WO2024149012A1 - 叠层太阳能电池 - Google Patents

叠层太阳能电池 Download PDF

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WO2024149012A1
WO2024149012A1 PCT/CN2023/138544 CN2023138544W WO2024149012A1 WO 2024149012 A1 WO2024149012 A1 WO 2024149012A1 CN 2023138544 W CN2023138544 W CN 2023138544W WO 2024149012 A1 WO2024149012 A1 WO 2024149012A1
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transport layer
battery
carrier transport
solar cell
layer
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解俊杰
吴兆
刁一凡
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Longi Green Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/12—Electrical configurations of PV cells, e.g. series connections or parallel connections
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Definitions

  • the present application relates to the technical field of solar cells, and in particular to a stacked solar cell.
  • the theoretical upper limit of the energy conversion efficiency of a single-junction solar cell with a single absorption layer is limited by the Shockley-Queisser theoretical limit. No matter what kind of absorption layer material, as a single-junction solar cell, its efficiency cannot exceed 33.7%. Therefore, according to different absorption windows, different absorption layer materials are used for superposition to prepare a multi-junction absorption layer structure of a stacked solar cell, and its efficiency can exceed the above upper limit. According to theoretical research, the efficiency of a two-junction stacked cell can reach 44-46%, and the efficiency of a three-junction stack can exceed 50%.
  • the perovskite-crystalline silicon tandem battery which uses the "perovskite battery” as the upper battery and the “crystalline silicon battery” as the lower battery, has both cost and efficiency advantages and is considered to be the tandem battery with the greatest prospects for large-scale application.
  • the conversion efficiency of the perovskite-crystalline silicon tandem battery has reached 31.3%, and there is still great room for improvement.
  • the current series connection structure of perovskite-crystalline silicon stacked cells either uses a composite layer or a tunnel junction series connection structure, in which the tunnel junction series connection structure is composed of heavily doped n-type silicon and heavily doped p-type silicon contacting to form a silicon-based tunnel junction.
  • the heavily doped n-Si conduction band electrons tunnel to the heavily doped p-Si valence band based on the quantum tunneling effect to achieve conductive series connection.
  • there are a large number of free carriers and crystalline silicon defects in the heavily doped silicon and there will be strong Auger recombination and defect recombination effects during the electron transmission process, resulting in a large efficiency loss, affecting the battery efficiency.
  • the present application proposes a stacked solar cell.
  • the present application provides a stacked solar cell, the specific scheme is as follows:
  • a stacked solar cell comprising: an upper layer battery and a lower layer battery stacked in sequence;
  • the upper cell includes a second carrier transport layer
  • the lower cell includes a second carrier transport layer
  • the second carrier transport layer of the upper battery and the second carrier transport layer of the lower battery form a series tunnel junction.
  • the conductivity types of the second carrier transport layer of the upper battery and the second carrier transport layer of the lower battery are opposite.
  • the second carrier transport layer of the upper battery and the second carrier transport layer of the lower battery are respectively a P-type conductive layer or an N-type conductive layer.
  • the width of the space charge region at the interface between the second carrier transport layer of the upper battery and the second carrier transport layer of the lower battery in the tunnel junction is greater than 0 and less than or equal to 10 nm.
  • the upper battery also includes a first carrier transport layer and an absorption layer;
  • the lower battery also includes a first carrier transport layer and an absorption layer.
  • the upper cell is selected from a perovskite solar cell, a copper indium gallium selenide solar cell, a cadmium telluride solar cell or a III-V compound solar cell.
  • first carrier transport layer of the upper battery is an electron transport layer and the second carrier transport layer of the upper battery is a hole transport layer; or,
  • the first carrier transport layer of the upper battery is a hole transport layer and the second carrier transport layer of the upper battery is an electron transport layer.
  • the material of the electron transport layer of the upper battery is one or more of C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , Nb 2 O 5 or an N-type semiconductor material with a work function greater than 0 and less than or equal to 5.0 eV.
  • the lower layer cell is a narrow bandgap solar cell.
  • the lower layer battery is a thin film battery or a single crystal silicon battery.
  • first carrier transport layer of the lower battery is an electron transport layer and the second carrier transport layer of the lower battery is a hole transport layer;
  • the first carrier transport layer of the lower battery is a hole transport layer and the second carrier transport layer of the lower battery is an electron transport layer.
  • the material of the electron transport layer of the lower battery is one or more of C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , Nb 2 O 5 , and N-type semiconductor materials with a work function greater than 0 and less than or equal to 4.4 eV.
  • the material of the hole transport layer of the lower battery is one or more of nickel oxide, CuSCN, cuprous iodide, cuprous oxide, cupric oxide, cuprous chromate, Spiro-OMeTAD, PTAA, PEDOT-PSS, PEDOT, P3HT, TFB (poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)]), F8, a P-type semiconductor material with a work function greater than or equal to 5.2 eV, and an N-type semiconductor material with a work function greater than or equal to 6 eV.
  • the present application provides a non-silicon-based tunnel junction structure for an upper battery-lower battery series structure.
  • the design principle of the tunnel junction structure is to combine the material selection of the carrier transport layer of the upper battery and the lower battery, and on the basis of meeting the requirements of energy level matching, use the transport layer of the upper battery and the (non-silicon-based) transport layer of the lower battery to construct a tunnel junction, thereby solving the above-mentioned strong composite effect problem of the silicon-based tunnel junction.
  • FIG1 is a schematic diagram of the structure of a perovskite-crystalline silicon tandem cell in the prior art
  • FIG2 is a schematic diagram of the structure of a stacked solar cell in the present application.
  • FIG3 is a schematic diagram of the conductive principle of the tunnel junction in the present application.
  • FIG4 is a schematic diagram of the structure of a stacked solar cell in Example 1;
  • FIG5 is a schematic diagram of the structure of a stacked solar cell in Example 2.
  • the perovskite-crystalline silicon tandem battery which uses the "perovskite battery” as the upper battery and the “crystalline silicon battery” as the lower battery, has both cost and efficiency advantages and is considered to be the tandem battery with the greatest prospects for large-scale application.
  • the conversion efficiency of the perovskite-crystalline silicon tandem battery has reached 31.3%, and there is still great room for improvement.
  • FIG. 1 it is a schematic diagram of the device structure of a two-terminal structured perovskite-crystalline silicon tandem battery.
  • 1 is the upper battery
  • 2 is the lower battery
  • 3 is the series structure between the upper and lower batteries.
  • TCO transparent conductive oxide
  • 3 is a TCO composite layer, which is usually made of transparent conductive oxide materials such as ITO, FTO, and AZO.
  • transparent conductive oxide materials such as ITO, FTO, and AZO.
  • the parasitic absorption and poor lateral conductivity of TCO will lead to large efficiency losses, affecting the efficiency of the stacked cell;
  • 3 is a tunnel junction, which is composed of heavily doped n-type silicon and heavily doped p-type silicon contact ("31 is n ++ -Si, 32 is p ++ -Si" or "31 is p ++ -Si, 32 is n ++ -Si"), a silicon-based tunnel junction, and the heavily doped n-Si conduction band electrons tunnel to the heavily doped p-Si valence band based on the quantum tunneling effect to achieve conductive series connection.
  • the present application provides a stacked solar cell, comprising: an upper battery 1 and a lower battery 2 stacked in sequence; the upper battery 1 comprises a second carrier transport layer 13; the lower battery 2 comprises a second carrier transport layer 23; the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 form a series tunnel junction.
  • the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 have opposite conductivity types.
  • the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 are respectively P-type conductive layers or N-type conductive layers, the second carrier transport layer of the upper battery is a P-type conductive layer, and the second carrier transport layer of the lower battery is an N-type conductive layer; or the second carrier transport layer of the upper battery is an N-type conductive layer, and the second carrier transport layer of the lower battery is an N-type conductive layer.
  • the second carrier transport layer of the layer battery is a P-type conductive layer.
  • E cp , E vp , E fp , E cn , E vn , and E fn can be found in commonly used semiconductor manuals, or can be obtained by combining the two testing methods of “ultraviolet visible absorption spectroscopy” and “ultraviolet photoelectron spectroscopy” for analysis and testing.
  • the conduction band refers to the energy space formed by free electrons, that is, the energy range of electrons moving freely in a solid structure.
  • the bottom of the conduction band is the lowest energy level of the conduction band.
  • the distance from the bottom of the conduction band to the energy level of free electrons in a vacuum is called the affinity of the semiconductor, that is, the energy required to take an electron carrier from the inside of the semiconductor to the vacuum.
  • the valence band also known as the valence band, refers to a low energy band formed by the energy levels of atomic orbitals that are filled with electrons.
  • the electrons in the atomic orbitals and in a bonding state are called valence electrons.
  • the many energy levels occupied by these valence electrons can be merged and regarded as a single continuous energy range.
  • the top of the valence band refers to the energy level with the highest energy in the valence band; the bottom of the conduction band refers to the energy level with the lowest energy in the conduction band.
  • Bandgap refers to the energy range where the energy state density is zero in the band structure.
  • the Fermi level refers to the highest energy level in the energy band of a solid that is filled with electrons when the Fermi level temperature is absolute zero.
  • the width of the space charge region at the interface between the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 in the tunnel junction is greater than 0 and less than or equal to 10 nm, preferably greater than 0 and less than or equal to 5 nm, and further preferably greater than 0 and less than or equal to 2 nm.
  • the width of the space charge region at the interface of the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 in the tunnel junction is also referred to as the junction region of the tunnel junction.
  • the junction region of the tunnel junction must be narrow enough to achieve the tunneling of electrons from the conduction band of the N region to the valence band of the P region. If the junction region is too wide, the tunneling resistance is too large and even tunneling is impossible.
  • the width of the junction region of the tunnel junction is greater than 0 and less than or equal to 10nm, preferably greater than 0 and less than or equal to 5nm, and more preferably greater than 0 and less than or equal to 2nm;
  • the width of the junction region of the tunnel junction can be 0.01nm, 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1.0nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm, 1.6nm, 1.7nm, 1.8nm, 1.9nm, 2.0nm, 2.1nm, 2.2nm, 2.3nm m, 2.4nm, 2.5nm, 2.6nm, 2.7nm, 2.8nm, 2.9nm, 3.0nm, 3.1nm, 3.2nm, 3.3nm, 3.4nm, 3.5nm, 3.6nm, 3.7nm, 3.8nm, 3.9nm, 4.0nm, 4.1nm, 4.2nm, 4.3nm, 4.4nm, 4.5nm, 4.6nm, 4.7nm,
  • the width of the junction region of the tunnel junction can be detected by methods commonly used in the art, for example, the thickness of the junction region can be tested by a TOF-SIMS device.
  • TOF-SIMS Time of Flight Secondary Ion Mass Spectrometry
  • TOF-SIMS is an extremely high-resolution measurement technology that uses primary ions to excite the sample surface to generate extremely small amounts of secondary ions, and determines the mass of the ions based on the different flight times of the secondary ions due to their different masses.
  • the forward bias is further increased, the N-region conduction band electrons will drift to the P-region conduction band, and the current that continues to increase at this time will not be a tunneling current, but will become a conventional PN junction conduction mechanism.
  • the upper battery 1 further includes a first carrier transport layer 12 and an absorption layer 11 , that is, the upper battery 1 is provided with the first carrier transport layer 12 , the absorption layer 11 and the second carrier transport layer 13 in sequence.
  • the upper cell 1 is a wide bandgap solar cell, preferably
  • the bandgap width of the absorption layer of the upper battery is 1.5-2.5eV, preferably 1.6-1.9eV; for example, the bandgap width of the absorption layer of the upper battery can be 1.5eV, 1.6eV, 1.7eV, 1.8eV, 1.9eV, 2.0eV, 2.1eV, 2.2eV, 2.3eV, 2.4eV, 2.5eV or any range therebetween.
  • the upper cell is a thin-film solar cell structure, a whole-surface single-junction thin-film cell, or a thin-film solar cell module with lines connected in series.
  • the upper cell 1 is selected from a perovskite solar cell, a copper indium gallium selenide solar cell, a cadmium telluride solar cell or a III-V compound solar cell, preferably a perovskite solar cell.
  • the first carrier transport layer 12 and the second carrier transport layer 13 of the upper battery 1 have opposite conductivity types, the first carrier transport layer 12 of the upper battery 1 is an electron transport layer and the second carrier transport layer 13 of the upper battery 1 is a hole transport layer; or, the first carrier transport layer 12 of the upper battery 1 is a hole transport layer and the second carrier transport layer 13 of the upper battery 1 is an electron transport layer.
  • the material of the electron transport layer of the upper battery is an N-type semiconductor material.
  • the material of the electron transport layer of the upper battery is one or more of C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , Nb 2 O 5 or an N-type semiconductor material with a work function greater than 0 and less than or equal to 5.0 eV.
  • C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , and Nb 2 O 5 are N-type semiconductor materials.
  • the N-type semiconductor material with a work function greater than 0 and less than or equal to 5.0 eV is NaOH-modified ITO, Na2SO4 - modified ITO or Al-doped ZnO. Since the surface work function of the material will change depending on the surface treatment method. In some embodiments of the present application, the work function of NaOH-modified ITO is 3.71 eV, the work function of Na2SO4 - modified ITO is 4.53 eV, and the work function of Al-doped ZnO is 4.62 eV.
  • the material of the hole transport layer of the upper battery is nickel oxide, CuSCN, cuprous iodide, cuprous oxide, cupric oxide, cuprous chromate, Spiro-OMeTAD, PTAA, PEDOT-PSS, PEDOT, P3HT, TFB (poly [(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl) diphenylamine)]), F8, work function greater than or equal to 5.0 eV
  • a P-type semiconductor material with a work function greater than or equal to 6eV and an N-type semiconductor material with a work function greater than or equal to 6eV.
  • the material of the hole transport layer of the upper battery is usually an n-type semiconductor material. It can be an organic semiconductor or an inorganic semiconductor, among which nickel oxide, CuSCN, cuprous iodide, cuprous oxide, cupric oxide, cuprous chromate, Spiro-OMeTAD, PTAA, PEDOT-PSS, PEDOT, P3HT, TFB (poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)]), and F8 are all n-type semiconductor materials.
  • n-type semiconductor material can be an organic semiconductor or an inorganic semiconductor, among which nickel oxide, CuSCN, cuprous iodide, cuprous oxide, cupric oxide, cuprous chromate, Spiro-OMeTAD, PTAA, PEDOT-PSS, PEDOT, P3HT, TFB (poly[(9,9-d
  • the P-type semiconductor material with a work function greater than or equal to 5.0 eV is a (1-x) NiO2 :xNiO solid solution. Since the surface work function of the material varies depending on the surface treatment method, in some embodiments of the present application, the work function of the (1-x) NiO2 :xNiO solid solution varies depending on the surface treatment method, and its work function is 6.0 eV.
  • the N-type semiconductor material with a work function greater than or equal to 6 eV is selected from one or more of molybdenum oxide, vanadium oxide, and tungsten oxide.
  • the lower battery 2 further includes a first carrier transport layer 22 and an absorption layer 21 , that is, the lower battery 2 is provided with the first carrier transport layer 22 , the absorption layer 21 and the second carrier transport layer 23 in sequence.
  • the lower battery 2 is a narrow bandgap solar cell.
  • the bandgap width of the absorption layer of the lower battery 2 is 0.7-1.4eV, preferably 0.9-1.2eV; for example, the bandgap width of the absorption layer of the lower battery can be 0.7eV, 0.8eV, 0.9eV, 1.0eV, 1.1eV, 1.2eV, 1.3eV, 1.4eV or any range therebetween.
  • the lower battery 2 is a thin film battery or a monocrystalline silicon battery, preferably a monocrystalline silicon battery; further preferably PERC, Topcon, HJT, POLO or DASH, preferably HJT, DASH; more preferably DASH.
  • the material of the electron transport layer of the lower battery is an N-type semiconductor material, preferably an organic semiconductor material or an inorganic semiconductor material.
  • the material of the electron transport layer of the lower battery is C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , One or more of SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , Nb 2 O 5 , and an N-type semiconductor material having a work function greater than 0 and less than or equal to 4.4 eV.
  • C60, PC61BM, PC71BM, ICBA, tin oxide, zinc oxide, titanium oxide, CdS, CdSe, WO 3 , ZnSnO 4 , SrTiO 3 , Ga 2 O 3 , In 2 O 3 , Ta 2 O 5 , MoS 2 , and Nb 2 O 5 are N-type semiconductor materials.
  • the material of the hole transport layer of the lower battery may be a p-type semiconductor material, which may be an organic semiconductor or an inorganic semiconductor.
  • the material of the hole transport layer of the lower battery is one or more of nickel oxide, CuSCN, cuprous iodide, cuprous oxide, cupric oxide, cuprous chromate, Spiro-OMeTAD, PTAA, PEDOT-PSS, PEDOT, P3HT, TFB (poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)]), F8, a P-type semiconductor material with a work function greater than or equal to 5.2 eV, and an N-type semiconductor material with a work function greater than or equal to 6 eV.
  • the P-type semiconductor material with a work function greater than or equal to 5.2 eV is NiO 2+x .
  • the work function of NiO 2+x is 6.0 eV.
  • the N-type semiconductor material with a work function greater than or equal to 6 eV is one or more of molybdenum oxide, vanadium oxide, and tungsten oxide.
  • work function is also called work function or work function, and is defined in solid physics as the minimum energy required to move an electron from the inside of a solid to the surface of the object.
  • Work function can be measured by UPS (ultraviolet photoelectron spectroscopy).
  • the bandgap refers to the energy difference between the top energy level of the valence band and the bottom energy level of the conduction band.
  • the bandgap can be measured by UPS (ultraviolet photoelectron spectroscopy) and UV-vis (ultraviolet visible absorption spectroscopy) collaborative analysis.
  • 4 is an electrode; 1 is an upper perovskite battery, wherein 11 is a perovskite absorption layer, 12 is a first carrier transport layer, and 13 is a second carrier transport layer; 2 is a lower battery, wherein 21 is a crystalline silicon absorption layer, 22 is a first carrier transport layer, and 23 is a second carrier transport layer; the first carrier transport layer 12 of the upper battery and the second carrier transport layer 13 of the upper battery have opposite conductivity types, the first carrier transport layer 22 of the lower battery and the second carrier transport layer 23 of the lower battery have opposite conductivity types, and the second carrier transport layer 13 of the upper battery and the second carrier transport layer 23 of the lower battery have opposite conductivity types, and together form a series tunnel junction 5.
  • the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 form a series tunnel junction.
  • the series tunnel junction satisfies the following: the conductivity types of the second carrier transport layer 13 of the upper battery 1 and the second carrier transport layer 23 of the lower battery 2 are opposite; and the following formulas (1) to (3) are satisfied: E vp ⁇ E cn (Formula 1), E fp ⁇ E vp (Formula 2); and E fn ⁇ E cn (Formula 3); the width of the junction region of the tunnel junction is greater than 0 and less than or equal to 10nm, preferably greater than 0 and less than or equal to 5nm, and more preferably greater than 0 and less than or equal to 2nm.
  • the material of the second carrier transport layer 23 of the lower battery can be MoOx or V2O5 or WO3 .
  • the material of the second carrier transport layer 13 of the upper battery when the material of the second carrier transport layer 13 of the upper battery is PEDOT:PSS, the material of the second carrier transport layer 23 of the lower battery can be V 2 O 5 .
  • the material of the second carrier transport layer 23 of the lower battery can be NiO.
  • the upper cell is a perovskite cell
  • the lower cell is a DASH structure crystalline silicon cell.
  • the perovskite cell and the DASH structure crystalline silicon cell form a stacked solar cell, where:
  • 41 is an ITO upper electrode
  • 21 is an N-type single crystal silicon absorption layer with a band gap of 1.12 eV;
  • 22 is a NiO x hole transport layer
  • the upper cell is a perovskite cell
  • the lower cell is a perovskite cell
  • the perovskite cell of the upper cell and the perovskite cell of the lower cell form a stacked solar cell, wherein:
  • 41 is an ITO upper electrode
  • 21 is the CsSnI 3 perovskite absorber layer with a band gap of 1.25 eV;
  • 22 is a SnO 2 electron transport layer
  • Example 5 The only difference between Example 5 and Example 1 is that the width of the junction region of the tunnel junction is 10 nm, and the other conditions are the same.
  • Example 6 The only difference between Example 6 and Example 1 is that the width of the junction region of the tunnel junction is 12 nm, and the other conditions are the same.
  • Example 6 since the width of the junction region of the tunnel junction is greater than 10 nm, if the junction region is too wide, the tunneling resistance will be too large, resulting in failure to achieve tunneling.

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Abstract

一种叠层太阳能电池，包括：依次层叠设置的上层电池（1）、下层电池（2）；上层电池（1）包括第二载流子传输层（13）；下层电池（2）包括第二载流子传输层（23）；上层电池（1）的第二载流子传输层（13）和下层电池（2）的第二载流子传输层（23）构成串联隧道结（5）。该串联隧道结（5）的设计原则是结合上层电池（1）和下层电池（2）载流子传输层的材料选择，在满足能级匹配的要求的基础上，利用上层电池（1）的第二载流子传输层（13）和下层电池（2）的非硅基第二载流子传输层（23）构建串联隧道结（5），从而解决硅基隧道结较强复合效应的问题。

Description

叠层太阳能电池
相关申请的引用
本申请要求在2023年01月10日提交中国专利局、申请号为202310033153.5，名称为“叠层太阳能电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及太阳能电池技术领域，具体涉及一种叠层太阳能电池。
背景技术
具有单一吸收层的单结太阳能电池，其能量转换效率的理论上限受到Shockley-Queisser理论极限的限制，无论什么样的吸收层材料，作为单结结构的太阳能电池，其效率无法超过33.7％。因此，根据吸收窗口的不同，分别采用不同的吸收层材料进行叠加，制备多结吸收层结构的叠层太阳能电池，其效率可以突破上述上限。据理论研究，两结叠层电池的效率可达到44-46％，三结叠层的效率可超过50％。
在现有的叠层电池的技术路线当中，以“钙钛矿电池”为上层电池，“晶硅电池”为下层电池构建的钙钛矿-晶硅叠层电池，兼具成本和效率优势，被认为是最具大规模应用前景的叠层电池。经过不到10年的发展，目前钙钛矿-晶硅叠层电池的转换效率已经达到了31.3％，且仍有极大的提升空间。
但目前的钙钛矿-晶硅叠层电池中的串联结构要么使用复合层，要么使用隧道结串联结构，其中隧道结串联结构由重掺杂的n型硅和重掺杂的p型硅接触组成一个硅基隧道结，重掺n-Si导带电子基于量子隧穿效应隧穿至重掺p-Si的价带，实现导电串联。然后，重掺硅中具有大量的自由载流子和晶硅缺陷，电子传输过程中会有较强的俄歇复合和缺陷复合效应，导致较大的效率损失，影响电池效率。
发明内容
针对上述问题，本申请提出了一种叠层太阳能电池。
本申请提供一种叠层太阳能电池，具体方案如下：
一种叠层太阳能电池，包括：依次层叠设置的上层电池、下层电池；
上层电池包括第二载流子传输层；
下层电池包括第二载流子传输层；
上层电池的第二载流子传输层和下层电池的第二载流子传输层构成串联隧道结。
进一步，上层电池的第二载流子传输层和下层电池的第二载流子传输层的导电类型相反。
进一步，上层电池的第二载流子传输层和下层电池的第二载流子传输层分别为P型导电层或N型导电层，
其中，在P型导电层的导带底、价带顶和费米能级的位置分别用Ec-p、Ev-p、Ef-p来表示，N型导电层的导带底、价带顶和费米能级的位置分别用Ec-n、Ev-n、Ef-n来表示的情况下，需要满足如下公式(1)～(3)：
Ev-p≥Ec-n(公式1)
Ef-p≤Ev-p(公式2)；且
Ef-n≥Ec-n(公式3)。
进一步，隧道结中上层电池的第二载流子传输层和下层电池的第二载流子传输层界面处的空间电荷区域的宽度大于0且小于等于10nm。
进一步，上层电池还包括第一载流子传输层和吸收层；
下层电池还包括第一载流子传输层和吸收层。
进一步，上层电池为宽带隙太阳能电池。
进一步，上层电池选自钙钛矿太阳能电池、铜铟镓硒太阳能电池、碲化镉太阳能电池或III-V族化合物太阳能电池。
进一步，上层电池的第一载流子传输层为电子传输层且上层电池的第二载流子传输层为空穴传输层；或者，
上层电池的第一载流子传输层为空穴传输层且上层电池的第二载流子传输层为电子传输层。
进一步，上层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5或功函数大于0且小于等于5.0eV的N型半导体材料中的一种或两种以上。
进一步，上层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.0eV的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
进一步，下层电池为窄带隙太阳能电池。
进一步，下层电池为薄膜电池或单晶硅电池。
进一步，下层电池的第一载流子传输层为电子传输层且下层电池的第二载流子传输层为空穴传输层；或者，
下层电池的第一载流子传输层为空穴传输层且下层电池的第二载流子传输层为电子传输层。
进一步，下层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5、功函数大于0且小于等于4.4eV的N型半导体材料中的一种或两种以上。
进一步，下层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.2eV的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
本申请技术效果如下：
上层电池第二载流子传输层和下层电池第二载流子传输层导电类型相反。两个导电类型相反的半导体接触后，当它们满足一定能带、厚度和结构满足一定要求时，可以形成隧道结，电子从P区的价带注入至N区的导带，实现导通串联的功能。
本申请提供了一种用于上层电池-下层电池串联结构的非硅基隧道结结构。该隧道结结构的设计原则是结合上层电池和下层电池载流子传输层的材料选择，在满足能级匹配的要求的基础上，利用上层电池的传输层和下层电池的(非硅基)传输层构建隧道结，从而解决硅基隧道结的上述较强复合效应的问题。
附图说明
附图用于更好地理解本申请，不构成对本申请的不当限定。其中：
图1为现有技术中的钙钛矿-晶硅叠层电池的结构示意图；
图2为本申请中的叠层太阳能电池的结构示意图；
图3为本申请中的隧道结的导电原理示意图；
图4为实施例1中的叠层太阳能电池的结构示意图；
图5为实施例2中的叠层太阳能电池的结构示意图；
附图标记说明
1：上层电池，2：下层电池，3：上下电池之间的串联结构，
4：电极；11：钙钛矿吸收层，12：第一载流子传输层，13：第二载
流子传输层；21：晶硅吸收层，22：第一载流子传输层，23：第二载流子传输层；13和23共同组成串联隧道结5。
具体实施例
以下对本申请的示范性实施例做出说明，其中包括本申请实施例的各种细节以助于理解，应当将它们认为仅仅是示范性的。因此，本领域普通技术人员应当认识到，可以对这里描述的实施例做出各种改变和修改，而不会背离本申请的范围和精神。同样，为了清楚和简明，以下的描述中省略了对公知功能和结构的描述。在本申请中上下位置依据光线 入射方向而定，光线入射处为上。
在现有的叠层电池的技术路线当中，以“钙钛矿电池”为上层电池，“晶硅电池”为下层电池构建的钙钛矿-晶硅叠层电池，兼具成本和效率优势，被认为是最具大规模应用前景的叠层电池。经过不到10年的发展，目前钙钛矿-晶硅叠层电池的转换效率已经达到了31.3％，且仍有极大的提升空间。
如图1所示，为两端结构的钙钛矿-晶硅叠层电池的器件结构示意图。图中，1为上层电池，2为下层电池，3为上下电池之间的串联结构。目前使用在叠层电池上的串联结构主要有两种：一、TCO(透明导电氧化物)复合层，如图1中a所示；二、隧道结串联结构，如图1中b所示。
在图1的a中，3为TCO复合层，通常用ITO、FTO、AZO等透明导电氧化物材料制备。然而，TCO的寄生吸收、较差的横向电导率会导致较大的效率损失，影响叠层电池的效率；
在图1的b中，3为隧道结，由重掺杂的n型硅和重掺杂的p型硅接触组成(“31为n++-Si，32为p++-Si”或“31为p++-Si，32为n++-Si”)一个硅基隧道结，重掺n-Si导带电子基于量子隧穿效应隧穿至重掺p-Si的价带，实现导电串联。然后，重掺硅中具有大量的自由载流子和晶硅缺陷，电子传输过程中会有较强的俄歇复合和缺陷复合效应，导致较大的效率损失，影响电池效率。
因此，在钙钛矿-晶硅叠层电池中，在分别优化钙钛矿上层电池、晶硅下层电池的基础上，设计高效率、低损失的上下层电池之间的串联结构，是进一步提升转换效率所亟需解决的关键技术问题。
本申请提供了一种叠层太阳能电池，包括：依次层叠设置的上层电池1、下层电池2；上层电池1包括第二载流子传输层13；下层电池2包括第二载流子传输层23；上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23构成串联隧道结。
在本申请的一些实施方式中，上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23的导电类型相反。
在本申请的一些实施方式中，上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23分别为P型导电层或N型导电层，上层电池的第二载流子传输层为P型导电层，下层电池的第二载流子传输层为N型导电层；或者上层电池的第二载流子传输层为N型导电层，下 层电池的第二载流子传输层为P型导电层。
其中，在P型导电层的导带底、价带顶和费米能级的位置分别用Ec-p、Ev-p、Ef-p来表示，N型导电层的导带底、价带顶和费米能级的位置分别用Ec-n、Ev-n、Ef-n来表示的情况下，需要满足如下公式(1)～(3)：
Ev-p≥Ec-n(公式1)
Ef-p≤Ev-p(公式2)；且
Ef-n≥Ec-n(公式3)。
在本申请中，Ec-p、Ev-p、Ef-p、Ec-n、Ev-n、Ef-n可以在常用的半导体手册中查询，也可以通过“紫外可见吸收光谱”和“紫外光电子能谱”两种测试方法结合分析测试得到。
在本申请中，导带是指导带是由自由电子形成的能量空间，即固体结构内自由运动的电子所具有的能量范围。导带底是导带的最低能级，在半导体中，导带底到真空中自由电子能级的间距，称为半导体的亲和能，即是把一个电子载流子从半导体内部拿到真空中去所需要的能量。
价带，也称为价电带，指已充满电子的原子轨道能级所形成的低能量带，其中，处在原子轨道中并呈键合状态的电子称为价电子，由这些价电子所占有的许多能级可加以归并并视为一个单一的连续的能量范围。价带顶是指价带中能量最高的能级位置；导带底是指导带中能量最低的能级位置。
禁带，指在能带结构中能态密度为零的能量区间。
在本申请中，费米能级是指费米能级温度为绝对零度时固体能带中充满电子的最高能级。
在本申请的一些实施方式中，隧道结中上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23界面处的空间电荷区域的宽度大于0且小于等于10nm，优选为大于0且小于等于5nm，进一步优选为大于0且小于等于2nm。
在本申请中，隧道结中上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23界面处的空间电荷区域的宽度也称为隧道结的结区，该隧道结的结区一定要足够窄，才能实现电子从N区导带向P区价带的隧穿。如果结区过宽的话，隧穿阻力过大，甚至无法隧穿。一般要实现有效隧穿，隧道结的结区的宽度大于0且小于等于10nm，优选为大于0且小于等于5nm，进一步优选为大于0且小于等于2nm；
例如，隧道结的结区的宽度可以为0.01nm、0.1nm、0.2nm、0.3nm、0.4nm、0.5nm、0.6nm、0.7nm、0.8nm、0.9nm、1.0nm、1.1nm、1.2nm、1.3nm、1.4nm、1.5nm、1.6nm、1.7nm、1.8nm、1.9nm、2.0nm、2.1nm、2.2nm、2.3nm、2.4nm、2.5nm、2.6nm、2.7nm、2.8nm、2.9nm、3.0nm、3.1nm、3.2nm、3.3nm、3.4nm、3.5nm、3.6nm、3.7nm、3.8nm、3.9nm、4.0nm、4.1nm、4.2nm、4.3nm、4.4nm、4.5nm、4.6nm、4.7nm、4.8nm、4.9nm、5.0nm、5.1nm、5.2nm、5.3nm、5.4nm、5.5nm、5.6nm、5.7nm、5.8nm、5.9nm、6.0nm、6.1nm、6.2nm、6.3nm、6.4nm、6.5nm、6.6nm、6.7nm、6.8nm、6.9nm、7.0nm、7.1nm、7.2nm、7.3nm、7.4nm、7.5nm、7.6nm、7.7nm、7.8nm、7.9nm、8.0nm、8.1nm、8.2nm、8.3nm、8.4nm、8.5nm、8.6nm、8.7nm、8.8nm、8.9nm、9.0nm、9.1nm、9.2nm、9.3nm、9.4nm、9.5nm、9.6nm、9.7nm、9.8nm、9.9nm、10.0nm或其之间的任意范围。
在本申请中，隧道结的结区的宽度可以通过本领域常用的方法进行检测，例如可以通过TOF-SIMS设备来测试结区的厚度，TOF-SIMS(Time of Flight Secondary Ion Mass Spectrometry)是通过用一次离子激发样品表面，打出极其微量的二次离子，根据二次离子因不同的质量而飞行到探测器的时间不同来测定离子质量的极高分辨率的测量技术。
在本申请中，利用本申请的方案，可以实现N区导带电子注入P去价带的空态，产生隧穿电流，具体如下：在图3的a中，N型半导体和P型半导体接触，在未加外电压的情况下，N型半导体和P型半导体的费米能级对齐，此时无电流；在隧道结上施加正向偏压，P区费米能级下移，N区费米能级上移，N区导带电子注入P去价带的空态，产生隧穿电流；当Ef-n-Ec-n＝Ev-p-Ef-p时，隧穿电流达到最大，如图3的b所示；继续施加正向偏压，当Ec-n＝Ev-p时，N区导带电子无法注入P区价带的空态，隧穿电流达到最小值，如图3的c所示。当继续增大正向偏压时，N导带电子将漂移至P区导带，这时候再继续增大的电流将不是隧穿电流，将变为常规的PN结导电机制。
如图2所示，上层电池1还包括第一载流子传输层12和吸收层11，即上层电池1依次设置有第一载流子传输层12、吸收层11和第二载流子传输层13。
在本申请的一些实施方式中，上层电池1为宽带隙太阳能电池，优 选地，上层电池的吸收层的禁带宽度为1.5-2.5eV，优选为1.6-1.9eV；例如，上层电池的吸收层的禁带宽度可以为1.5eV、1.6eV、1.7eV、1.8eV、1.9eV、2.0eV、2.1eV、2.2eV、2.3eV、2.4eV、2.5eV或其之间的任意范围。
在本申请的一些实施方式中，上层电池为薄膜太阳能电池结构、整面的单结薄膜电池或划线串联的薄膜太阳能电池组件。
在本申请的一些实施方式中，上层电池1选自钙钛矿太阳能电池、铜铟镓硒太阳能电池、碲化镉太阳能电池或III-V族化合物太阳能电池，优选为钙钛矿太阳能电池。
在本申请的一些实施方式中，上层电池1的第一载流子传输层12和第二载流子传输层13导电类型相反，上层电池1的第一载流子传输层12为电子传输层且上层电池1的第二载流子传输层13为空穴传输层；或者，上层电池1的第一载流子传输层12为空穴传输层且上层电池1的第二载流子传输层13为电子传输层。
在本申请的一些实施方式中，上层电池的电子传输层的材料为N型半导体材料。
在本申请的一些实施方式中，上层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5或功函数大于0且小于等于5.0eV的N型半导体材料中的一种或两种以上。
在本申请中，C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5为N型半导体材料。
在本申请中，功函数大于0且小于等于5.0eV的N型半导体材料为NaOH改性的ITO、Na2SO4改性的ITO或Al掺杂的ZnO。由于材料的表面功函数是会依据表面处理的方式不同，而发生变化。在本申请的一些实施方式中，NaOH改性的ITO的功函数为3.71eV，Na2SO4改性的ITO的功函数为4.53eV，Al掺杂的ZnO的功函数为4.62eV。
在本申请的一些实施方式中，上层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.0eV 的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
在本申请中，上层电池的空穴传输层的材料通常是n型半导体材料。可以是有机半导体，也可以是无机半导体，其中氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8均为N型半导体材料。
在本申请中，功函数大于等于5.0eV的P型半导体材料为(1-x)NiO2:x NiO固溶体。由于材料的表面功函数是会依据表面处理的方式不同，而发生变化。在本申请的一些实施方式中，(1-x)NiO2:x NiO固溶体的功函数根据表面处理的方式不同，其功函数为6.0eV。
在本申请中，功函数大于等于6eV的N型半导体材料选自氧化钼、氧化钒、氧化钨中的一种或两种以上。
如图2所示，下层电池2还包括第一载流子传输层22和吸收层21，即下层电池2依次设置有第一载流子传输层22、吸收层21和第二载流子传输层23。
如图2所示，在本申请的一些实施方式中，下层电池2为窄带隙太阳能电池，优选地，下层电池2的吸收层的禁带宽度为0.7-1.4eV，优选为0.9-1.2eV；例如，下层电池的吸收层的禁带宽度可以为0.7eV、0.8eV、0.9eV、1.0eV、1.1eV、1.2eV、1.3eV、1.4eV或其之间的任意范围。
如图2所示，在本申请的一些实施方式中，下层电池2为薄膜电池或单晶硅电池，优选为单晶硅电池；进一步优选为PERC、Topcon、HJT、POLO或DASH，优选为HJT、DASH；更优选为DASH。
在本申请的一些实施方式中，下层电池的第一载流子传输层和第二载流子传输层导电类型相反，下层电池的第一载流子传输层为电子传输层且下层电池的第二载流子传输层为空穴传输层；或者，下层电池的第一载流子传输层为空穴传输层且下层电池的第二载流子传输层为电子传输层。
在本申请的一些实施方式中，下层电池的电子传输层的材料为N型半导体材料，优选为有机半导体材料或无机半导体材料。
在本申请的一些实施方式中，下层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、 SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5、功函数大于0且小于等于4.4eV的N型半导体材料中的一种或两种以上。
在本申请中，C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5为N型半导体材料。
在本申请的一些实施方式中，下层电池的空穴传输层的材料为可以是p型半导体材料。可以是有机半导体，也可以是无机半导体。
在本申请的一些实施方式中，下层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.2eV的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
在本申请中，功函数大于等于5.2eV的P型半导体材料为NiO2+x。在本申请的一些实施方式中，NiO2+x的功函数为6.0eV。
在本申请中，功函数大于等于6eV的N型半导体材料为氧化钼、氧化钒、氧化钨中的一种或两种以上。
在本申请中，功函数又称功函、逸出功，在固体物理中被定义成：把一个电子从固体内部刚刚移到此物体表面所需的最少的能量。功函数可以通过UPS(紫外光电子能谱)的方法进行测量。
在本申请中，禁带宽度是指价带顶能级和导带底能级之间的能级差值。禁带宽度可以通过UPS(紫外光电子能谱)和UV-vis(紫外可见光吸收光谱)协同分析测的。
在本申请的一些实施方式中，如图2所示，4为电极；1为上层钙钛矿电池，其中11为钙钛矿吸收层，12为第一载流子传输层，13为第二载流子传输层；2为下层电池，其中21为晶硅吸收层，22为第一载流子传输层，23为第二载流子传输层；上层电池的第一载流子传输层12和上层电池的第二载流子传输层13导电类型相反，下层电池的第一载流子传输层22和下层电池的第二载流子传输层23导电类型相反，上层电池的第二载流子传输层13和下层电池的第二载流子传输层23导电类型相反，共同组成串联隧道结5，当上层电池的第二载流子传输层13为P型，下层电池的第二载流子传输层23为N型，当上层电池的第二载流子传输层 13为N型，下层电池的第二载流子传输层23为P型。
在本申请的一些实施方式中，上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23构成串联隧道结。串联隧道结满足如下：上层电池1的第二载流子传输层13和下层电池2的第二载流子传输层23的导电类型相反；且满足如下公式(1)～(3)：Ev-p≥Ec-n(公式1)，Ef-p≤Ev-p(公式2)；且Ef-n≥Ec-n(公式3)；隧道结的结区的宽度大于0且小于等于10nm，优选为大于0且小于等于5nm，进一步优选为大于0且小于等于2nm。
在本申请的一些实施方式中，当上层电池的第二载流子传输层13的材料为Spiro-OMeTAD时，下层电池的第二载流子传输层23的材料可以为MoOx或V2O5或WO3。其中，Spiro-OMeTAD为P型，Ev-p＝-5.2eV，Ef-p＝-5.25eV；V2O5为N型，Ec-n＝-6.5eV，Ef-n＝-6.4eV；WO3为N型，Ec-n＝-6.4eV，Ef-n＝-6.3eV；MoOx为N型，Ec-n＝-6.42eV，Ef-n＝-6.35eV；隧道结的结区的宽度大于0且小于等于10nm。可以看出，此时，满足公式(1)～(3)，实现遂穿串联。
在本申请的一些实施方式中，当上层电池的第二载流子传输层13的材料为PEDOT:PSS时，下层电池的第二载流子传输层23的材料可以为V2O5。其中，PEDOT:PSS为P型，Ev-p＝-5.2eV，Ef-p＝-5.3eV；V2O5为N型，Ec-n＝-6.5eV，Ef-n＝-6.4eV；隧道结的结区的宽度大于0且小于等于10nm。可以看出，此时，满足公式(1)～(3)，实现遂穿串联。
在本申请的一些实施方式中，当上层电池的第二载流子传输层13的材料为WO3时，下层电池的第二载流子传输层23的材料可以为NiO。其中，WO3为N型，Ec-n＝-6.4eV，Ef-n＝-6.3eV；NiO为P型，Ev-p＝-5.4eV，Ef-p＝-5.5eV；隧道结的结区的宽度大于0且小于等于10nm。可以看出，此时，满足公式(1)～(3)，实现遂穿串联。
实施例1
如图4所示，上层电池为钙钛矿电池，下层电池为DASH结构晶硅电池，钙钛矿电池和DASH结构晶硅电池组成叠层太阳能电池，其中：
41为ITO上电极；
12为C60电子传输层；
11为CsPbI3钙钛矿吸收层，带隙1.7eV；
13为PEDOT:PSS(P型)，Ev-p＝-5.2eV，Ef-p＝-5.3eV；
23为V2O5(N型)，Ec-n＝-6.5eV，Ef-n＝-6.4eV；
13和23共同组成串联隧道结，隧道结的结区的宽度为2nm；
21为N型单晶硅吸收层，带隙为1.12eV；
22为NiOx空穴传输层；
42为银栅线下电极。
实施例2
如图5所示，上层电池为钙钛矿电池，下层电池为钙钛矿电池，上层电池的钙钛矿电池和下层电池的钙钛矿电池组成叠层太阳能电池，其中：
41为ITO上电极；
12为PTAA空穴传输层；
11为CsPbI3钙钛矿吸收层，带隙1.7eV；
13为WO3(N型)，Ec-n＝-6.4eV，Ef-n＝-6.3eV；；
23为NiO(P型)，Ev-p＝-5.4eV，Ef-p＝-5.5eV；
13和23共同组成串联隧道结，隧道结的结区的宽度为5nm
21为CsSnI3钙钛矿吸收层，带隙1.25eV；
22为SnO2电子传输层；
42为ITO导电玻璃衬底。
实施例3
实施例3与实施例1的区别仅在于，13为Spiro-OMeTAD(P型)，Ev-p＝-5.2eV，Ef-p＝-5.25eV；23为V2O5(N型)，Ec-n＝-6.5eV，Ef-n＝-6.4eV；其余条件相同。
实施例4
实施例4与实施例1的区别仅在于，13为Spiro-OMeTAD(P型)，Ev-p＝-5.2eV，Ef-p＝-5.25eV；23为WO3(N型)，Ec-n＝-6.4eV，Ef-n＝-6.3eV；其余条件相同。
实施例5
实施例5与实施例1的区别仅在于，隧道结的结区的宽度为10nm，其余条件相同。
实施例6
实施例6与实施例1的区别仅在于，隧道结的结区的宽度为12nm，其余条件相同。
对比例1
对比例1与实施例1的区别仅在于，13为Spiro-OMeTAD(P型)，Ev-p＝-5.2eV，Ef-p＝-5.25eV；23为SnO2(N型)，Ec-n＝-4.3eV，Ef-n＝-4.33eV；其余条件相同。
对比例2
对比例2与实施例1的区别仅在于，13为PEDOT:PSS(P型)，Ev-p＝-5.2eV，Ef-p＝-5.3eV；23为ZnO(N型)，Ec-n＝-4.0eV，Ef-n＝-4.2eV；其余条件相同。
表1
表1中12表示上层电池的第一载流子传输层，13表示上层电池的第二载流子传输层，23表示下层电池的第二载流子传输层，22表示下层电池的第一载流子传输层。
现有的复合串联层：该串联结构依赖于电子和空穴在具有电阻的导电材料(如金属、透明导电氧化物等)中的复合，而其电阻会引起能量的损失，导致电流的降低。而在本申请中，由于隧穿复合串联和现有的复合层的导电机制不同，导致其串联电阻极低，可以认为是零电阻串联。本申请的隧道结中，由于电子是n型材料价带到p型材料导带直接跃迁，跃迁机制依赖于量子隧穿模式。该模式没有隧穿势垒，没有能量的损失。
实施例6因隧道结的结区的宽度大于10nm，结区过宽的话，隧穿阻力过大，导致不能实现遂穿。
对比例1-2因不满足公式(1)～(3)，串联电阻较大，导致不能实现遂穿。
尽管以上结合对本申请的实施方案进行了描述，但本申请并不局限于上述的具体实施方案和应用领域，上述的具体实施方案仅仅是示意性的、指导性的，而不是限制性的。本领域的普通技术人员在本说明书的启示下和在不脱离本申请权利要求所保护的范围的情况下，还可以做出很多种的形式，这些均属于本申请保护之列。

Claims (15)

  1. 一种叠层太阳能电池，包括：依次层叠设置的上层电池、下层电池；
    上层电池包括第二载流子传输层；
    下层电池包括第二载流子传输层；
    上层电池的第二载流子传输层和下层电池的第二载流子传输层构成串联隧道结。
  2. 根据权利要求1的叠层太阳能电池，
    上层电池的第二载流子传输层和下层电池的第二载流子传输层的导电类型相反。
  3. 根据权利要求2的叠层太阳能电池，
    上层电池的第二载流子传输层和下层电池的第二载流子传输层分别为P型导电层或N型导电层，
    其中，在P型导电层的导带底、价带顶和费米能级的位置分别用Ec-p、Ev-p、Ef-p来表示，N型导电层的导带底、价带顶和费米能级的位置分别用Ec-n、Ev-n、Ef-n来表示的情况下，需要满足如下公式(1)～(3)：
    Ev-p≥Ec-n(公式1)
    Ef-p≤Ev-p(公式2)；且
    Ef-n≥Ec-n(公式3)。
  4. 根据权利要求1～3中任一项的叠层太阳能电池，
    隧道结中上层电池的第二载流子传输层和下层电池的第二载流子传输层界面处的空间电荷区域的宽度大于0且小于等于10nm。
  5. 根据权利要求1～4中任一项的叠层太阳能电池，
    上层电池还包括第一载流子传输层和吸收层；
    下层电池还包括第一载流子传输层和吸收层。
  6. 根据权利要求5的叠层太阳能电池，
    上层电池为宽带隙太阳能电池。
  7. 根据权利要求6的叠层太阳能电池，
    上层电池选自钙钛矿太阳能电池、铜铟镓硒太阳能电池、碲化镉太阳能电池或III-V族化合物太阳能电池。
  8. 根据权利要求5的叠层太阳能电池，
    上层电池的第一载流子传输层为电子传输层且上层电池的第二载流子传输层为空穴传输层；或者，
    上层电池的第一载流子传输层为空穴传输层且上层电池的第二载流子传输层为电子传输层。
  9. 根据权利要求8的叠层太阳能电池，
    上层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5或功函数大于0且小于等于5.0eV的N型半导体材料中的一种或两种以上。
  10. 根据权利要求8的叠层太阳能电池，
    上层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.0eV的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
  11. 根据权利要求5的叠层太阳能电池，
    下层电池为窄带隙太阳能电池。
  12. 根据权利要求11的叠层太阳能电池，
    下层电池为薄膜电池或单晶硅电池。
  13. 根据权利要求5的叠层太阳能电池，
    下层电池的第一载流子传输层为电子传输层且下层电池的第二载流子传输层为空穴传输层；或者，
    下层电池的第一载流子传输层为空穴传输层且下层电池的第二载流 子传输层为电子传输层。
  14. 根据权利要求13的叠层太阳能电池，
    下层电池的电子传输层的材料为C60、PC61BM、PC71BM、ICBA、氧化锡、氧化锌、氧化钛、CdS、CdSe、WO3、ZnSnO4、SrTiO3、Ga2O3、In2O3、Ta2O5、MoS2、Nb2O5、功函数大于0且小于等于4.4eV的N型半导体材料中的一种或两种以上。
  15. 根据权利要求13的叠层太阳能电池，
    下层电池的空穴传输层的材料为氧化镍、CuSCN、碘化亚铜、氧化亚铜、氧化铜、铬酸亚铜、Spiro-OMeTAD、PTAA、PEDOT-PSS、PEDOT、P3HT、TFB(聚[(9,9-二辛基芴-2,7-二基)-共-(4,4’-(N-(4-仲丁基苯基)二苯胺)])、F8、功函数大于等于5.2eV的P型半导体材料和功函数大于等于6eV的N型半导体材料中的一种或两种以上。
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