Flexible three-junction laminated solar cell and preparation method thereof

Abstract

The invention provides a flexible three-junction laminated solar cell structure, and belongs to the technical field of flexible laminated solar cells. The structure of the flexible three-junction laminated solar cell sequentially comprises a CIGS layer, an interface layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, an intermediate layer, a hole transport layer, a perovskite absorption layer, a passivation layer, a hole transport layer, a buffer layer, a transparent conductive layer, an anti-reflection layer and a metal electrode from bottom to top. The flexible three-junction laminated solar cell is simple in preparation process, high in photoelectric conversion efficiency, high in adaptability and suitable for various practical purposes.

Description

Technical Field

[0001] The present invention relates to the technical field of flexible stacked solar cells, and particularly relates to a flexible triple-junction stacked solar cell and a preparation method thereof. Background Art

[0002] Perovskite stacked solar cells are a new type of high-efficiency optoelectronic conversion device. With perovskite materials as the core photovoltaic layer, they achieve multi-band light absorption through a stacked structure, thereby significantly improving the optoelectronic conversion efficiency. Each sub-cell in the stacked solar cell is designed for sunlight of different wavelengths. Short-wavelength light is absorbed by the wide-bandgap material, while long-wavelength light is transmitted to the lower narrow-bandgap material for absorption. This mechanism of wavelength-segmented absorption significantly improves the utilization rate of light energy. Perovskite materials have a small bandgap and a high light absorption coefficient, which can not only effectively absorb long-wavelength light but also reduce the requirement for material thickness. Due to their excellent performance, perovskite stacked solar cells have received extensive attention and applications in the field of photovoltaic technology.

[0003] Currently, existing perovskite solar cells usually use rigid substrates, which limits their applications in the field of flexible optoelectronics. Moreover, compared with triple-junction cells, the theoretical efficiency limits of single-junction or double-junction cells are lower. Flexible stacked solar cells use flexible substrate materials, enabling them to adapt to different surface shapes, facilitating transportation and installation, being easy to integrate, and being more impact-resistant and not easily broken. Triple-junction stacked solar cells can utilize a wider range of solar spectra. Each junction is optimized for light of different wavelengths, thereby overall improving the optoelectronic conversion efficiency. And by adjusting the thickness and materials of different layers, the performance of the battery can be optimized to meet different actual application requirements.

[0004] Therefore, it is of great practical significance to develop a flexible triple-junction stacked solar cell. Summary of the Invention

[0005] The present invention provides a flexible triple-junction stacked solar cell structure and a preparation method. By replacing the conventional flexible double-stack solar cell with a flexible triple-junction stacked solar cell, the applicability and optoelectronic conversion efficiency of the solar cell are improved.

[0006] To achieve the above object, the specific solution provided by the present invention is as follows: A flexible triple-junction stacked solar cell, characterized by comprising a CIGS layer, an interface layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, an intermediate layer, a hole transport layer, a perovskite absorption layer, a hole transport layer, a buffer layer, a transparent conductive layer, an antireflection layer, and a metal electrode.

[0007] The CIGS layer is a sub-cell including a Cu(In,Ga)Se2 absorption layer.

[0008] The interface layer is one or more of a transparent conductive film, graphene, or metal, with a thickness of 0.001 - 1000 nm.

[0009] The hole transport layer is PTAA, NiO x , P3HT, V2O5, MoO x , PEDOT:PSS, WO x , Sprio-OMeTAD, CuSCN, Cu2O, CuI, Spiro-TTB, F4-TCNQ, F6-TCNNQ, m-MTDATA, TPD, 2PACz, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA, or TAPC, with a thickness of 0.001 - 1000 nm.

[0010] The perovskite absorption layer consists of a monovalent cation (A), a divalent cation (B), and a monovalent anion (X), with a structural general formula of ABX3. The monovalent cation includes one or more ions among amino, amidino, lithium, sodium, potassium, rubidium, and cesium; the divalent cation includes one or more ions among beryllium, magnesium, calcium, strontium, barium, titanium, copper, zinc, tin, lead, tungsten, gallium, mercury, bismuth, palladium, arsenic, germanium, silver, indium, selenium, and rhodium; the monovalent anion includes one or more ions among chlorine, bromine, iodine, pseudohalogens (CN, OCN, SCN), with a thickness of 0.001 - 100 μm.

[0011] The passivation layer is one or more of Si3N4, SiN x , Al2O3, SiO2, AlN, InSb, SiC, TiO2, fullerene derivatives (C 60 , C 70 ), microcrystalline silicon, or amorphous silicon, with a thickness of 0.001 - 50 nm. The electron transport layer is one or more of SnO2, BCP, TiO2, ZnO, ZrO2, fullerenes and their derivatives (C 60 , C 70 , PCBM), TiSnO x , ICBA, or SnZnO x , with a thickness of 0.001 - 500 nm.

[0012] The intermediate layer includes one or more of the hole transport layer, perovskite absorption layer, passivation layer, electron transport layer, buffer layer, and antireflection layer in a flexible triple-junction tandem solar cell.

[0013] The buffer layer is V2O5, PMMA, TiO 2、 MoOx, Ag, Au, Cu, SnO2, ZnO, TAl2O3, SiO2, Si3N4, fullerene derivatives (C60 , C 70， PCBM), microcrystalline silicon, or amorphous silicon, with a thickness of 0.001 - 100 nm.

[0014] The transparent conductive layer is one or more of ITO, IZO, AZO, graphene, or metal (gold, silver, copper, aluminum) nanowires, with a thickness of 0.001 - 1000 nm.

[0015] The antireflection layer includes one or more of LiF, MgF2, polydimethylsiloxane (PDMS) film, AlN, ZnS, Si3N4, SiO2, TiO2, or a flexible film with a matte surface structure, with a thickness of 0.001 - 5 mm.

[0016] The metal electrode is one or more of aluminum, silver, titanium, palladium, nickel, chromium, or copper, with a thickness of 0.001 - 1000 nm.

[0017] A method for preparing a flexible triple - junction stacked solar cell, the preparation method comprising the following steps: S1. Provide a CIGS bottom - cell substrate based on a steel substrate, and prepare an interface layer on the substrate by methods including but not limited to spin - coating, evaporation, sputtering, and spraying.

[0018] S2. Prepare a hole - transport layer on the interface layer by methods including but not limited to spin - coating, evaporation, sputtering, and spraying.

[0019] S3. Prepare a perovskite absorption layer on the hole - transport layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal spray decomposition, doctor - blading, printing, or slot - coating.

[0020] S4. Prepare a passivation layer on the perovskite absorption layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). S5. Prepare a buffer layer on the passivation layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0021] S6. Prepare an electron - transport layer on the buffer layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0022] S7. Prepare an intermediate layer on the electron - transport layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal spray decomposition, doctor - blading, printing, or slot - coating.

[0023] S8. Prepare a hole - transport layer on the intermediate layer by methods including but not limited to spin - coating, evaporation, sputtering, and spraying.

[0024] S9. The perovskite absorption layer is prepared on the hole transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray decomposition, blade coating, printing, or slot coating.

[0025] S10. The passivation layer is prepared on the perovskite absorption layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0026] S11. The buffer layer is prepared on the passivation layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0027] S12. The electron transport layer is prepared on the buffer layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0028] S13. The transparent conductive layer is prepared on the electron transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray decomposition, blade coating, printing, or slot coating.

[0029] S14. The metal electrode is prepared on the transparent conductive layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0030] S15. The antireflection layer is prepared on the metal electrode by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). Description of the Drawings

[0031] Figure 1 is a schematic structural diagram of the tandem solar cell described in the present invention; wherein, (1) is the CIGS layer, (2) is the interface layer, (3) is the hole transport layer, (4) is the perovskite absorption layer, (5) is the electron transport layer, (6) is the intermediate layer, (7) is the hole transport layer, (8) is the perovskite absorption layer, (9) is the hole transport layer, (10) is the buffer layer, (11) is the transparent conductive layer, (12) is the metal electrode, and (13) is the antireflection layer. Detailed Embodiments

[0032] To enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in detail below with reference to the drawings and specific embodiments.

[0033] Refer to Figure 1 , a flexible triple-junction tandem solar cell of the present invention has a specific structure as Figure 1As shown, where (1) is the CIGS layer, (2) is the interface layer, (3) is the hole transport layer, (4) is the perovskite absorption layer, (5) is the electron transport layer, (6) is the intermediate layer, (7) is the hole transport layer, (8) is the perovskite absorption layer, (9) is the hole transport layer, (10) is the buffer layer, (11) is the transparent conductive layer, (12) is the metal electrode, and (13) is the antireflection layer.

[0034] The CIGS layer described is Cu(In,Ga)Se2.

[0035] The interface layer is one or more of TiO2, PEDOT:PSS, PPEA, Sprio-OMeTAD, MB-NiO, CBL, HBPDC, with a thickness of 0.001 - 1000 nm.

[0036] The hole transport layer is PTAA, NiO x , P3HT, V2O5, MoO x , PEDOT:PSS, WO x , Sprio-OMeTAD, CuSCN, Cu2O, CuI, Spiro-TTB, F4-TCNQ, F6-TCNNQ, m-MTDATA, TPD, 2PACz, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA or TAPC, with a thickness of 0.001 - 1000 nm.

[0037] The perovskite absorption layer consists of monovalent cations (A), divalent cations (B), and monovalent anions (X), with a general structural formula of ABX3. Among them, the monovalent cations include one or more ions selected from amino, amidinium, lithium, sodium, potassium, rubidium, cesium; the divalent cations include one or more ions selected from beryllium, magnesium, calcium, strontium, barium, titanium, copper, zinc, tin, lead, tungsten, gallium, mercury, bismuth, palladium, arsenic, germanium, silver, indium, selenium, rhodium; the monovalent anions include one or more ions selected from chlorine, bromine, iodine, pseudohalogens (CN, OCN, SCN), with a thickness of 0.001 - 100 μm.

[0038] The passivation layer is one or more of Si3N4, SiN x , Al2O3, SiO2, AlN, InSb, SiC, TiO2, fullerene derivatives (C 60 , C 70 ), microcrystalline silicon or amorphous silicon, with a thickness of 0.001 - 50 nm.

[0039] The electron transport layer is SnO2, BCP, TiO2, ZnO, ZrO2, fullerenes and their derivatives (C 60 , C70 , PCBM), TiSnO x , ICBA or SnZnO x or one or more of them, with a thickness of 0.001 - 500 nm.

[0040] The intermediate layer includes one or more of a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, a buffer layer, and an antireflection layer in a flexible triple - junction stacked solar cell.

[0041] The buffer layer is one or more of V2O5, PMMA, TiO 2、 MoOx, Ag, Au, Cu, SnO2, ZnO, TAl2O3, SiO2, Si3N4, fullerene derivatives (C 60 , C 70， PCBM), microcrystalline silicon or amorphous silicon, with a thickness of 0.001 - 100 nm.

[0042] The transparent conductive layer is one or more of ITO, IZO, AZO, graphene, or metal (gold, silver, copper, aluminum) nanowires, with a thickness of 0.001 - 1000 nm.

[0043] The antireflection layer includes one or more of LiF, MgF2, polydimethylsiloxane (PDMS) film, AlN, ZnS, Si3N4, SiO2, TiO2, or a flexible film with a textured surface structure, with a thickness of 0 - 5 mm.

[0044] The metal electrode is one or more of aluminum, silver, titanium, palladium, nickel, chromium, or copper, with a thickness of 0.001 - 1000 nm.

[0045] A method for preparing a flexible triple - junction stacked solar cell, the preparation method comprising the following steps: S1. Provide a CIGS bottom - cell substrate based on a steel substrate, and prepare an interface layer on the substrate by methods including but not limited to spin - coating, evaporation, sputtering, and spraying.

[0046] S2. Prepare a hole transport layer on the interface layer by methods including but not limited to spin - coating, evaporation, sputtering, and spraying.

[0047] S3. Prepare a perovskite absorption layer on the hole transport layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal spray pyrolysis, doctor - blading, printing, or slot - coating.

[0048] S4. Prepare a passivation layer on the perovskite absorption layer by methods including but not limited to spin - coating, evaporation, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0049] S5. A buffer layer is prepared on the passivation layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0050] S6. An electron transport layer is prepared on the buffer layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0051] S7. An intermediate layer is prepared on the electron transport layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal spray pyrolysis, blade coating, printing, or slot coating.

[0052] S8. A hole transport layer is prepared on the intermediate layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying.

[0053] S9. A perovskite absorption layer is prepared on the hole transport layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal spray pyrolysis, blade coating, printing, or slot coating.

[0054] S10. A passivation layer is prepared on the perovskite absorption layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0055] S11. A buffer layer is prepared on the passivation layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0056] S12. An electron transport layer is prepared on the buffer layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0057] S13. A transparent conductive layer is prepared on the electron transport layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal spray pyrolysis, blade coating, printing, or slot coating.

[0058] S14. A metal electrode is prepared on the transparent conductive layer by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0059] S15. An antireflection layer is prepared on the metal electrode by a method including, but not limited to, spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

[0060] The following is a more detailed description with specific examples: Example 1

[0061] Please refer to Figure 1 , this example provides a method for preparing a flexible perovskite-perovskite-CIGS tandem solar cell, including the following steps: Starting from the CIGS bottom cell substrate of a stainless steel substrate, NiO deposited by magnetron sputtering x layer; depositing a self-assembled monolayer (SAM) and a high-quality doped perovskite (about 1.5 eV) on the NiO x layer, depositing a LiF (or substitute) layer and a C 60 (or substitute) layer on the perovskite; depositing a SnO2 layer by ALD; depositing an ultrathin gold (Au) layer on the SnO2 layer; depositing a NiO x layer and a SAM layer by magnetron sputtering; preparing a wide-bandgap perovskite on the SAM layer; depositing an Al2O3 passivation layer (by ALD), a LiF (or substitute) layer and a C 60 (or substitute) layer on the perovskite layer; depositing ITO, a metal frame and an antireflection layer, as well as a LiF back layer, to complete the preparation of the triple-junction cell. The open-circuit voltage of the triple-junction device test can reach more than 2.7V.

[0062] The above embodiments are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, these embodiments can be variously changed, modified, substituted and deformed. These technical solutions obtained by equivalent substitution of the claims of the present invention all fall within the protection scope of the present invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A flexible triple-junction stacked solar cell, characterized in that: The flexible triple-junction tandem solar cell, from bottom to top, successively includes a CIGS layer, an interface layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, an intermediate layer, a hole transport layer, a perovskite absorption layer, a passivation layer, a hole transport layer, a buffer layer, a transparent conductive layer, an antireflection layer, and a metal electrode.

2. The flexible triple-junction stacked solar cell according to claim 1, wherein: The CIGS layer is a sub-cell including a Cu(In,Ga)Se2 absorption layer.

3. The flexible triple-junction stacked solar cell according to claim 1, wherein: The interface layer is one or several of a transparent conductive film, graphene, or a metal, with a thickness of 0.001 - 1000 nm.

4. The flexible triple-junction stacked solar cell according to claim 1, wherein: The hole transport layer is PTAA, NiO x , P3HT, V2O5, MoO x , PEDOT:PSS, WO x , Sprio-OMeTAD, CuSCN, Cu2O, CuI, Spiro-TTB, F4-TCNQ, F6-TCNNQ, m-MTDATA, TPD, 2PACz, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA or TAPC, and the thickness is 0.001-1000 nm.

5. The flexible triple-junction stacked solar cell according to claim 1, wherein: The perovskite absorption layer is composed of a monovalent cation (A), a divalent cation (B), and a monovalent anion (X), with a structural general formula of ABX3. Among them, the monovalent cation includes one or more ions among amino, amidino, lithium, sodium, potassium, rubidium, and cesium; the divalent cation includes one or more ions among beryllium, magnesium, calcium, strontium, barium, titanium, copper, zinc, tin, lead, tungsten, gallium, mercury, bismuth, palladium, arsenic, germanium, silver, indium, selenium, and rhodium; the monovalent anion includes one or more ions among chlorine, bromine, iodine, pseudohalogen (CN, OCN, SCN), and has a thickness of 0.001 - 100 μm.

6. The flexible triple-junction stacked solar cell according to claim 1, wherein: The passivation layer mentioned above is one or more of Si3N4, SiN x , Al2O3, SiO2, AlN, InSb, SiC, TiO2, fullerene derivatives (C 60 , C 70 ), microcrystalline silicon or amorphous silicon, and the thickness is 0.001 - 50 nm.

7. The flexible triple-junction stacked solar cell according to claim 1, characterized in that: The electron transport layer is one or more of SnO2, TiO2, ZnO, ZrO2, fullerene and derivatives (C 60 , C 70 , PCBM), TiSnO x , ICBA, BCP or SnZnO x , with a thickness of 0.001 - 500 nm.

8. The flexible triple-junction stacked solar cell according to claim 1, wherein: The intermediate layer includes one or several of the hole transport layer, perovskite absorption layer, passivation layer, electron transport layer, buffer layer, and antireflection layer in the flexible triple-junction tandem solar cell described in claim 1.

9. The flexible triple-junction stacked solar cell according to claim 1, wherein: The buffer layer is one or more of V2O5, PMMA, MoOx, Ag, Au, Cu, SnO2, ZnO, TiO2, Al2O3, SiO2, Si3N4, fullerene derivatives (C 60 , C 70， PCBM), microcrystalline silicon or amorphous silicon, and has a thickness of 0.001 - 100 nm.

10. A method for preparing the flexible triple-junction stacked solar cell according to any one of claims 1-9, characterized in that, It includes the following steps: S1. Provide an ultra-thin crystalline silicon or a CIGS bottom cell substrate based on a steel substrate, and prepare the interface layer on the substrate by methods including but not limited to spin coating, evaporation coating, sputtering, and spraying. S2. Prepare the hole transport layer on the interface layer by methods including but not limited to spin coating, evaporation coating, sputtering, and spraying. S3. Prepare the perovskite absorption layer on the hole transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray decomposition, scraping, printing, or slot coating. S4. Prepare the passivation layer on the perovskite absorption layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). S5. Prepare the buffer layer on the passivation layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). S6. Prepare the electron transport layer on the buffer layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). S7. Prepare the intermediate layer on the electron transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray decomposition, scraping, printing, or slot coating. S8. Prepare the hole transport layer on the intermediate layer by methods including but not limited to spin coating, evaporation coating, sputtering, and spraying. S9. Prepare the perovskite absorption layer on the hole transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray decomposition, scraping, printing, or slot coating. S10. Prepare the passivation layer on the perovskite absorption layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD). S11. Prepare a buffer layer on the passivation layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD); S12. Prepare an electron transport layer on the buffer layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD); S13. Prepare a transparent conductive layer on the electron transport layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal spray pyrolysis, doctor blading, printing, or slot die coating; S14. Prepare a metal electrode on the transparent conductive layer by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD); S15. Prepare an antireflection layer on the metal electrode by methods including but not limited to spin coating, evaporation coating, sputtering, spraying, thermal growth, or atomic layer deposition (ALD).

Images