CN115188887A - Large-area perovskite battery and preparation method thereof - Google Patents
Large-area perovskite battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of perovskite cells, in particular to a large-area perovskite cell and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of perovskite batteries, in particular to a large-area perovskite battery and a preparation method thereof.
Background
The perovskite cell is a solar cell using a perovskite-type organic metal halide semiconductor as a light absorbing material, and belongs to a third generation solar cell, also referred to as a new concept solar cell. When the perovskite cell is used for current carrier transmission, as TCO has lower conductivity due to larger sheet resistance, the current carrier is seriously compounded on the interface of the first transmission layer and the perovskite light absorption layer, the extraction of the current carrier by the perovskite cell device is reduced, and the TCO conductive substrate needs float glass with better flatness, so that the substrate needs to be subjected to special polishing treatment, and the manufacturing cost of the perovskite cell is increased.
Disclosure of Invention
The invention aims to provide a large-area perovskite battery and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the utility model provides a large tracts of land perovskite battery, includes transparent stratum basale, TCO composite bed, first transmission layer, perovskite light absorption layer, second transmission layer, the conductive electrode layer that sets gradually from bottom to top, be equipped with ultra-thin conducting layer between transparent stratum basale and the TCO composite bed, ultra-thin conducting layer deposit is in the one side that transparent stratum basale is close to the TCO composite bed, and the TCO composite bed includes field passivation dense layer and TCO layer, TCO layer and field passivation dense layer deposit on ultra-thin conducting layer in turn.
Preferably, the transparent substrate layer is at least one of glass, PET, PEN, PEI and PMMA.
Preferably, the field passivation dense layer is at least one of aluminum oxide, titanium oxide, silicon oxide, zirconium oxide, zinc oxide, nickel oxide, magnesium oxide and copper oxide.
Preferably, the field passivation dense layer and the ultrathin conducting layer are N-type semiconductors, P-type semiconductors or conductors.
Preferably, the ultrathin conductive layer is a metal or carbon electrode.
Preferably, the TCO layer is at least one of FTO fluorine-doped tin oxide glass, ITO indium-doped tin oxide glass, AZO aluminum-doped zinc oxide glass, ATO aluminum-doped tin oxide glass and IGO indium-doped oxide-gallium glass.
Preferably, the first transmission layer is an N-type semiconductor.
Preferably, the first transmission layer is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
Preferably, the first transmission layer is a P-type semiconductor.
Preferably, the first transmission layer is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc, and PTAA.
Preferably, the perovskite light absorption layer is an ABX3 type perovskite material.
Preferably, A in the ABX3 type is at least one of Cs +, CH (NH 2) 2+, CH3NH3+, and C (NH 2) 3+, B in the ABX3 type is at least one of Pb2+ and Sn2+, and X in the ABX3 type is at least one of Br-, I-, and Cl-.
Preferably, the second transport layer is an N-type semiconductor.
Preferably, the second transmission layer is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
Preferably, the second transport layer is a P-type semiconductor.
Preferably, the second transport layer is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc, and PTAA.
Preferably, the conductive electrode layer is FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped gallium oxide, ag, cu, al or Au.
A preparation method of a large-area perovskite battery comprises the following steps:
the method comprises the following steps: ultrasonically cleaning the transparent substrate layer for 20min by sequentially adopting a detergent, deionized water, acetone and ethanol, then purging the transparent substrate layer with high-purity nitrogen, and then cleaning the transparent substrate layer for 10min by using an oxygen plasma cleaning machine to obtain a clean transparent substrate layer;
step two: depositing an ultra-thin conductive layer on the transparent substrate layer;
step three: depositing a field passivation compact layer on the ultrathin conducting layer in a mask mode, wherein the field passivation compact layer is made of aluminum oxide;
step four: depositing a TCO layer on the field passivation dense layer in a mask mode to form a composite substrate, wherein the TCO layer is made of ITO;
step five: depositing a first transport layer on the composite substrate;
step six: depositing a perovskite light absorbing layer on the first transport layer;
step seven: depositing a second transport layer on the perovskite light absorbing layer;
step eight: and depositing a transparent conductive electrode layer on the second transmission layer to obtain the perovskite cell piece.
Preferably, the thickness of the ultrathin conducting layer is 10nm-100nm.
Preferably, the thickness of the field passivation dense layer is 10nm-100nm.
Preferably, the thickness of the ITO is 10nm-100nm.
Preferably, the thickness of the first transport layer is 20nm to 40nm.
Preferably, the thickness of the perovskite light absorption layer is 400nm to 500nm.
Preferably, the thickness of the conductive electrode layer is 60nm to 80nm.
Preferably, the deposition mode of the ultra-thin conductive layer in the second step is magnetron sputtering, thermal evaporation or screen printing.
Preferably, the deposition mode of the field passivation dense layer in the third step is that the mask plate is matched with ALD deposition or laser etching to completely passivate the dense layer.
Preferably, the ITO in the fourth step is prepared by adopting a mask sputtering mode.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the large-area perovskite battery and the preparation method thereof, the ultrathin conducting layer is deposited on the transparent substrate layer in advance, so that the conducting performance of TCO can be improved, the light transmittance of the TCO is not influenced, and the damage of Na + and K + possibly existing in the transparent substrate layer to the perovskite thin film is avoided.
2. According to the large-area perovskite battery and the preparation method thereof, the field passivation dense layer with high fixed charge density is deposited according to the specific pattern, when a current carrier reaches the surface of the first transmission layer through the perovskite light absorption layer, the current carrier can migrate in the opposite direction in a field passivation mode to reduce interface recombination, the extraction of the current carrier by a perovskite battery device is increased, and the photoelectric conversion efficiency of the perovskite battery is improved.
Drawings
Fig. 1 is a schematic view of the overall structure of a perovskite battery of the present invention.
FIG. 2 is a schematic top view of a TCO composite layer according to the present invention.
The meaning of the reference symbols in the figures is: 1. a transparent substrate layer; 2. an ultra-thin conductive layer; 30. a field-passivated dense layer; 31. a TCO layer; 4. a first transport layer; 5. a perovskite light-absorbing layer; 6. a second transport layer; 7. and a conductive electrode layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the equipment or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first embodiment is as follows:
a large-area perovskite battery refers to the fig. 1-2, and comprises a transparent substrate layer 1, a TCO composite layer, a first transmission layer 4, a perovskite light absorption layer 5, a second transmission layer 6 and a conductive electrode layer 7 which are sequentially arranged from bottom to top, wherein an ultrathin conductive layer 2 is arranged between the transparent substrate layer 1 and the TCO composite layer, the ultrathin conductive layer 2 is deposited on one surface of the transparent substrate layer 1 close to the TCO composite layer, the TCO composite layer comprises a field passivation dense layer 30 and a TCO layer 31, and the TCO layer 31 and the field passivation dense layer 30 are alternately deposited on the ultrathin conductive layer 2; the method has the advantages that the ultrathin conducting layer is deposited on the transparent substrate layer in advance, so that the conductivity of the TCO can be increased, the light transmittance of the TCO is not influenced, and the perovskite thin film can be prevented from being damaged by Na + and K + possibly existing in the transparent substrate layer.
The transparent substrate layer 1 is at least one of glass, PET, PEN, PEI and PMMA.
The ultra-thin conducting layer 2 is a metal or carbon electrode.
The field passivation dense layer 30 is at least one of alumina, titanium oxide, silicon oxide, zirconium oxide, zinc oxide, nickel oxide, magnesium oxide and copper oxide; the field passivation dense layer has a certain fixed negative charge density or positive charge density function, and can move carriers with opposite polarities in PIN junctions in the perovskite to opposite directions.
The field passivation dense layer 30 and the ultra-thin conductive layer 2 are N-type semiconductors, P-type semiconductors or conductors.
The TCO layer 31 is at least one of FTO fluorine-doped tin oxide glass, ITO indium-doped tin oxide glass, AZO aluminum-doped zinc oxide glass, ATO aluminum-doped tin oxide glass, IGO indium-doped oxide-gallium glass.
The first transmission layer 4 is an N-type semiconductor.
The first transmission layer 4 is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
The first transfer layer 4 is a P-type semiconductor.
The first transmission layer 4 is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc and PTAA.
The perovskite light absorption layer 5 is an ABX3 type perovskite material.
A in the ABX3 type is at least one of Cs +, CH (NH 2) 2+, CH3NH3+ and C (NH 2) 3+, B in the ABX3 type is at least one of Pb2+ and Sn2+, and X in the ABX3 type is at least one of Br-, I-and Cl-; thus, the perovskite light absorption layer 5 has a good light absorption effect, and is favorable for improving the photoelectric conversion efficiency.
For example, A is Cs +, B is Pb2+, and X is Br-; as another example, A is Cs + and CH (NH 2) 2+, B is Pb2+, and X is Br-; for another example, A is Cs +, B is Pb2+ and Sn2+, and X is Br-; for example, A is Cs +, B is Pb2+, X is Br-and I-; as another example, A is CH3NH3+ and C (NH 2) 3+, B is Pb2+, and X is I-and Cl-; as another example, A is Cs +, CH (NH 2) 2+, CH3NH3+, and C (NH 2) 3+, B is Pb2+ and Sn2+, and X is Br-, I-, and Cl-.
The second transport layer 6 is an N-type semiconductor.
The second transmission layer 6 is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
The second transport layer 6 is a P-type semiconductor.
The second transmission layer 6 is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc and PTAA.
The conductive electrode layer 7 is made of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped tin oxide, ag, cu, al or Au.
When the first transfer layer 4 is a P-type semiconductor, the second transfer layer 6 is an N-type semiconductor; when the first transfer layer 4 is an N-type semiconductor, the second transfer layer 6 is a P-type semiconductor.
Example two:
a preparation method of a large-area perovskite battery comprises the following steps:
the method comprises the following steps: ultrasonically cleaning the transparent substrate layer 1 for 20min by sequentially adopting a detergent, deionized water, acetone and ethanol, then purging the transparent substrate layer 1 by using high-purity nitrogen, and cleaning the transparent substrate layer for 10min by using an oxygen plasma cleaning machine to obtain a clean transparent substrate layer 1;
step two: depositing an ultrathin conductive layer 2 on a transparent substrate layer 1;
step three: depositing a field passivation compact layer 30 on the ultrathin conducting layer 2 in a mask mode, wherein the field passivation compact layer 30 is made of aluminum oxide; the alumina has high density negative charge concentration, low preparation cost and simple electron concentration of an electron transport layer;
step four: depositing a TCO layer 31 on the field passivation dense layer 30 in a mask mode to form a composite substrate, wherein the TCO layer 31 is made of ITO;
step five: depositing a first transfer layer 4 on the above composite substrate;
step six: depositing a perovskite light absorbing layer 5 on the first transmission layer 4;
step seven: depositing a second transmission layer 6 on the perovskite light absorption layer 5;
step eight: and depositing a transparent conductive electrode layer 7 on the second transmission layer 6 to obtain the perovskite cell piece.
The thickness of the ultrathin conducting layer 2 is 10nm-100nm; the thickness of the ultra-thin conductive layer 2 may be 10nm, 50nm, and 100nm, and when the thickness of the ultra-thin conductive layer 2 is less than 10nm, the conductivity may be low; when the thickness of the ultra-thin conductive layer 2 is greater than 100nm, the cost is too high, and the conductivity of the ultra-thin conductive layer 2 is not obviously improved.
The thickness of the field passivation dense layer 30 is 10nm-100nm; the thickness of the field passivation dense layer 30 may be 10nm, 50nm, and 100nm.
The thickness of the ITO is 10nm-100nm; the thickness of the ITO can be 10nm, 50nm and 100nm, and when the thickness of the ITO is less than 10nm, the conductivity is low; when the thickness of the ITO is more than 100nm, the cost is too high, and the conductivity of the ITO cannot be obviously improved.
The thickness of the first transmission layer 4 is 20nm-40nm; the thickness of the first transmission layer 4 can be 20nm, 30nm and 40nm, the carrier transmission performance of the first transmission layer 4 with the thickness between 20nm and 40nm is better, when the thickness of the first transmission layer 4 is more than 40nm, the manufacturing cost is too high, and the carrier transmission performance of the first transmission layer 4 cannot be obviously improved along with the increase of the thickness.
The thickness of the perovskite light absorption layer 5 is 400nm-500nm; for example, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, or 500nm. In this way, the thickness of the perovskite light absorption layer 5 is in an appropriate range, so that the light absorption effect is better. Preferably, the thickness of the perovskite light absorption layer 5 is 450nm.
The thickness of the conductive electrode layer 7 is 60nm-80nm.
And in the second step, the deposition mode of the ultrathin conducting layer 2 is magnetron sputtering, thermal evaporation or screen printing.
In the third step, the deposition mode of the field passivation dense layer 30 is that the mask plate is matched with ALD deposition or laser etching to completely passivate the dense layer.
And the ITO in the fourth step is prepared in a mask sputtering mode.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (27)
1. The utility model provides a large tracts of land perovskite battery, includes transparent stratum basale (1), TCO composite bed, first transmission layer (4), perovskite light absorption layer (5), second transmission layer (6), conductive electrode layer (7) that set gradually from bottom to top, its characterized in that: an ultrathin conductive layer (2) is arranged between the transparent substrate layer (1) and the TCO composite layer, the ultrathin conductive layer (2) is deposited on one surface, close to the TCO composite layer, of the transparent substrate layer (1), the TCO composite layer comprises a field passivation dense layer (30) and a TCO layer (31), and the TCO layer (31) and the field passivation dense layer (30) are alternately deposited on the ultrathin conductive layer (2).
2. A large area perovskite battery as claimed in claim 1 wherein: the transparent substrate layer (1) is at least one of glass, PET, PEN, PEI and PMMA.
3. The large area perovskite battery of claim 1, wherein: the field passivation dense layer (30) is at least one of aluminum oxide, titanium oxide, silicon oxide, zirconium oxide, zinc oxide, nickel oxide, magnesium oxide and copper oxide.
4. A large area perovskite battery as claimed in claim 1 wherein: the field passivation dense layer (30) and the ultrathin conducting layer (2) are N-type semiconductors, P-type semiconductors or conductors.
5. The large area perovskite battery of claim 4, wherein: the ultrathin conducting layer (2) is a metal or carbon electrode.
6. A large area perovskite battery as claimed in claim 1 wherein: the TCO layer (31) is at least one of FTO fluorine-doped tin oxide glass, ITO indium-doped tin oxide glass, AZO aluminum-doped zinc oxide glass, ATO aluminum-doped tin oxide glass and IGO indium-doped oxide-gallium glass.
7. A large area perovskite battery as claimed in claim 1 wherein: the first transmission layer (4) is an N-type semiconductor.
8. The large area perovskite battery of claim 7, wherein: the first transmission layer (4) is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
9. A large area perovskite battery as claimed in claim 1 wherein: the first transmission layer (4) is a P-type semiconductor.
10. A large area perovskite battery as claimed in claim 9, wherein: the first transmission layer (4) is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc and PTAA.
11. The large area perovskite battery of claim 1, wherein: the perovskite light absorption layer (5) is made of ABX3 type perovskite material.
12. The large area perovskite battery of claim 11, wherein: a in the ABX3 type is at least one of Cs +, CH (NH 2) 2+, CH3NH3+ and C (NH 2) 3+, B in the ABX3 type is at least one of Pb2+ and Sn2+, and X in the ABX3 type is at least one of Br-, I-and Cl-.
13. The large area perovskite battery of claim 1, wherein: the second transmission layer (6) is an N-type semiconductor.
14. The large area perovskite battery of claim 13, wherein: the second transmission layer (6) is at least one of SnO2, tiO2, znSnO4, C60 and PCBM.
15. A large area perovskite battery as claimed in claim 1 wherein: the second transmission layer (6) is a P-type semiconductor.
16. A large area perovskite battery as claimed in claim 15, wherein: the second transmission layer (6) is at least one of Spiro-oMeTad, niOx, cuSCN, cuPc and PTAA.
17. A large area perovskite battery as claimed in claim 1 wherein: the conductive electrode layer (7) is made of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped gallium oxide, ag, cu, al or Au.
18. A preparation method of a large-area perovskite battery is characterized by comprising the following steps:
the method comprises the following steps: ultrasonically cleaning the transparent substrate layer (1) for 20min by sequentially adopting a detergent, deionized water, acetone and ethanol, then purging the transparent substrate layer with high-purity nitrogen, and cleaning the transparent substrate layer for 10min by using an oxygen plasma cleaning machine to obtain a clean transparent substrate layer (1);
step two: depositing an ultrathin conductive layer (2) on a transparent substrate layer (1);
step three: depositing a field passivation dense layer (30) on the ultrathin conducting layer (2) in a mask mode, wherein the field passivation dense layer (30) is made of aluminum oxide;
step four: depositing a TCO layer (31) on the field passivation dense layer (30) in a mask mode to form a composite substrate, wherein the TCO layer (31) is made of ITO;
step five: depositing a first transfer layer (4) on said composite substrate;
step six: depositing a perovskite light absorbing layer (5) on the first transmission layer (4);
step seven: depositing a second transmission layer (6) on the perovskite light absorption layer (5);
step eight: and depositing a transparent conductive electrode layer (7) on the second transmission layer (6) to obtain the perovskite cell piece.
19. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the ultrathin conducting layer (2) is 10nm-100nm.
20. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the field passivation dense layer (30) is 10nm-100nm.
21. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the ITO is 10nm-100nm.
22. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the first transmission layer (4) is 20nm-40nm.
23. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the perovskite light absorption layer (5) is 400nm-500nm.
24. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: the thickness of the conductive electrode layer (7) is 60nm-80nm.
25. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: and in the second step, the deposition mode of the ultrathin conducting layer (2) is magnetron sputtering, thermal evaporation or screen printing.
26. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: and in the third step, the deposition mode of the field passivation compact layer (30) is that the mask plate is matched with ALD deposition or laser etching to completely passivate the compact layer.
27. The method of claim 18, wherein the step of preparing a large area perovskite battery comprises: and the ITO in the fourth step is prepared in a mask sputtering mode.
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