A kind of preparation method and perovskite solar battery of self assembled monolayer and perovskite solar battery |
| CN110600612A (en) * | 2019-06-11 | 2019-12-20 | 华东理工大学 | P-i-n type perovskite battery hole transport layer based on self-assembly engineering |
| CN114512613A (en) * | 2022-02-21 | 2022-05-17 | 四川大学 | Intermediate connecting layer structure of perovskite/perovskite two-end laminated solar cell and preparation method and application thereof |
| CN114824094A (en) * | 2022-05-06 | 2022-07-29 | 天合光能股份有限公司 | Charge transmission layer structure of perovskite/crystalline silicon laminated solar cell and perovskite/crystalline silicon laminated solar cell |
| CN115215901A (en) * | 2022-08-03 | 2022-10-21 | 厦门大学 | Self-assembly hole transport material based on 7H-dibenzocarbazole and synthetic method |
| CN115440891A (en) * | 2022-09-29 | 2022-12-06 | 南开大学 | Perovskite base solar cell |
Non-Patent Citations (2)
| Title |
|---|
| Dávid Forgács, et al..Efficient Monolithic Perovskite/Perovskite Tandem Solar Cells.Adv. Energy Mater..2016,第7卷page 1602121(1-6) & Supporting Information. * |
| Efficient Monolithic Perovskite/Perovskite Tandem Solar Cells;Dávid Forgács, et al.;Adv. Energy Mater.;第7卷;page 1602121(1-6) & Supporting Information * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116171053A (en) | 2023-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110600614B (en) | Tunneling junction structure of perovskite/perovskite two-end laminated solar cell | |
| CN105024013A (en) | Novel planar heterojunction perovskite solar cell with high efficiency and long life manufactured by adopting low-temperature solution method | |
| CN110335945B (en) | Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof | |
| CN116171053B (en) | Full perovskite laminated solar cell and preparation method thereof | |
| KR20190021135A (en) | Method of manufacturing solar cell | |
| CN107394044B (en) | Perovskite solar cell with conductive electrode and electron transmission layer and preparation method | |
| CN116847670A (en) | Perovskite solar cell of passivation composite hole transport layer | |
| CN118510298A (en) | Composite electrode and preparation method and application thereof | |
| CN113644195A (en) | All-inorganic perovskite/organic laminated solar cell and preparation method thereof | |
| CN108365105B (en) | Perovskite solar cell and preparation method thereof | |
| CN112490298B (en) | Cadmium selenide single crystal film preparation method, solar cell preparation method and product | |
| KR102591913B1 (en) | Solar cell | |
| CN109935652B (en) | CdTe nano crystal solar cell and preparation method thereof | |
| Huang et al. | Efficient and stable hybrid conjugated polymer/perovskite quantum dot solar cells | |
| CN117177595A (en) | Photoelectric device, preparation method thereof, photovoltaic module and photovoltaic system | |
| CN114512613B (en) | Intermediate connecting layer structure of perovskite/perovskite two-end laminated solar cell and preparation method and application thereof | |
| CN108470836B (en) | Preparation method of perovskite thin film and solar cell | |
| KR20230067926A (en) | Organic-inorganic Perovskite Solar Cell and Manufacturing Method Thereof | |
| KR20220079148A (en) | High-performance perovskite solar cell using anti-solvent and Method for anufacturing the smae | |
| CN110993795A (en) | Solar cell based on copper oxide quantum dot interface layer and preparation method of interface layer | |
| CN111092156B (en) | Perovskite solar cell and preparation method thereof | |
| Wen et al. | Resting temperature of PbI2 in perovskite solar cells | |
| CN114765200B (en) | Single-substrate four-terminal cascading perovskite-cadmium telluride laminated solar cell | |
| CN118695632A (en) | Intermediate layer structure of laminated battery and preparation method and application thereof | |
| CN118301959A (en) | Sb2O3Material perovskite solar cell application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |