WO2022127669A1 - 叠层光伏器件 - Google Patents

叠层光伏器件 Download PDF

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Publication number
WO2022127669A1
WO2022127669A1 PCT/CN2021/136475 CN2021136475W WO2022127669A1 WO 2022127669 A1 WO2022127669 A1 WO 2022127669A1 CN 2021136475 W CN2021136475 W CN 2021136475W WO 2022127669 A1 WO2022127669 A1 WO 2022127669A1
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Prior art keywords
light
trapping structure
light trapping
photovoltaic device
stacked photovoltaic
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PCT/CN2021/136475
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English (en)
French (fr)
Inventor
吴兆
徐琛
李子峰
解俊杰
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Longi Green Energy Technology Co Ltd
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Longi Green Energy Technology Co Ltd
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Priority to EP21905598.5A priority Critical patent/EP4266383A4/en
Priority to AU2021404771A priority patent/AU2021404771B2/en
Priority to JP2023532241A priority patent/JP7498368B2/ja
Priority to US18/037,286 priority patent/US12268037B2/en
Publication of WO2022127669A1 publication Critical patent/WO2022127669A1/zh
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H10F10/142—Photovoltaic cells having only PN homojunction potential barriers comprising multiple PN homojunctions, e.g. tandem cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/19—Photovoltaic cells having multiple potential barriers of different types, e.g. tandem cells having both PN and PIN junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/40—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising photovoltaic cells in a mechanically stacked configuration
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/488—Reflecting light-concentrating means, e.g. parabolic mirrors or concentrators using total internal reflection
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/703—Surface textures, e.g. pyramid structures of the semiconductor bodies, e.g. textured active layers
    • 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
    • Y02E10/544—Solar cells from Group III-V materials

Definitions

  • the present disclosure relates to the field of solar photovoltaic technology, and in particular, to a stacked photovoltaic device.
  • the stacked photovoltaic device can divide sunlight into multiple bands, from the front to the back, successively use cells with gradually decreasing band gaps to absorb sunlight of different energies, so as to reduce the energy loss in the visible light band and improve the photoelectric conversion efficiency.
  • Layered photovoltaic devices have broad application prospects.
  • the light absorption is incomplete or the optical loss is serious, which reduces the photoelectric conversion efficiency of the device.
  • the present disclosure provides a laminated photovoltaic device, aiming at solving the problems of serious optical loss and low photoelectric conversion efficiency of the laminated photovoltaic device.
  • a stacked photovoltaic device comprising: an upper layer battery unit, a lower layer battery unit, and a layer disposed between the upper layer battery unit and the lower layer battery unit the first light trapping structure between; the band gap width of the upper battery unit is greater than the band gap width of the lower battery unit;
  • the stacked photovoltaic device further includes at least one of a second light trapping structure on the side of the backlight surface of the lower battery unit and a third light trapping structure on the side of the upper battery unit facing the light surface;
  • the first light trapping structure, the second light trapping structure, and the third light trapping structure are all selected from metal or semiconductor materials, and the localized surface plasmons generated by the three correspond to different light wave response peaks respectively;
  • the stacked photovoltaic device has a first cross section perpendicular to the light-facing surface of the stacked photovoltaic device, and the first light trapping structure, the second light trapping structure, and the third light trapping structure are located in the first light trapping structure.
  • Discrete microstructures are formed on a cross section, the average sizes of the discrete microstructures projected onto the light surface of the stacked photovoltaic device are d1, d2, and d3, respectively, and the average spacing between the microstructures is w1, w2, w3;
  • the microstructure is in the The projected average size of the stacked photovoltaic device on the light surface and the average spacing between the adjacent microstructures satisfy:
  • the average size of the microstructures projected on the light surface of the stacked photovoltaic device and the average spacing between adjacent microstructures are as follows relation:
  • the light After the light is incident on the stacked photovoltaic device, the light enters the bottom of the first light trapping structure through scattering and undergoes multiple reflections, which can increase the optical path to a certain extent.
  • the free electrons in the first light trapping structure are coupled with the incident light to form a multi-mode resonance light trapping effect.
  • the phenomenon of localized plasmon mode enhancement the incident light is restricted by the localized plasmonic mode enhancement and exists in the peripheral area of the surface of the first light trapping structure, resulting in a light trapping effect.
  • the first light trapping structure is coupled with the incident light to generate surface plasmons, which convert the incident light into a waveguide mode that conducts in the transverse direction, which changes the direction of the incident light and greatly increases the optical path of the incident light. , which can effectively improve the light trapping effect, and then, an excellent light absorption effect can be achieved through a smaller thickness of the absorption layer, which can reduce the thickness of the absorption layer in each battery unit, thereby reducing the thickness of each battery unit and reducing the stack photovoltaic.
  • the overall thickness of the device is coupled with the incident light to generate surface plasmons, which convert the incident light into a waveguide mode that conducts in the transverse direction, which changes the direction of the incident light and greatly increases the optical path of the incident light.
  • the free electrons in the second light trapping structure and/or the third light trapping structure are coupled with the incident light to form a multi-mode resonance light trapping effect , increasing the absorption of incident light.
  • the second light trapping structure forms a multi-mode resonance light trapping effect for the incident light with a longer wavelength band in the lower cell
  • the third light trapping structure forms a multimode resonance light trapping for the incident light in the shorter wavelength band in the upper cell. The effect is to increase the absorption of incident light.
  • the localized surface plasmons generated by the first light trapping structure, the second light trapping structure and the third light trapping structure correspond to different light wave response peaks respectively.
  • the incident light is fully utilized to improve the absorption of incident light.
  • the average size and average spacing of the first light-trapping structure, the second light-trapping structure, and the third light-trapping structure are w1, w2, and w3, respectively, and have the following relationships:
  • the scattering cross sections of each adjacent two-layer light trapping structure are matched for wavelength, which can fully ensure the incoming amount of incident light, so that less light is emitted from the laminated photovoltaic device, and the absorption amount of incident light is further improved.
  • FIG. 1 shows a schematic diagram of a first cross section perpendicular to the light-facing surface of a stacked photovoltaic device in an embodiment of the present disclosure
  • FIG. 2 shows a schematic structural diagram of a first light trapping structure in an embodiment of the present disclosure
  • FIG. 3 shows a schematic diagram of a partial structure of a stacked photovoltaic device in an embodiment of the present disclosure
  • FIG. 4 shows a schematic partial structure diagram of another stacked photovoltaic device in an embodiment of the present disclosure
  • FIG. 5 shows a schematic diagram of a second cross-section perpendicular to the light-facing surface of the stacked photovoltaic device in an embodiment of the present disclosure
  • FIG. 6 shows a schematic diagram of a third cross-section perpendicular to the light-facing surface of the stacked photovoltaic device in an embodiment of the present disclosure
  • FIG. 7 shows a schematic diagram of a first cross-section perpendicular to the light-facing surface of the fourth type of the stacked photovoltaic device in the embodiment of the present disclosure.
  • FIG. 1 shows a schematic diagram of a first cross-section perpendicular to the light-facing surface of a first type of stacked photovoltaic device in an embodiment of the present disclosure.
  • the stacked photovoltaic device includes an upper layer battery unit 2 , a lower layer battery unit 1 , and a first light trapping structure 3 located between the upper layer battery unit 2 and the lower layer battery unit 1 .
  • the band gap width of the upper layer battery cell 2 is larger than the band gap width of the lower layer battery cell 1 .
  • the band gap width of the upper layer battery unit 2 is 1.5-3 eV, and further, the band gap width of the upper layer battery unit 2 is 1.7-2.3 eV.
  • the number of the upper-layer battery cells 2 and the lower-layer battery cells 1 included in the stacked photovoltaic device is not specifically limited.
  • the specific types of the upper-layer battery unit 2 and the lower-layer battery unit 1 are not limited.
  • the upper layer battery unit 2 may be a perovskite battery, a GaAs thin film solar battery, a wide band gap CIGS solar battery or the like.
  • the lower battery unit 1 is a crystalline silicon battery or a thin film battery, and the choices of the lower battery unit 1 are various.
  • the light-facing surface of the lower layer battery unit 1 is a plane structure, which facilitates the arrangement of the first light trapping structure 3 and the upper layer battery unit 2 .
  • the stacked photovoltaic device further includes at least one of a second light trapping structure 5 located on the backlight side of the lower battery unit 1 and a third light trapping structure 4 located on the light side side of the upper battery unit 1. It is not specifically limited whether the layer photovoltaic device has both the second light trapping structure 5 and the third light trapping structure 4, or only has one of the two.
  • the laminated photovoltaic device shown in FIG. 1 has both the second light trapping structure 5 and the third light trapping structure 4 .
  • the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4 are all selected from metal or semiconductor materials, and the concentration of free electrons in the three is relatively large. The concentrations may all be greater than or equal to 1 ⁇ 10 20 cm ⁇ 3 .
  • the free electrons in the three can be coupled with the incident light, forming a multi-mode resonance light trapping effect, resulting in a localized surface plasmon, that is, LSP (Localized Surface Plasmon), which improves the absorption of incident light.
  • LSP Localized Surface Plasmon
  • the first light trapping structure 3 also has the function of conductively connecting the upper layer battery unit 2 and the lower layer battery unit 1 .
  • the localized surface plasmons generated by the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4 correspond to different light wave response peaks respectively.
  • the incident light in the wavelength range is fully utilized to improve the absorption of incident light.
  • the light-facing surface of the stacked photovoltaic device is the side of the stacked photovoltaic device that receives light, and the backlight surface of the stacked photovoltaic device is opposite to the light-facing surface.
  • Lines with arrows in Figure 1 are used to characterize incident light.
  • FIG. 1 is a schematic diagram of a first cross-section.
  • the projection of the first section perpendicular to the light-facing surface of the stacked photovoltaic device on the light-facing surface of the stacked photovoltaic device may be parallel to any side of the light-facing surface of the stacked photovoltaic device, or perpendicular to the light-facing surface of the stacked photovoltaic device
  • the projection of the first cross section of the stacked photovoltaic device on the light-facing surface of the stacked photovoltaic device may intersect with a certain edge of the stacked photovoltaic device's light-facing surface.
  • the first cross section shown in FIG. 1 may be parallel to a certain side of the light-facing surface of the stacked photovoltaic device.
  • the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 form discrete microstructures on the above-mentioned first cross section, and the discrete microstructures can be projected as line segments on the light surface of the stacked photovoltaic device.
  • the first light trapping structure 3 forms a discrete microstructure projected onto the light surface of the stacked photovoltaic device, that is, a line segment parallel to the marked line of w1.
  • the discrete microstructures corresponding to the first light-trapping structure 3, the second light-trapping structure 5, and the third light-trapping structure 4, respectively, have an average size projected on the light surface of the stacked photovoltaic device respectively d1, d2, and d3, and the microstructures The average spacings between the structures are w1, w2, and w3, respectively.
  • the discrete microstructures corresponding to the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4, respectively are stacked in layers.
  • the average size of the photovoltaic device projected onto the light surface satisfies: d3 ⁇ d1 ⁇ d2.
  • FIG. 2 shows a schematic structural diagram of a first light trapping structure in an embodiment of the present disclosure.
  • the two intersecting dotted lines in Fig. 2 divide Fig. 2 into four parts, namely (a), (b), (c), (d).
  • the top view is the top view
  • the bottom view is the front view.
  • the schematic top view is a schematic structural diagram of the first light trapping structure viewed from the light-facing backlight surface of the stacked photovoltaic device.
  • the front view is a schematic view of the structure of the first light trapping structure viewed from a direction parallel to the first cross section.
  • the above-mentioned front view can also be understood as a schematic structural representation of the first light trapping structure forming discrete microstructures on the above-mentioned first cross-section. (a), (b), (c), and (d) respectively show the structural schematic diagrams of several first light trapping structures.
  • the first light trapping structure 3 forms a discrete microstructure on the above-mentioned first cross section, which is the circle 32 in the lower figure in FIG. 2( a ), and the microstructure is on the light-facing surface of the stacked photovoltaic device.
  • the size of the up projection is d21, and the average size of each d21 is d1.
  • the average spacing between the microstructures is w1.
  • the first light trapping structure 3 forms a discrete microstructure on the above-mentioned first cross section.
  • the projected size of the remaining parts between several holes 6 on the light surface of the stacked photovoltaic device is d22
  • the average size of each d22 is d1 .
  • the average spacing between the remaining parts between several holes 6 is w1 .
  • the first light trapping structure 3 forms a discrete microstructure on the above-mentioned first cross-section, which is the structure 31 in the lower figure of FIG. 2( c ), and the microstructure is on the light-facing surface of the stacked photovoltaic device.
  • the size of the projection is d23, and the average size of each d23 is d1.
  • the average spacing between the microstructures is w1.
  • the first light trapping structure 3 forms a discrete microstructure on the above-mentioned first cross-section, which is the structure 31 in the lower figure of FIG. 2(d).
  • the size of the up-projection is d24, and the average size of each d24 is d1.
  • the average spacing between the parallel lines 31 of the microstructure strips is w1.
  • the second light trapping structure 5 and the third light trapping structure 4 form discrete microstructures on the first cross section similar to the discrete microstructures formed by the first light trapping structure 3 on the first cross section. Repeat.
  • the average sizes of the discrete microstructures of the second light trapping structure 5 and the third light trapping structure 4 projected on the light surface of the laminated photovoltaic device are d2 and d3 respectively.
  • the average spacing between the microstructures is w2, w3, respectively.
  • the above-mentioned d2 and d3 are also similar to the above-mentioned d1, and the above-mentioned w2 and w3 are also corresponding and similar to the above-mentioned w1.
  • the first light trapping structure 3 forms discrete microstructures on the above-mentioned first cross-section, and the average size d1 of the discrete microstructures projected on the light surface of the stacked photovoltaic device, and the values of d1
  • the value range is: 500nm ⁇ d1 ⁇ 10nm, specifically, the value of d1 can be 10nm, 20nm, 30nm, 40nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, etc.
  • the first light trapping structure 1 forms a spacing w1 between discrete microstructures on the above-mentioned first cross section, 800nm ⁇ w1 ⁇ 10nm, and the size of the first light trapping structure 3 is small.
  • the light After the incident light is incident on the stacked photovoltaic device, The light enters the lower part of the first light trapping structure 3 through scattering and undergoes multiple reflections, so that the shielding effect of the first light trapping structure 3 is small, the incident amount of light is increased, and the optical path is increased, so as to improve the performance of the stacked photovoltaic device. Photoelectric conversion efficiency.
  • the above average size and average spacing do not limit the degree of dispersion; more preferably, considering the actual situation of the process, 500nm ⁇ d1 ⁇ 100nm, the size distribution satisfies the normal distribution, and ⁇ corresponds to d1 ⁇ 20%, that is, the size of d1 is located in the range of d1 ⁇ 20% The probability of being within is 68.2% and the probability of being within d1 ⁇ 40% is 95.4%.
  • the first light trapping structure 3 with a small size and high free electron concentration is coupled with the incident light to form a multi-mode resonance light trapping effect, and the first light trapping structure 3 is coupled with the incident light , resulting in a localized plasmon mode enhancement phenomenon located on the surface of the first light trapping structure 3.
  • the incident light is restricted by the localized plasma mode enhancement and exists in the peripheral area of the surface of the first light trapping structure 3, resulting in a light trapping effect.
  • the carriers can be separated and collected within a short migration distance, which is beneficial to stacking The improvement of photoelectric conversion efficiency of layer photovoltaic devices.
  • the first light trapping structure 3 is coupled with the incident light to generate surface plasmons, convert the incident light into a waveguide mode that conducts in the transverse direction, and change the transmission direction of the incident light. increases the optical path of the incident light.
  • the incident light transmitted laterally is basically located near the interface of the light-facing surface of the first light-trapping structure 3, which can effectively improve the light-trapping effect.
  • an excellent light-absorbing effect can be achieved by an absorbing layer with a smaller thickness, which can reduce the amount of light. The thickness of the absorber layer in the cell, thereby reducing the thickness of each cell, and reducing the overall thickness of the stacked photovoltaic device.
  • the aforementioned second light trapping structure 5 and the third light trapping structure 4 have similar light trapping effects to the aforementioned first light trapping structure 3 .
  • the value range of d3 is: 300nm ⁇ d3 ⁇ 1nm, specifically, the value of d3 can be such as 1nm, 2nm , 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, etc.; the third light trapping structure forms the spacing w3 between discrete microstructures on the first cross section , 500nm ⁇ w3 ⁇ 1nm;
  • the above average size and average spacing do not limit the degree of dispersion; more preferably, considering the actual situation of the process, 300nm ⁇ d3 ⁇ 50nm, the size distribution satisfies the normal distribution, ⁇ corresponds to d3 ⁇ 20%, that is, the size of d1 is located in the range of d3 ⁇ 20% The probability of being within is 68.2% and the probability of being within d3 ⁇ 40% is 95.4%.
  • the average size d2 projected by the discrete microstructures on the light surface of the stacked photovoltaic device the value range of d2 is: 1200nm ⁇ d2 ⁇ 20nm; the second light trapping structure is on the above-mentioned first cross-section
  • the spacing w2 between the discrete microstructures is formed, 50 ⁇ m ⁇ w2 ⁇ 20nm.
  • the above average size and average spacing do not limit the degree of dispersion; more preferably, considering the actual situation of the process, 1200nm ⁇ d2 ⁇ 300nm, the size distribution satisfies the normal distribution, and ⁇ corresponds to d2 ⁇ 20%, that is, the size of d1 is located in the range of d2 ⁇ 20% The probability of being within is 68.2% and the probability of being within d2 ⁇ 40% is 95.4%.
  • the three-layer light trapping structure can produce plasmon effects for ultraviolet and blue light bands, visible light bands, red light and infrared bands respectively;
  • the second light trapping structure 5, the third light trapping structure 4 and the first light trapping structure 3 have different corresponding peaks of light wave responses, and further the second light trapping structure 5, the third light trapping structure 4 and the first light trapping structure described above are different. Structure 3 cooperates with each other, making full use of incident light in almost all wavelength ranges, and improving the absorption of incident light. (Basic solution, with three-layer light trapping structure)
  • the matching of the light trapping structures of each layer is adjusted so that the incident light enters the lower light trapping structure of the upper layer through scattering. And multiple reflections occur, which can increase the optical path to a certain extent and improve the overall light trapping effect.
  • the derivation process of the scattering interface matching between the two light trapping structures is as follows:
  • the proposed structure has an intermediate scattering structure and a backscattering structure
  • the wavelengths of the intermediate scattering structure and the backscattering structure are different. Absorption rate, we get that the size ratio of the two should be
  • the physical size of the excimer must be much smaller than the wavelength of the band it is aimed at, so the second light trapping structure on the topmost layer needs to be the smallest in size and needs to be less than 300nm, and the first light trapping structure in the middle is less than 500nm; in addition, the size of the two
  • the relationship is not limited additionally, only the above-mentioned relationship (1) is limited; the third light trapping structure at the bottom of the device is not limited;
  • the second light trapping structure and the third light trapping structure on the top and the bottom do not need to be conductive, and more preferably, they can be conductive and function as surface electrodes.
  • first cross-section in the innumerable first cross-sections perpendicular to the light-facing surface of the tandem photovoltaic device which can be an innumerable number of first cross-sections.
  • the average size and average spacing of the first light trapping structure, the second light trapping structure, and the third light trapping structure may also have the following relationship, for example: or/and,
  • a person skilled in the art can adaptively design the endpoint value of the above relational expression according to the actual situation, which is not limited in this embodiment of the present application.
  • the height of the first light-trapping structure 3 is only greater than 10 nm and less than 500 nm.
  • the surface with the first light-trapping structure 3 is relatively flat, providing better growth for the upper battery unit 2 or deposition interface.
  • the above-mentioned first light trapping structure 3 has higher electrical conductivity and higher recombination rate, which reduces the series resistance of the stacked photovoltaic device.
  • the first light trapping structure 3 in the embodiment of the present disclosure mainly has three functions: first, the function of connecting the upper battery unit 2 and the lower battery unit 1 in series, the first light trapping structure 3 has relatively High conductivity and high recombination rate reduce the series resistance of stacked photovoltaic devices. Second, through the light trapping effect of the above three aspects, the interface reflection is reduced and long-wavelength light is transmitted, so as to achieve excellent light absorption effect, and reduce the thickness of the absorption layer in each battery unit, thereby reducing the thickness of each battery unit. The overall thickness of the tandem photovoltaic device. Third, the bottom cell with the first light trapping structure 3 is relatively flat toward the light surface, which provides a relatively good growth or deposition interface for the upper cell unit 2 .
  • the materials or dimensions of the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4 can be adjusted according to the size or material of each part in the stacked photovoltaic device, so that the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4 can be adjusted.
  • the light trapping structures of the first light trapping structure 3 , the second light trapping structure 5 and the third light trapping structure 4 are more preferable. In the embodiments of the present disclosure, this is not specifically limited.
  • the material or size of the first light trapping structure 3 is adjusted to make the light trapping structure of the first light trapping structure 3 better and further reduce optical losses.
  • the second light trapping structure 5 forms discrete microstructures on the first cross-section, and the average size of the discrete microstructures projected on the light surface of the stacked photovoltaic device is d2.
  • d2 For any first cross-section, d2 ⁇ 1200 nm, so that the light wave response peak of the localized surface plasmon of the second light trapping structure 5 is more matched with the wavelength of the light incident on the second light trapping structure 5, which further improves the absorption of light.
  • the third light trapping structure 4 forms discrete microstructures on the first cross-section, and the average size of the discrete microstructures projected on the light surface of the stacked photovoltaic device is d3.
  • d3 ⁇ 300nm, so that the light wave response peak of the localized surface plasmon of the third light trapping structure 4 is more matched with the wavelength of the light incident on the third light trapping structure 4, which further improves the absorption of light.
  • the light wave response peak of the localized surface plasmon of the first light trapping structure 3 is within the wavelength range of the absorbed light of the lower battery unit 1, and after the light is incident on the first light trapping structure 3, the first trapping The light structure 3 has a scattering effect on light, and the light enters the lower part of the first light trapping structure 3 through the scattering effect and enters the lower battery unit 1, and the energy of the light incident on the first light trapping structure 3 is basically not lost, to a certain extent.
  • the optical path can be increased. that is satisfied,
  • the light wave response peak of the localized surface plasmon of the third light trapping structure 4 is within the wavelength range of the absorbed light of the upper battery unit 2, and after the light is incident on the third light trapping structure 4, the third trapping The light structure 4 has a scattering effect on light, and the light enters the lower part of the third light trapping structure 4 through the scattering effect and enters the upper battery unit 2, and the energy of the light incident on the third light trapping structure 4 is basically not lost, to a certain extent.
  • the optical path can be increased. that is satisfied,
  • the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 are selected from granular (as shown in (a) 32 in FIG. 2 ), linear (As shown in (d) 31 in FIG. 2 , the hole-digging structure ((b) in FIG. 2 ), the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 have various forms .
  • the shape of the above-mentioned particles is one of spherical, hemispherical, linear intersecting structure, cylinder, and cone.
  • the shape of the above hole is one of a circle, an approximate circle, and a polygon.
  • the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 have various forms. As shown with reference to FIG. 2, the shape of the hole 6 in (b) is circular.
  • the upper battery unit includes a first absorption layer; the lower battery unit includes a second absorption layer, and the distance between the first light trapping structure and the first absorption layer or the second absorption layer is at least not greater than 2 nm, that is, the first The distance between the absorption layer and the first light trapping structure is d5, d5 ⁇ 2nm, and/or the distance between the second absorption layer and the first light trapping structure is d6, d6 ⁇ 2nm.
  • the region where the localized plasmon mode of the first light trapping structure is enhanced is about 2 nm of the surface of the first light trapping structure.
  • the first absorption layer and/or the second absorption layer are arranged on the surface peripheral area of the first light trapping structure, and the first absorption layer and/or the second absorption layer are just located in the localized plasma mode of the first light trapping structure In the enhanced region, it is beneficial to improve the photoelectric conversion efficiency of the stacked photovoltaic device.
  • This part mainly makes full use of the light trapping effect of the above-mentioned second aspect of the first light trapping structure.
  • the metal in the first light trapping structure, the second light trapping structure, and the third light trapping structure is selected from at least one of gold, silver, aluminum, copper, gallium, and indium, and the first trap formed by the above materials is
  • the light structure, the second light trapping structure, and the third light trapping structure have higher free electron concentrations, which are beneficial to improve the light trapping effect.
  • the semiconductor materials in the first light trapping structure, the second light trapping structure, and the third light trapping structure are selected from at least one of aluminum-doped zinc oxide and indium-doped tin oxide, and the first light trapping structure formed by the above materials.
  • the free electron concentration of the structure, the second light trapping structure and the third light trapping structure is higher, which is beneficial to improve the light trapping effect.
  • FIG. 3 shows a schematic partial structure diagram of a stacked photovoltaic device in an embodiment of the present disclosure.
  • FIG. 4 shows a schematic partial structure diagram of another stacked photovoltaic device in an embodiment of the present disclosure.
  • the stacked photovoltaic device further includes: a dielectric layer 7 , and the dielectric layer 7 is formed of a dielectric material filled in the gap of the first light trapping structure 3 .
  • the dielectric layer 7 is filled in the gaps between the particles 32
  • the dielectric 7 is filled in the holes 6 dug in the plane plate 33 .
  • the height of the first light trapping structure is greater than or equal to the height of the dielectric layer 7 .
  • FIG. 1 shows a schematic partial structure diagram of a stacked photovoltaic device in an embodiment of the present disclosure.
  • FIG. 4 shows a schematic partial structure diagram of another stacked photovoltaic device in an embodiment of the present disclosure.
  • the stacked photovoltaic device further includes: a dielectric layer 7 , and the dielectric
  • the height d23 of the particles 32 is larger than the height d31 of the dielectric layer 7 .
  • the height d3 of the flat plate 33 is equal to the height of the dielectric layer 7 .
  • the height d23 of the intersection line 31 is larger than the height d31 of the dielectric layer 7 .
  • the height d11 of the parallel lines 31 is larger than the height d31 of the dielectric layer 7 .
  • the cross line 31 in FIG. 4 is a grid-like structure, using silver or silver alloy material, the cross section is approximately rectangular or trapezoidal, the bottom (the area in contact with the light-facing surface of the lower battery unit 1) has a width of 50 nm and a height of 30 nm to construct a honeycomb. It has a grid-like structure, and the hexagonal side length is 300nm-800nm, which is obtained by the method of mask evaporation.
  • the gaps between the intersection lines 31 are filled with a dielectric layer 7, and the dielectric layer 7 is made of silicon oxide and has a thickness of 5nm-20nm.
  • the dielectric constant of the dielectric layer material is 1.2-200, and the dielectric layer material is selected from at least one of silicon oxide, aluminum oxide, silicon nitride, tantalum oxide, and aluminum nitride.
  • a dielectric layer may not be filled in the gap of the first light trapping structure, so that the absorption layer of the upper battery unit and the absorption layer of the lower battery unit are less distant from the first light trapping structure, and the first trapping structure is fully used.
  • the light trapping effect of the second aspect of the light structure is fully used.
  • FIG. 5 shows a schematic diagram of a second cross section perpendicular to the light-facing surface of the stacked photovoltaic device in an embodiment of the present disclosure.
  • the substrate 21 of the upper battery unit 2 includes a first absorber layer.
  • the thickness of the first absorber layer is 50 nm-200 nm.
  • the thickness of the absorption layer of the perovskite material is 500nm-200nm, because the first structure 3 has a good light trapping effect, and the first absorption layer can be made thinner, which is the existing It is about one-tenth of the technology, which is beneficial to reduce the thickness of the upper battery unit 2, and is beneficial to the thinning of the stacked photovoltaic device.
  • the thickness of the second absorption layer of the lower battery unit 1 is crystalline silicon
  • the thickness of the second absorption layer is less than 100 ⁇ m.
  • the thickness of the crystalline silicon absorption layer is about 150um, because the first structure has a good light trapping effect, and the lower battery unit can be made thinner, which is beneficial to reduce the thickness of the lower battery unit 1. It is beneficial to the thinning of stacked photovoltaic devices.
  • the stacked photovoltaic device further includes an upper functional layer 9 located on the light-facing surface of the upper battery unit 2 .
  • the upper functional layer 9 is one or more layers, and has functions such as surface passivation, selective contact, carrier transport or anti-reflection. This embodiment of the present disclosure does not specifically limit this.
  • the stacked photovoltaic device further includes a lower functional layer 10 located on the backlight side of the lower battery unit 1 .
  • the lower functional layer 10 is one or more layers, and has functions such as surface passivation, selective contact, carrier transport or anti-reflection.
  • the lower functional layer 10 can be prepared by methods such as diffusion or deposition. This embodiment of the present disclosure does not specifically limit this.
  • the stacked photovoltaic device further includes a top electrode located on the light-facing side of the upper cell 2 , and a bottom electrode located on the backlight side of the lower cell 1 .
  • Embodiments of the present disclosure also provide a method for producing a stacked photovoltaic device.
  • the method roughly includes the following steps:
  • Step 101 providing lower layer battery cells.
  • Step 102 producing a first light trapping structure on the light-facing surface of the lower-layer battery unit by means of mask evaporation.
  • Step 103 an upper layer battery unit is prepared on the light-facing surface of the first light trapping structure; the band gap width of the upper layer battery unit is larger than the band gap width of the lower layer battery unit.
  • Step 104 producing a second light trapping structure on the side of the backlight surface of the lower layer battery unit, and/or producing a third light trapping structure on the side facing the light side of the upper layer battery unit;
  • the first light trapping structure, The second light trapping structure and the third light trapping structure are both selected from metal or semiconductor materials, and the localized surface plasmons generated by the three correspond to different light wave response peaks respectively;
  • the stacked photovoltaic device has a vertical On the first cross-section of the laminated photovoltaic device facing the light surface, the first light-trapping structure, the second light-trapping structure, and the third light-trapping structure form discrete microstructures on the first cross-section , the average sizes of the discrete microstructures projected onto the light surface of the stacked photovoltaic device are d1, d2, and d3, respectively, and the average spacings between the microstructures are w1, w2, and w3, respectively; In the first cross section, the average size of the microstructure projected on the light
  • the second absorption layer of the lower battery unit 1 is made of crystalline silicon, an n-type silicon substrate is used, the thickness of the substrate is 50um, the substrate has a planar structure (polished or unpolished), and the backlight surface is a suede surface. Light trapping structure.
  • the p-type layer is diffused on the backlight surface of the crystalline silicon substrate to form the lower battery unit 1 .
  • the lower functional layer 10 can be a p-type polycrystalline transmission layer or a p-type amorphous silicon.
  • a diffused or deposited field effect layer or passivation layer may exist on the light surface of the lower cell 1 , or a localized passivation layer, such as silicon oxide, may exist at the contact position of the first light trapping structure 3 .
  • first light trapping structure 3 on the light-facing surface of the lower battery unit 1, and the first light trapping structure 3 forms a discrete microstructure on the first cross section, which is silver nanoparticles, which are approximately cylindrical, with an average diameter of 30nm-200nm and a cylindrical height. Approximately equal to the diameter, the ball spacing is 20nm-500nm (for example, the specific diameter of the silver nanoparticle is 50nm, the height is 50nm, and the distance between the particles is 80nm, not a perfect cylinder, slightly tapered), forming a uniform The distributed lattice structure is obtained by mask evaporation.
  • nanoparticles composed of one or more materials such as gold, aluminum, copper, gallium, and indium can also be used.
  • the space between the nanoparticles of the first light trapping structure 3 is filled with a dielectric layer 7, and the material of the dielectric layer 7 is aluminum oxide, and the thickness is 5-20nm (the thickness does not exceed the height of the nanoparticles or the first light trapping structure 3, such as The height of the first light trapping structure 3 is 100 nm, and the thickness of the aluminum oxide is not more than 100 nm.
  • the upper battery unit 2 is deposited on the first light trapping structure 3.
  • the first absorption layer 21 of the upper battery unit 2 is a wide-bandgap perovskite
  • the matrix 21 of the upper battery unit 2 includes the perovskite absorption layer 21, C60 electron transport layer and nickel oxide hole transport layer
  • the thickness of the upper battery unit 2 is 50nm-300nm.
  • an upper functional layer 9 on the light-facing surface of the upper solar cell which is a one-layer or multi-layer structure, and has the function of surface anti-reflection.
  • the lower layer battery unit 1 has a second light trapping structure 5 on the backlight surface side
  • the upper layer battery unit 2 has a third light trapping structure 4 on the light surface side.
  • the discrete microstructures formed on the first cross section of the second light trapping structure 5 and the third light trapping structure 4 are also nanoparticles;
  • a variety of materials, the materials of the three-layer light trapping structure seed nanoparticles can be the same or different; as Example 1, the third light trapping structure is approximately a cylinder, with an average diameter of 30nm, a height of 30nm, and an average spacing of 50nm;
  • the second light trapping structure It is approximately a cylinder with an average diameter of 100 nm, a height of 100 nm, and an average spacing of 1 ⁇ m.
  • the first light trapping structure 3, the second light trapping structure 5, and the third light trapping structure 4 correspond to the average size d1, d2, d3 and the corresponding average spacing respectively.
  • w1, w2, w3 have the following relationship: and / or
  • the third light trapping structure and the first light trapping structure satisfy this relationship,
  • the third light trapping structure can be silver nanoparticles with a diameter of 20 nm and an average spacing of 102 nm, and the size of the second light trapping structure is not limited;
  • the second light trapping structure and the first light trapping structure satisfy this relationship,
  • the first light trapping structure is silver nanoparticles with a diameter of 50 nm and a spacing between particles of 100 nm
  • the second light trapping structure can be silver nanoparticles with a diameter of 1000 nm and an average spacing of 167 nm, and the size of the third light trapping structure is not limited;
  • the second light trapping structure can be silver nanoparticles with a diameter of 1000 nm and an average spacing of 167 nm
  • the third light trapping structure can be silver nanoparticles Diameter 20nm, average pitch 89nm.
  • FIG. 6 shows a schematic diagram of a first cross-section of a third type of stacked photovoltaic device in an embodiment of the present disclosure, which is perpendicular to the light-facing surface.
  • the second absorption layer of the lower battery unit 1 is a crystalline silicon solar cell, which adopts an n-type silicon substrate with a thickness of 10 ⁇ m. Polishing is acceptable); the crystalline silicon substrate diffuses the p-type layer on the backlight surface to make the lower battery unit 1 .
  • a lower functional layer 10 exists on the backlight surface of the lower battery unit 1 , and the lower functional layer 10 has a one-layer or multi-layer structure and has the functions of surface passivation and anti-reflection.
  • the lower functional layer 10 can be a p-type polycrystalline transmission layer or a p-type amorphous silicon.
  • a second light trapping structure 5 is provided on the side of the backlight surface of the lower layer battery unit 1 , for example, the second light trapping structure 5 adopts a hole in the lower functional layer 10 .
  • the opening is filled with metal aluminum, which can be drawn out as a back electrode.
  • a diffused or deposited field effect layer or passivation layer may exist on the light-facing surface of the lower battery unit 1 , or a localized passivation layer, such as silicon oxide, may exist at the contact position of the first light trapping structure 3 .
  • first light trapping structure 3 on the light-facing surface of the lower battery unit 1, and the first light trapping structure 3 forms a discrete microstructure on the first cross section.
  • the height is approximately equal to half the diameter of the sphere, and the distance between the spheres is 20nm-500nm (for example, a specific embodiment is 50nm in diameter, 25nm in height, and 80nm in distance), not a perfect hemisphere, forming a uniformly distributed lattice structure, using a mask It is obtained by the method of annealing after evaporation.
  • the dielectric layer 7 is made of silicon oxide and has a thickness of 5nm-20nm (the thickness does not exceed the height of the first light trapping structure 3, such as the height of the first light trapping structure 3 is 50nm, the thickness of silicon oxide is not more than 50nm).
  • the upper battery unit 2 is deposited on the first light trapping structure 3.
  • the first absorption layer of the upper battery unit 2 is a wide-bandgap perovskite
  • 21 is the substrate of the upper battery unit 2
  • the substrate 21 includes a perovskite absorption layer.
  • the thickness of the upper battery unit 2 is 50nm-300nm.
  • the upper functional layer 9 is a one-layer or multi-layer structure, which has the function of surface anti-reflection.
  • the upper layer battery unit 2 has a third light trapping structure 4 on the side of the light surface.
  • the discrete microstructures formed on the first cross section of the third light trapping structure 4 are also nanoparticles.
  • the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 correspond to the average sizes d1 , d2 , and d3 and the corresponding mean spacings w1 , w2 , and w3 respectively.
  • FIG. 7 shows a schematic diagram of a first cross-section perpendicular to the light-facing surface of the fourth type of stacked photovoltaic device in an embodiment of the present disclosure.
  • the second absorption layer of the lower battery unit 1 is crystalline silicon, which adopts an n-type silicon substrate with a thickness of 10um. Yes); the crystalline silicon substrate diffuses the p-type layer on the backlight surface to make the lower battery unit 1 .
  • a lower functional layer 10 exists on the backlight surface of the lower battery unit 1, and the lower functional layer 10 has a one-layer or multi-layer structure and has the functions of surface passivation and anti-reflection.
  • the lower functional layer 10 can be a p-type polycrystalline transmission layer or a p-type amorphous silicon.
  • a second light trapping structure 5 is provided on the side of the backlight surface of the lower layer battery unit 1 , for example, the second light trapping structure 5 adopts a hole in the lower functional layer 10 .
  • the opening is filled with metal aluminum, which can be drawn out as a back electrode.
  • a diffused or deposited field effect layer or passivation layer may exist on the light-facing surface of the lower battery unit 1 , or a localized passivation layer, such as silicon oxide, may exist at the contact position of the first light trapping structure 3 .
  • the lower battery unit 1 has a first light trapping structure 3 facing the light surface.
  • the first light trapping structure 3 forms discrete microstructures on the first cross section as parallel lines, using silver or silver alloy material, and the cross section is approximately rectangular or trapezoidal,
  • the bottom ie, the contact area with the light-facing surface of the lower battery unit 1) has a width of 80 nm, a height of 50 nm, and a spacing between parallel lines of 200 nm-500 nm, which is obtained by mask evaporation. Or bottom width 200nm, pitch 500nm.
  • dielectric layer 7 in the space between the parallel lines, and the dielectric layer 7 is made of silicon oxide with a thickness of 5-20 nm; the silicon oxide layer can be a common layer with the above-mentioned lower cell 1-facing passivation layer.
  • the upper battery unit 2 is deposited on the first light trapping structure 3.
  • the first absorption layer of the upper battery unit 2 is a wide-bandgap gallium arsenide
  • 21 is the base of the upper battery unit 2
  • the base 21 includes p-type arsenide.
  • which is an aluminum gallium arsenide compound.
  • the light-facing surface of the base body 21 is provided with an upper transmission layer 23, and 23 is a GaAs cell window layer, which is an aluminum indium phosphorous compound; the thickness of the upper cell 2 is 200nm-500nm.
  • an upper functional layer 9 on the light-facing surface of the upper battery unit 2 which is a one-layer or multi-layer structure, and has the function of surface anti-reflection.
  • the upper layer battery unit 2 has a third light trapping structure 4 on the side of the light surface.
  • the discrete microstructures formed on the first cross section of the third light trapping structure 4 are also nanoparticles.
  • the first light trapping structure 3 , the second light trapping structure 5 , and the third light trapping structure 4 correspond to the average sizes d1 , d2 , d3 and the corresponding average spacings w1 , w2 , w3 respectively Has the following relationship: and / or; That is, taking the first light trapping structure as an example with a size of 200 nm and a spacing of 500 nm, the second light trapping structure with a size of 800 nm and a spacing of 250 nm, and the third light trapping structure with a size of 100 nm and a spacing of 500 nm.

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Abstract

本公开提供一种叠层光伏器件，涉及太阳能光伏技术领域。叠层光伏器件包括层叠设置的上层电池单元、下层电池单元、以及两者之间的第一导电陷光结构；叠层光伏器件还包括位于下层电池单元背光面一侧的第二陷光结构和位于上层电池单元向光面一侧的第三陷光结构中的至少一个；第一陷光结构、第二陷光结构、第三陷光结构三者产生的局域表面等离激元分别对应不同的光波响应峰值；第一陷光结构、第二陷光结构、第三陷光结构在第一截面上形成分立的微结构，分立的微结构在叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，微结构间的平均间距分别为w1、w2、w3；式I，式II 。叠层光伏器件提高了陷光效果，降低了吸收层厚度。

Description

叠层光伏器件
相关申请的交叉引用
本公开要求在2020年12月17日提交中国专利局、申请号为202011497965.8、名称为“叠层光伏器件”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及太阳能光伏技术领域，特别是涉及一种叠层光伏器件。
背景技术
叠层光伏器件可以将太阳光分成多个波段，从正面到背面，依次采用带隙逐渐减小的电池单元吸收不同能量的太阳光，以减少可见光波段能量损失，提升光电转换效率，因此，叠层光伏器件具有广泛的应用前景。
叠层光伏器件中，光吸收不完全或光学损失较为严重进而降低了器件的光电转换效率。
概述
本公开提供一种叠层光伏器件，旨在解决叠层光伏器件的光学损失较为严重、光电转换效率低的问题。
根据本公开的第一方面，提供了一种叠层光伏器件，所述叠层光伏器件包括：层叠设置的上层电池单元、下层电池单元、以及位于所述上层电池单元和所述下层电池单元之间的第一陷光结构；所述上层电池单元的带隙宽度大于所述下层电池单元的带隙宽度；
所述叠层光伏器件还包括位于所述下层电池单元背光面一侧的第二陷光结构和位于所述上层电池单元向光面一侧的第三陷光结构中的至少一个；
所述第一陷光结构、所述第二陷光结构、所述第三陷光结构均选自金属或半导体材料，三者产生的局域表面等离激元分别对应不同的光波响应峰值；
所述叠层光伏器件具有垂直于所述叠层光伏器件向光面的第一截面，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构在所述第一截面上形成分立的微结构，所述分立的微结构在所述叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，所述微结构间的平均间距分别为w1、w2、w3；
当仅存在双层陷光结构时，即存在第一陷光结构与第二陷光结构时或存在第一陷光结构与第三陷光结构时，满足如下关系，所述微结构在所述叠层光伏器件向光面上的投影平均尺寸和相邻所述微结构间的平均间距满足：
Figure PCTCN2021136475-appb-000001
或
Figure PCTCN2021136475-appb-000002
当存在三层陷光结构时，至少存在一个所述第一截面，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
Figure PCTCN2021136475-appb-000003
和/或，
Figure PCTCN2021136475-appb-000004
光入射在叠层光伏器件后，光通过散射作用进入第一陷光结构的下方且发生多次反射，在一定程度上可以增加光程。同时，第一陷光结构中的自由电子与入射的光产生耦合，形成多模谐振陷光效果，一方面，第一陷光结构与入射光耦合，产生位于第一陷光结构的表面的局域等离子模态增强现象，入射光受到局域等离子模态增强的限制存在于第一陷光结构的表面周边区域，产生陷光效果。另一方面，第一陷光结构与入射光耦合，产生表面等离子激元，将入射光转换为沿横向传导的波导模态，改变了入射光的传导方向，极大的增加入射光的光程，可以有效地提高陷光效果，进而，通过较小厚度的吸收层即可达到优良的光吸收效果，可以降低各个电池单元中吸收层的厚度，进而降低各个电池单元的厚度，降低叠层光伏器件的整体厚度。光照射在第 二陷光结构和/或第三陷光结构上之后，第二陷光结构和/或第三陷光结构中的自由电子与入射的光产生耦合，形成多模谐振陷光效果，提升对入射光的吸收量。同时，第二陷光结构在下层电池单元内形成针对较长波段入射光的多模谐振陷光效果，第三陷光结构在上层电池单元内形成针对较短波段入射光的多模谐振陷光效果，提升对入射光的吸收量。第一陷光结构、第二陷光结构、第三陷光结构三者产生的局域表面等离激元分别对应不同的光波响应峰值，进而，通过三者的配合，几乎针对全部波长范围的入射光都进行了充分利用，提升了对入射光的吸收量。第一陷光结构、第二陷光结构、第三陷光结构的平均尺寸、平均间距分别为w1、w2、w3具有如下关系：
Figure PCTCN2021136475-appb-000005
Figure PCTCN2021136475-appb-000006
使得每相邻的两层陷光结构的散射截面针对波长均匹配，能够充分保证入射光的进入量，使得从叠层光伏器件射出的光更少，进一步提升对入射光的吸收量。
上述说明仅是本公开技术方案的概述，为了能够更清楚了解本公开的技术手段，而可依照说明书的内容予以实施，并且为了让本公开的上述和其它目的、特征和优点能够更明显易懂，以下特举本公开的具体实施方式。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对本公开实施例的描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1示出了本公开实施例中的第一种垂直于叠层光伏器件向光面的第一截面的示意图；
图2示出了本公开实施例中的第一陷光结构的结构示意图；
图3示出了本公开实施例中的一种叠层光伏器件的局部结构示意图；
图4示出了本公开实施例中的另一种叠层光伏器件的局部结构示意图；
图5示出了本公开实施例中的第二种垂直于叠层光伏器件向光面的第一截面的示意图；
图6示出了本公开实施例中的第三种垂直于叠层光伏器件向光面的第一截面的示意图；
图7示出了本公开实施例中的第四种垂直于叠层光伏器件向光面的第一截面的示意图。
附图编号说明：
1-下层电池单元，2-上层电池单元，21-上层电池单元的基底，22-上层电池单元的下传输层，23-上层电池单元的上传输层，3-第一陷光结构，31-交叉线或平行线，32-粒子，33-平面板材，4-第三陷光结构，5-第二陷光结构，6-孔，7-电介质层，9-上功能层，10-下功能层。
具体实施例
下面将结合本公开实施例中的附图，对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。
图1示出了本公开实施例中的第一种垂直于叠层光伏器件向光面的第一截面的示意图。参照图1所示，该叠层光伏器件包括层叠设置的上层电池单元2、下层电池单元1、以及位于上层电池单元2和下层电池单元1之间第一陷光结构3。上层电池单元2的带隙宽度大于下层电池单元1的带隙宽度。如，上层电池单元2的带隙宽度为1.5-3eV，进一步，上层电池单元2的带隙宽度为1.7-2.3eV。
需要说明的是，叠层光伏器件中包括的上层电池单元2和下层电池单元1的数量不作具体限定。针对上层电池单元2和下层电池单元1的具体类型不作限定。可选的，上层电池单元2可以为钙钛矿电池、GaAs薄膜太阳电池、 宽带隙CIGS太阳电池等。可选的，下层电池单元1为晶体硅电池或薄膜电池，下层电池单元1的选择多样。
可选的，下层电池单元1的向光面为平面结构，便于第一陷光结构3和上层电池单元2的设置。
叠层光伏器件还包括位于下层电池单元1背光面一侧的第二陷光结构5和位于上层电池单元1向光面一侧的第三陷光结构4中的至少一个，具体的，该叠层光伏器件是第二陷光结构5、第三陷光结构4均有，还是只具有两者中的一个不作具体限定。如图1所示的叠层光伏器件，第二陷光结构5、第三陷光结构4均有。
第一陷光结构3、第二陷光结构5、第三陷光结构4均选自金属或半导体材料，进而三者中的自由电子的浓度均较大，例如，三者中的自由电子的浓度均可以大于或等于1×10 20cm -3。三者中的自由电子与入射的光均能产生耦合，形成多模谐振陷光效果，产生局域表面等离激元，即LSP(Localized Surface Plasmon)，提升了对入射光的吸收量。需要说明的是，第一陷光结构3还具有导电连接上层电池单元2和下层电池单元1的作用。
第一陷光结构3、第二陷光结构5、第三陷光结构4三者产生的局域表面等离激元分别对应不同的光波响应峰值，进而，通过三者的配合，几乎针对全部波长范围的入射光都进行了充分利用，提升了对入射光的吸收量。
叠层光伏器件向光面为叠层光伏器件接收光的一面，叠层光伏器件背光面与向光面相对。图1中带有箭头的线用于表征入射光。垂直于叠层光伏器件向光面的第一截面有无数个。例如，图1所示即为一种第一截面的示意图。垂直于叠层光伏器件向光面的第一截面在叠层光伏器件向光面上的投影可以与叠层光伏器件向光面的任一个边平行，或者，垂直于叠层光伏器件向光面的第一截面在叠层光伏器件向光面上的投影可以与叠层光伏器件向光面的某一个边相交。本公开实施例中对第一截面具体是哪一个不作具体限定。图1所示的第一截面可以与叠层光伏器件向光面的某一个边平行。
第一陷光结构3、第二陷光结构5、第三陷光结构4在上述第一截面上形成分立的微结构，分立的微结构在叠层光伏器件向光面上投影可以为线段。例如，第一陷光结构3形成分立的微结构在叠层光伏器件向光面上投影即为与w1的标注线平行的线段。第一陷光结构3、第二陷光结构5、第三陷光结构4分别对应的分立的微结构，在叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，微结构间的平均间距分别为w1、w2、w3，如图1所示，第一陷光结构3、第二陷光结构5、第三陷光结构4分别对应的分立的微结构，在叠层光伏器件向光面上投影的平均尺寸满足：d3<d1<d2。图2示出了本公开实施例中的第一陷光结构的结构示意图。图2中两条相交的虚线将图2分为四个部分，分别为(a)、(b)、(c)、(d)。每个部分中，位于上方的为俯视示意图，位于下方的为正视示意图。俯视示意图为从叠层光伏器件的向光面向背光面看，第一陷光结构的结构示意。正视图为从平行于第一截面的方向看，第一陷光结构的结构示意。上述正视图也可以理解为第一陷光结构在上述第一截面上形成分立的微结构的结构示意。(a)、(b)、(c)、(d)分别示出了几种第一陷光结构的结构示意图。
参照图2(a)所示，第一陷光结构3在上述第一截面上形成分立的微结构为图2(a)中下图的圆形32，微结构在叠层光伏器件向光面上投影的尺寸为d21，各个d21的平均尺寸为d1。微结构间的平均间距为w1。
参照图2(b)下图所示，第一陷光结构3在上述第一截面上形成分立的微结构为平面板材33挖孔6后，几个孔6之间的剩余部分，微结构平面板材33挖孔6后，几个孔6之间的剩余部分在叠层光伏器件向光面上投影的尺寸为d22，各个d22的平均尺寸为d1。微结构平面板材33挖孔6后，几个孔6之间的剩余部分间的平均间距为w1。
参照图2(c)所示，第一陷光结构3在上述第一截面上形成分立的微结构为图2(c)下图中的结构31，微结构在叠层光伏器件向光面上投影的尺寸为d23，各个d23的平均尺寸为d1。微结构间的平均间距为w1。
参照图2(d)所示，第一陷光结构3在上述第一截面上形成分立的微结构为图2(d)下图中的结构31，微结构31在叠层光伏器件向光面上投影的尺寸为d24，各个d24的平均尺寸为d1。微结构条平行线31间的平均间距为w1。
第二陷光结构5、第三陷光结构4在上述第一截面上形成分立的微结构与第一陷光结构3在上述第一截面上形成分立的微结构相似，为了避免重复此处不再赘述。第二陷光结构5、第三陷光结构4分立的微结构在叠层光伏器件向光面上投影的平均尺寸分别为d2、d3，第二陷光结构5、第三陷光结构4的微结构间的平均间距分别为w2、w3。上述d2、d3与前述d1也对应相似，上述w2、w3与上述w1也对应相似，为了避免重复此处不再赘述。
第一方面，参照图1所示，第一陷光结构3在上述第一截面上形成分立的微结构，分立的微结构在叠层光伏器件向光面上投影的平均尺寸d1，d1的取值范围为：500nm≥d1≥10nm，具体地，d1取值可以如10nm、20nm、30nm、40nm、50nm、100nm、150nm、200nm、250nm、300nm、350nm、400nm、450nm、500nm等。第一陷光结构1在上述第一截面上形成分立的微结构间的间距w1，800nm≥w1≥10nm，第一陷光结构3的尺寸均较小，入射光入射在叠层光伏器件后，光通过散射作用进入第一陷光结构3中的下方并发生多次反射，使得第一陷光结构3遮挡效应较小，提升了光的入射量进而提升光程，以提升叠层光伏器件的光电转换效率。上述平均尺寸与平均间距，不限定离散程度；更优地，考虑工艺实际情况，500nm≥d1≥100nm，尺寸分布满足正态分布，σ对应d1±20％，即d1尺寸位于d1±20％范围内的概率是68.2％，位于d1±40％范围内的概率是95.4％。
第二方面，参照图1所示，较小尺寸的且具有高自由电子浓度的第一陷光结构3与入射光耦合，形成多模谐振陷光效果，第一陷光结构3与入射光耦合，产生位于第一陷光结构3表面的局域等离子模态增强现象，入射光受到局域等离子模态增强的限制存在于第一陷光结构3的表面周边区域，产生 陷光效果。在上层电池单元2和/或下层电池单元1的吸收层位于第一陷光结构3的表面周边区域的情况下，可以使得载流子在较短的迁移距离内被分离和收集，有利于叠层光伏器件的光电转换效率的提升。
第三方面，参照图1所示，第一陷光结构3与入射光耦合，产生表面等离子激元，将入射光转换为沿横向传导的波导模态，改变了入射光的传导方向，极大的增加入射光的光程。横向传导的入射光基本位于第一陷光结构3的向光面的界面附近，可以有效地提高陷光效果，进而，通过较小厚度的吸收层即可达到优良的光吸收效果，可以降低各个电池单元中吸收层的厚度，进而降低各个电池单元的厚度，降低叠层光伏器件的整体厚度。
上述第二陷光结构5、第三陷光结构4与前述第一陷光结构3具有类似的陷光效果。
针对第三陷光结构，分立的微结构在叠层光伏器件向光面上投影的平均尺寸d3，d3的取值范围为：300nm≥d3≥1nm，具体地，d3取值可以如1nm、2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、50nm、100nm、150nm、200nm、250nm、300nm等；第三陷光结构在上述第一截面上形成分立的微结构间的间距w3，500nm≥w3≥1nm；
上述平均尺寸与平均间距，不限定离散程度；更优地，考虑工艺实际情况，300nm≥d3≥50nm，尺寸分布满足正态分布，σ对应d3±20％，即d1尺寸位于d3±20％范围内的概率是68.2％，位于d3±40％范围内的概率是95.4％。
针对第二陷光结构，分立的微结构在叠层光伏器件向光面上投影的平均尺寸d2，d2的取值范围为：1200nm≥d2≥20nm；第二陷光结构在上述第一截面上形成分立的微结构间的间距w2，50μm≥w2≥20nm。
上述平均尺寸与平均间距，不限定离散程度；更优地，考虑工艺实际情况，1200nm≥d2≥300nm，尺寸分布满足正态分布，σ对应d2±20％，即d1尺寸位于d2±20％范围内的概率是68.2％，位于d2±40％范围内的概率是 95.4％。
即300nm≥d3≥50nm、500nm≥d1≥100nm、1200nm≥d2≥300nm；三层陷光结构可以分别针对紫外与蓝光波段、可见光波段、红光与红外波段产生等离子激元效果；
上述第二陷光结构5、第三陷光结构4与前述第一陷光结构3对应的光波响应峰值不同，进而上述第二陷光结构5、第三陷光结构4与前述第一陷光结构3三者相互配合，几乎针对全部波长范围的入射光都进行了充分利用，提升了对入射光的吸收量。(基础方案，具备三层陷光结构)
为进一步提升整体陷光效果，在各层等离子激元陷光结构均具备多模谐振陷光效果的基础上，调节各层陷光结构匹配性使得入射光通过散射作用进入上层陷光结构的下方且发生多次反射，在一定程度上可以增加光程，提升整体陷光效果。两层陷光结构之间散射界面匹配性推导过程如下：
以金属颗粒散射为例，存在归一化散射因数，
Figure PCTCN2021136475-appb-000007
吸收层吸收的部分A＝1-δ·Q scat，δ为颗粒覆盖面积的比例，假定颗粒为正方形，颗粒边长为σ geom＝d，颗粒中心间距为σ gap＝2，
Figure PCTCN2021136475-appb-000008
Figure PCTCN2021136475-appb-000009
当颗粒位于两吸收层之间时，该散射因数越大，同时颗粒覆盖面积比例越小，对应的陷光效果越好；
当本提案结构存在中间散射结构以及背散射结构时，中间散射结构与背散射结构针对的波长不同，中间散射结构针对400-600nm波段，表面射结构针对200-300nm波段，假定二者具备相同的吸收率，我们得出二者的尺寸比例关系应为
Figure PCTCN2021136475-appb-000010
Figure PCTCN2021136475-appb-000011
基于上述关系，我们提出不同层结构之间的比例关系式(1)，即
Figure PCTCN2021136475-appb-000012
举例，中间结构尺寸取值d1＝100nm,w1＝500nm；
当上层结构取值d3＝50nm时，则得出：
Figure PCTCN2021136475-appb-000013
则500nm≤w3≤1414nm；
激元物理尺寸上必须远远小于其针对的波段波长，因此最顶层的第二陷光结构尺寸最小，需要小于300nm，中间的第一陷光结构小于500nm；除此之外对二者的尺寸关系不做额外限定，仅依靠上述关系式(1)做限定；对器件底部的第三陷光结构不做限定；
上述公式推导过程同理可以应用于第一与第二陷光结构；
顶部与底部的第二陷光结构与第三陷光结构不要求是否导电，更优地，可以导电且起到表面电极的功能。在垂直于叠层光伏器件向光面的无数个第一截面中至少存在一个第一截面，使得第一陷光结构、第二陷光结构、第三陷光结构的平均尺寸、平均间距分别为w1、w2、w3具有如下关系：
Figure PCTCN2021136475-appb-000014
Figure PCTCN2021136475-appb-000015
或/和，
Figure PCTCN2021136475-appb-000016
即二者满足其一，更优地三层陷光结构同时满足两公式条件，使得每相邻的两层陷光结构的散射截面针对波长均匹配，能够充分保证入射光的进入量，使得从叠层光伏器件射出的光更少，进一步提升对入射光的吸收量。在垂直于叠层光伏器件向光面的无数个第一截面中至少存在的一个第一截面，可以为无数个第一截面中，在叠层光伏器件向光面上的投影与叠层光伏器件向光面的任一个边平行的第一截面。当然，第一陷光结构、第二陷光结构、第三陷光结构的平均尺寸、平均间距也可以具有如下关系，例如：
Figure PCTCN2021136475-appb-000017
或/和，
Figure PCTCN2021136475-appb-000018
本领域技术人员可以根据实际情况对上述关系式的端点值进行适应性设计，本申请实施例对此不做限定。
同时，第一陷光结构3的高度仅大于10nm小于500nm，相比于um级别的绒面结构而言，具备第一陷光结构3的表面较为平整，为上层电池单元2提供较为优良的生长或沉积界面。而且，上述第一陷光结构3具有较高的电 导率，具备较高的复合速率，降低了叠层光伏器件的串联电阻。
综上所述，本公开实施例中的第一陷光结构3总结起来主要起3个方面的作用：一是串联上层电池单元2和下层电池单元1的作用，第一陷光结构3具有较高的电导率，具备较高的复合速率，降低了叠层光伏器件的串联电阻。二是通过上述三个方面的陷光效果，降低界面反射并透过长波段的光，达到优良的光吸收效果，并降低各个电池单元中吸收层的厚度，进而降低各个电池单元的厚度，降低叠层光伏器件的整体厚度。三是具备第一陷光结构3的底层电池向光面较为平整，为上层电池单元2提供较为优良的生长或沉积界面。
需要说明的是，可以根据叠层光伏器件中各个部分的尺寸或材料等，配合调整第一陷光结构3、第二陷光结构5、第三陷光结构4的材料或尺寸等，使得第一陷光结构3、第二陷光结构5、第三陷光结构4的陷光结构更优。在本公开实施例中，对此不作具体限定。例如，根据叠层光伏器件中不同结构对陷光波长范围的要求，调整第一陷光结构3的材料或尺寸等，使得第一陷光结构3的陷光结构更优，进一步减少光学损失。
可选的，第二陷光结构5在第一截面上形成分立的微结构，该分立的微结构在叠层光伏器件向光面上投影的平均尺寸为d2，对于任意第一截面，d2≤1200nm，进而使得第二陷光结构5的局域表面等离激元的光波响应峰值，与入射在第二陷光结构5上的光的波长更为匹配，进一步提升对光的吸收量。
可选的，第三陷光结构4在第一截面上形成分立的微结构，该分立的微结构在叠层光伏器件向光面上投影的平均尺寸为d3，对于任意的第一截面，d3≤300nm，进而使得第三陷光结构4的局域表面等离激元的光波响应峰值，与入射在第三陷光结构4上的光的波长更为匹配，进一步提升对光的吸收量。
可选的，第一陷光结构3的局域表面等离激元的光波响应峰值处在下层电池单元1的吸收光波长范围内，光入射在第一陷光结构3上之后，第一陷光结构3对光具有散射作用，光通过散射作用进入第一陷光结构3的下方， 进入下层电池单元1，入射在第一陷光结构3上的光的能量基本没有损失，在一定程度上可以增加光程。即满足，
Figure PCTCN2021136475-appb-000019
可选的，第三陷光结构4的局域表面等离激元的光波响应峰值处在上层电池单元2的吸收光波长范围内，光入射在第三陷光结构4上之后，第三陷光结构4对光具有散射作用，光通过散射作用进入第三陷光结构4的下方，进入上层电池单元2，入射在第三陷光结构4上的光的能量基本没有损失，在一定程度上可以增加光程。即满足，
Figure PCTCN2021136475-appb-000020
可选的，参照图2所示，第一陷光结构3、第二陷光结构5、第三陷光结构4选自颗粒状(如图2中的(a)32所示)、线状(如图2中的(d)31所示、挖孔结构(如图2中的(b))，第一陷光结构3、第二陷光结构5、第三陷光结构4的形式多样。
可选的，上述颗粒的形状为球形、半球形、线状交叉结构、圆柱体、锥体中的一种。上述孔的形状为圆形、近似圆形、多边形中的一种，第一陷光结构3、第二陷光结构5、第三陷光结构4的形式多样。如，参照图2所示，(b)中孔6的形状为圆形。
可选的，上层电池单元包括第一吸收层；下层电池单元包括第二吸收层，第一陷光结构至少与第一吸收层或第二吸收层之间的距离不大于2nm，即，第一吸收层与第一陷光结构之间的距离为d5，d5≤2nm，和/或，第二吸收层与第一陷光结构之间的距离为d6，d6≤2nm。通常情况下，第一陷光结构的局域等离子模态增强的区域为第一陷光结构的表面的2nm范围左右。即，将第一吸收层和/或第二吸收层设置在第一陷光结构的表面周边区域，第一吸收层和/或第二吸收层正好位于第一陷光结构的局域等离子模态增强的区域内，有利于叠层光伏器件的光电转换效率的提升。该部分主要是充分利用了第一陷光结构上述第二方面的陷光效果。
可选的，第一陷光结构、第二陷光结构、第三陷光结构中的金属选自金、银、铝、铜、镓、铟中的至少一种，上述材料形成的第一陷光结构、第二陷 光结构、第三陷光结构自由电子浓度更高，利于提升陷光效果。
可选的，第一陷光结构、第二陷光结构、第三陷光结构中的半导体材料选自掺铝氧化锌、掺铟氧化锡中的至少一种，上述材料形成的第一陷光结构、第二陷光结构、第三陷光结构自由电子浓度更高，利于提升陷光效果。
图3示出了本公开实施例中的一种叠层光伏器件的局部结构示意图。图4示出了本公开实施例中的另一种叠层光伏器件的局部结构示意图。参照图2、图3、图4所示，叠层光伏器件还包括：电介质层7，电介质层7由填充在第一陷光结构3的间隙中的电介质材料形成。例如，或者，电介质层7填充在粒子32之间的间隙中，或，电介质7填充中在平面板材33挖的孔6中。第一陷光结构的高度大于或等于电介质层7的高度。如，图2(a)中，粒子32的高度d23，大于电介质层7的高度d31。图2(b)中，平面板材33的高度d3，等于电介质层7的高度。图2(c)中，交叉线31的高度d23，大于电介质层7的高度d31。图2(d)中，平行线31的高度d11，大于电介质层7的高度d31。一方面，通过电介质层7的填充，使得在上层电池单元能够在更为平整的表面上制备，便于上层电池单元的制备，且减小了上层电池单元的应力，利于大尺寸的上层电池单元的形成。另一方面，电介质层填充有助于增强其包裹的等离子激元的多模谐振陷光效果。
图4中交叉线31为网格状结构，采用银或银的合金材料，截面近似为矩形或梯形，底部(与下层电池单元1的向光面接触的区域)宽度50nm，高度30nm，构建蜂窝状网格结构，六边形边长300nm-800nm，采用掩膜蒸镀的方法获得。交叉线31之间空隙中填充有电介质层7，电介质层7的材料为氧化硅，厚度为5nm-20nm。
可选的，电介质层材料的介电常数为1.2-200，电介质层材料选自：氧化硅、氧化铝、氮化硅、氧化钽、氮化铝中的至少一种。
可选的，在第一陷光结构的间隙中也可以不填充电介质层，使得上层电池单元的吸收层、下层电池单元的吸收层距离第一陷光结构的距离更小，充 分使用第一陷光结构的第二方面的陷光效果。
图5示出了本公开实施例中的第二种垂直于叠层光伏器件向光面的第一截面的示意图。可选的，参照图5所示，上层电池单元2的基底21中包括第一吸收层，在第一吸收层为钙钛矿材料的情况下，第一吸收层的厚度为50nm-200nm。相对于现有技术的钙钛矿材料的吸收层的厚度为500nm-200nm而言，本申请由于第一结构3具有良好的陷光效果，进而第一吸收层可以做的较薄，为现有技术的十分之一左右，利于减少上层电池单元2的厚度，利于叠层光伏器件的轻薄化。
可选的，在下层电池单元1的第二吸收层为晶体硅的情况下，第二吸收层的厚度小于100um。相对于现有技术的晶体硅吸收层的厚度为150um左右而言，本申请由于第一结构具有良好的陷光效果，进而下层电池单元可以做的较薄，利于减少下层电池单元1的厚度，利于叠层光伏器件的轻薄化。
可选的，该叠层光伏器件还包括位于上层电池单元2的向光面的上功能层9。上功能层9为一层或多层，具备表面钝化、选择性接触、传输载流子或减反射等功能。本公开实施例对此不作具体限定。
可选的，该叠层光伏器件还包括位于下层电池单元1的背光面的下功能层10。下功能层10为一层或多层，具备表面钝化、选择性接触、传输载流子或减反射等功能。下功能层10可以通过扩散或沉积等方法制得。本公开实施例对此不作具体限定。
该叠层光伏器件还包括位于上层电池单元2的向光面的顶电极，以及位于下层电池单元1的背光面的底电极。
本公开实施例还提供一种叠层光伏器件的生产方法。该方法大致包括如下步骤：
步骤101，提供下层电池单元。
步骤102，在所述下层电池单元的向光面，采用掩膜蒸镀的方式生产第一陷光结构。
步骤103，在所述第一陷光结构的向光面制备上层电池单元；所述上层电池单元的带隙宽度大于所述下层电池单元的带隙宽度。
步骤104，在所述下层电池单元背光面一侧生产第二陷光结构，和/或，在所述上层电池单元向光面一侧生产第三陷光结构；所述第一陷光结构、所述第二陷光结构、所述第三陷光结构均选自金属或半导体材料，三者产生的局域表面等离激元分别对应不同的光波响应峰值；所述叠层光伏器件具有垂直于所述叠层光伏器件向光面的第一截面，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构在所述第一截面上形成分立的微结构，所述分立的微结构在所述叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，所述微结构间的平均间距分别为w1、w2、w3；至少存在一个所述第一截面，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：满足
Figure PCTCN2021136475-appb-000021
和/或
Figure PCTCN2021136475-appb-000022
在本公开实施例中，该方法的上层电池单元、下层电池单元、第一陷光结构、第二陷光结构、第三陷光结构可以参照前述叠层光伏器件实施例中的相关记载，且能达到相同或相似的有益效果，为了避免重复，此处不再赘述。
需要说明的是，对于方法实施例，为了简单描述，故将其都表述为一系列的动作组合，但是本领域技术人员应该知悉，本公开实施例并不受所描述的动作顺序的限制，因为依据本公开实施例，某些步骤可以采用其他顺序或者同时进行。其次，本领域技术人员也应该知悉，说明书中所描述的实施例均属于优选实施例，所涉及的动作并不一定都是本公开实施例所必须的。
下面列举几种具体的实施例，进一步解释本申请。
实施例1
参照图5所示，下层电池单元1的第二吸收层为晶体硅，采用n型硅基体，基体厚度50um，基体向光面为平面结构(抛光或者不抛光均可)，背光面为绒面陷光结构。晶体硅基体背光面扩散p型层，制成下层电池单元1。下层电池单元1的背光面存在下功能层10，下功能层10为一层或多层结构，具 备表面钝化以及减反射的功能；在底电极对应位置可以存在局域重掺的选择性接触结构。下功能层10可以为p型多晶传输层或p型非晶硅，此种情况下下层电池单元1、下功能层10之间存在氧化硅或本征非晶硅界面层；下功能层10同时包含导电薄膜传输层，如掺铟氧化锡或掺铝氧化锌等。
下层电池单元1向光面可以存在扩散的或沉积的场效应层或钝化层，或在第一陷光结构3接触位置存在局域的钝化层，如氧化硅。
下层电池单元1的向光面存在第一陷光结构3，第一陷光结构3在第一截面上形成分立的微结构为银纳米粒子，近似为圆柱体，平均直径30nm-200nm，圆柱高度近似与直径相等，球间距20nm-500nm(如，具体的该银纳米粒子的直径为50nm，高度为50nm，粒子之间的间距为80nm，并非为完美圆柱体，略呈锥型)，形成均匀分布的点阵结构，采用掩膜蒸镀的方法获得。此外，还可以采用金、铝、铜、镓、铟等一种或多种材料构成的纳米粒子。
第一陷光结构3的纳米粒子之间的空隙填充有电介质层7，电介质层7的材料为氧化铝，厚度为5-20nm(厚度不超过纳米粒子或第一陷光结构3的高度，如第一陷光结构3高度为100nm，则氧化铝厚度不大于100nm。
第一陷光结构3上沉积上层电池单元2，本实施方式中，上层电池单元2的第一吸收层21为宽带隙钙钛矿，上层电池单元2的基体21包括钙钛矿吸收层21、C60电子传输层和氧化镍空穴传输层，氧化镍空穴传输层与第一陷光结构3之间存在上层电池单元2的下传输层22，向光面具备上传输层23，上传输层23为电子传输层；上层电池单元2厚度为50nm-300nm。
上层太阳电池向光面存在上功能层9，为一层或多层结构，起到表面减反射的功能。
下层电池单元1的背光面一侧具有第二陷光结构5，上层电池单元2向光面一侧具有第三陷光结构4。第二陷光结构5、第三陷光结构4的在第一截面上形成分立的微结构也均为纳米粒子；纳米粒子采用银材料，或金、铝、铜、镓、铟等一种或多种材料，三层陷光结构种纳米粒子的材料可以相同或不同； 作为实施例1，第三陷光结构近似为圆柱体，平均直径30nm，高度30nm，平均间距50nm；第二陷光结构近似为圆柱体，平均直径100nm，高度100nm，平均间距1μm。
更进一步地，为实现更佳的整体陷光效果，第一陷光结构3、第二陷光结构5、第三陷光结构4分别对应的平均尺寸d1、d2、d3和分别对应的平均间距w1、w2、w3具有如下关系：
Figure PCTCN2021136475-appb-000023
和/或
Figure PCTCN2021136475-appb-000024
作为实施例1的更优方案，第三陷光结构与第一陷光结构满足该关系，
Figure PCTCN2021136475-appb-000025
当第一陷光结构为银纳米粒子直径为50nm、粒子之间的间距为80nm时，第三陷光结构可以为银纳米粒子直径20nm、平均间距102nm，第二陷光结构尺寸不做限定；
作为实施例1的更优方案，第二陷光结构与第一陷光结构满足该关系，
Figure PCTCN2021136475-appb-000026
当第一陷光结构为银纳米粒子直径为50nm、粒子之间的间距为100nm时，第二陷光结构可以为银纳米粒子直径1000nm、平均间距167nm，第三陷光结构尺寸不做限定；
作为实施例1的更优方案，同时满足
Figure PCTCN2021136475-appb-000027
和
Figure PCTCN2021136475-appb-000028
当第一陷光结构为银纳米粒子直径为50nm、粒子之间的间距为100nm时，第二陷光结构可以为银纳米粒子直径1000nm、平均间距167nm，第三陷光结构可以为银纳米粒子直径20nm、平均间距89nm。
实施例2
参照图6所示，图6示出了本公开实施例中的第三种垂直于叠层光伏器件向光面的第一截面的示意图。下层电池单元1的第二吸收层为晶体硅太阳电池，采用n型硅基体，基体厚度10μm，基体向光面为平面结构(抛光或者不抛光均可)，背光面为平面结构(抛光或者不抛光均可)；晶体硅基体背光面扩散p型层，制成下层电池单元1。下层电池单元1的背光面存在下功能层10，下功能层10为一层或多层结构，具备表面钝化以及减反射的功能。下 功能层10可以为p型多晶传输层或p型非晶硅，此种情况下下层电池单元1、下功能层10之间存在氧化硅或本征非晶硅界面层；下功能层10同时包含导电薄膜传输层，如掺铟氧化锡或掺铝氧化锌等。
下层电池单元1的背光面一侧设置有第二陷光结构5，如，第二陷光结构5采用在下功能层10中开孔。采用金属铝填充开孔，可以作为背电极引出。
下层电池单元1的向光面可以存在扩散的或沉积的场效应层或钝化层，或在第一陷光结构3接触位置存在局域的钝化层，如氧化硅。
下层电池单元1的向光面存在第一陷光结构3，第一陷光结构3在第一截面上形成分立的微结构为银纳米粒子，近似为半球体，平均球径50nm-200nm，半球高度近似等于球径的一半，球间距20nm-500nm(如，一种具体的实施方式为直径50nm，高度25nm，间距80nm)，并非为完美半球体，形成均匀分布的点阵结构，采用掩膜蒸镀后退火的方法获得。
纳米粒子之间的空隙或间距中存在电介质层7，电介质层7材料为氧化硅，厚度为5nm-20nm(厚度不超过第一陷光结构3的高度，如第一陷光结构3的高度为50nm，则氧化硅厚度不大于50nm)。
第一陷光结构3上沉积上层电池单元2，本实施方式中，上层电池单元2的第一吸收层为宽带隙钙钛矿，21为上层电池单元2的基底，基底21包括钙钛矿吸收层、C60电子传输层和氧化镍空穴传输层，氧化镍空穴传输层与第一陷光结构3之间存在上层太阳电池下传输层22，向光面具备上传输层23，上传输层23为电子传输层；上层电池单元2厚度为50nm-300nm。
上层电池单元2的向光面存在上功能层9，上功能层9为一层或多层结构，起到表面减反射的功能。
上层电池单元2向光面一侧具有第三陷光结构4。第三陷光结构4的在第一截面上形成分立的微结构也为纳米粒子。
作为实施例2的更优方案，第一陷光结构3、第二陷光结构5、第三陷光结构4分别对应的平均尺寸d1、d2、d3和分别对应的平均间距w1、w2、w3 具有如下关系：
Figure PCTCN2021136475-appb-000029
和/或
Figure PCTCN2021136475-appb-000030
即以第一陷光结构尺寸为50nm、间距80nm为例，则第二陷光结构尺寸200nm、间距112nm，第三陷光结构尺寸50nm、间距320nm。
实施例3
参照图7所示，图7示出了本公开实施例中的第四种垂直于叠层光伏器件向光面的第一截面的示意图。下层电池单元1的第二吸收层为晶体硅，采用n型硅基体，基体厚度10um，基体向光面为平面结构(抛光或者不抛光均可)，背光面为平面结构(抛光或者不抛光均可)；晶体硅基体背光面扩散p型层，制成下层电池单元1。下层电池单元1的背光面存在下功能层10，下功能层10为一层或多层结构，具备表面钝化以及减反射的功能。下功能层10可以为p型多晶传输层或p型非晶硅，此种情况下下层电池单元1、下功能层10之间存在氧化硅或本征非晶硅界面层；下功能层10同时包含导电薄膜传输层，如掺铟氧化锡或掺铝氧化锌等。
下层电池单元1的背光面一侧设置有第二陷光结构5，如，第二陷光结构5采用在下功能层10中开孔。采用金属铝填充开孔，可以作为背电极引出。
下层电池单元1的向光面可以存在扩散的或沉积的场效应层或钝化层，或在第一陷光结构3接触位置存在局域的钝化层，如氧化硅。下层电池单元1向光面存在第一陷光结构3，第一陷光结构3在第一截面上形成分立的微结构为平行线，采用银或银的合金材料，截面近似为矩形或梯形，底部(即与下层电池单元1的向光面接触区域)宽度为80nm，高度为50nm，平行线之间的间距为200nm-500nm，采用掩膜蒸镀的方法获得。或底部宽度200nm、间距500nm。
平行线之间的空隙存在电介质层7，电介质层7材料为氧化硅，厚度为5-20nm；该氧化硅层可以与上述下层电池单元1向光面钝化层为共同的一层。
第一陷光结构3上沉积上层电池单元2，本实施方式中，上层电池单元2的第一吸收层为宽带隙砷化镓，21为上层电池单元2的基体，基体21包括p 型砷化镓吸收层、n型砷化镓发射极，p型砷化镓吸收层与第一陷光结构3之间存在上层电池单元2的下传输层22，同时22起到缓冲晶格失配的作用，为铝镓砷化合物。基体21的向光面具备上传输层23，同时23为砷化镓电池窗口层，为铝铟磷化合物；上层电池单元2厚度为200nm-500nm。
上层电池单元2的向光面存在上功能层9，为一层或多层结构，起到表面减反射的功能。
上层电池单元2向光面一侧具有第三陷光结构4。第三陷光结构4的在第一截面上形成分立的微结构也为纳米粒子。
作为实施例3的更优方案，第一陷光结构3、第二陷光结构5、第三陷光结构4分别对应的平均尺寸d1、d2、d3和分别对应的平均间距w1、w2、w3具有如下关系：
Figure PCTCN2021136475-appb-000031
和/或；
Figure PCTCN2021136475-appb-000032
即以第一陷光结构尺寸为200nm、间距500nm为例，第二陷光结构尺寸为800nm、间距250nm，第三陷光结构尺寸100nm、间距500nm。
上面结合附图对本公开的实施例进行了描述，但是本公开并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本公开的启示下，在不脱离本公开宗旨和权利要求所保护的范围情况下，还可做出很多形式，这些均属于本公开的保护之内。

Claims (35)

  1. 一种叠层光伏器件，其特征在于，包括：层叠设置的上层电池单元、下层电池单元、以及位于所述上层电池单元和所述下层电池单元之间的第一陷光结构；所述上层电池单元的带隙宽度大于所述下层电池单元的带隙宽度；
    所述叠层光伏器件还包括位于所述下层电池单元背光面一侧的第二陷光结构和位于所述上层电池单元向光面一侧的第三陷光结构中的至少一个；
    所述第一陷光结构、所述第二陷光结构、所述第三陷光结构各选自金属或半导体材料中的任一种，三者产生的局域表面等离激元分别对应不同的光波响应峰值；
    所述叠层光伏器件具有垂直于所述叠层光伏器件向光面的第一截面，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构在所述第一截面上形成分立的微结构，所述分立的微结构在所述叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，所述微结构间的平均间距分别为w1、w2、w3；
    至少存在一个所述第一截面，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
    Figure PCTCN2021136475-appb-100001
  2. 根据权利要求1所述的叠层光伏器件，其特征在于，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构选自颗粒状、线状、挖孔结构。
  3. 根据权利要求2所述的叠层光伏器件，其特征在于，所述颗粒的形状为球形、半球形、线状交叉结构、圆柱体、锥体中的一种；所述孔的形状为圆形、近似圆形、多边形中的一种。
  4. 根据权利要求1所述的叠层光伏器件，其特征在于，所述上层电池单元包括第一吸收层；所述下层电池单元包括第二吸收层；所述第一陷光结构至少与所述第一吸收层或所述第二吸收层之间的距离不大于2nm。
  5. 根据权利要求4所述的叠层光伏器件，其特征在于，所述第一吸收层为钙钛矿材料，厚度为50nm-200nm。
  6. 根据权利要求4所述的叠层光伏器件，其特征在于，所述第二吸收层为单晶硅，厚度小于100μm。
  7. 根据权利要求1-6中任一所述的叠层光伏器件，其特征在于，所述叠层光伏器件还包括：电介质层；所述电介质层由填充在所述第一陷光结构的间隙中的电介质材料形成；
    所述第一陷光结构的高度大于或等于所述电介质层的高度。
  8. 根据权利要求7所述的叠层光伏器件，其特征在于，所述电介质材料的介电常数为1.2-200；
    所述电介质材料选自氧化硅、氧化铝、氮化硅、氧化钽、氮化铝中的至少一种。
  9. 根据权利要求1-6中任一所述的叠层光伏器件，其特征在于，所述第一陷光结构的局域表面等离激元的光波响应峰值处在所述下层电池单元的吸收光波长范围内；所述第三陷光结构的局域表面等离激元的光波响应峰值处在所述上层电池单元的吸收光波长范围内。
  10. 根据权利要求1-6中任一所述的叠层光伏器件，其特征在于，对于任意的第一截面，所述d2≤1200nm，d3≤300nm。
  11. 根据权利要求1-6中任一所述的叠层光伏器件，其特征在于，所述金属选自金、银、铝、铜、镓、铟中的至少一种；
    所述半导体材料选自掺铝氧化锌、掺铟氧化锡中的至少一种。
  12. 一种叠层光伏器件，其特征在于，包括：层叠设置的上层电池单元、下层电池单元、以及位于所述上层电池单元和所述下层电池单元之间的第一陷光结构；所述上层电池单元的带隙宽度大于所述下层电池单元的带隙宽度；
    所述叠层光伏器件还包括位于所述下层电池单元背光面一侧的第二陷光结构和位于所述上层电池单元向光面一侧的第三陷光结构中的至少一个；
    所述第一陷光结构、所述第二陷光结构、所述第三陷光结构各选自金属或半导体材料中的任一种，三者产生的局域表面等离激元分别对应不同的光 波响应峰值。
  13. 根据权利要求12所述的叠层光伏器件，其特征在于，所述叠层光伏器件具有垂直于所述叠层光伏器件向光面的第一截面，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构在所述第一截面上形成分立的微结构，所述分立的微结构在所述叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3；
    至少存在一个所述第一截面，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
    d3<d1<d2。
  14. 根据权利要求12所述的叠层光伏器件，其特征在于，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构选自颗粒状、线状、挖孔结构。
  15. 根据权利要求14所述的叠层光伏器件，其特征在于，所述颗粒的形状为球形、半球形、线状交叉结构、圆柱体、锥体中的一种；所述孔的形状为圆形、近似圆形、多边形中的一种。
  16. 根据权利要求12所述的叠层光伏器件，其特征在于，所述上层电池单元包括第一吸收层；所述下层电池单元包括第二吸收层；所述第一陷光结构至少与所述第一吸收层或所述第二吸收层之间的距离不大于2nm。
  17. 根据权利要求16所述的叠层光伏器件，其特征在于，所述第一吸收层为钙钛矿材料，厚度为50nm-200nm。
  18. 根据权利要求16所述的叠层光伏器件，其特征在于，所述第二吸收层为单晶硅，厚度小于100um。
  19. 根据权利要求12-18中任一所述的叠层光伏器件，其特征在于，所述叠层光伏器件还包括：电介质层；所述电介质层由填充在所述第一陷光结构的间隙中的电介质材料形成；
    所述第一陷光结构的高度大于或等于所述电介质层的高度。
  20. 根据权利要求19所述的叠层光伏器件，其特征在于，所述电介质材 料的介电常数为1.2-200；
    所述电介质材料选自氧化硅、氧化铝、氮化硅、氧化钽、氮化铝中的至少一种。
  21. 根据权利要求12-18中任一所述的叠层光伏器件，其特征在于，所述第一陷光结构的局域表面等离激元的光波响应峰值处在所述下层电池单元的吸收光波长范围内；所述第三陷光结构的局域表面等离激元的光波响应峰值处在所述上层电池单元的吸收光波长范围内。
  22. 根据权利要求12-18中任一所述的叠层光伏器件，其特征在于，所述金属选自金、银、铝、铜、镓、铟中的至少一种；
    所述半导体材料选自掺铝氧化锌、掺铟氧化锡中的至少一种。
  23. 一种叠层光伏器件，其特征在于，包括：层叠设置的上层电池单元、下层电池单元、以及位于所述上层电池单元和所述下层电池单元之间的第一陷光结构；所述上层电池单元的带隙宽度大于所述下层电池单元的带隙宽度；
    所述叠层光伏器件还包括位于所述下层电池单元背光面一侧的第二陷光结构或位于所述上层电池单元向光面一侧的第三陷光结构；
    所述第一陷光结构选自金属或半导体材料中的任一种，所述第二陷光结构或所述第三陷光结构各选自金属或半导体材料中的任一种，所述第一陷光结构和所述第二陷光结构产生的局域表面等离激元分别对应不同的光波响应峰值；或所述第一陷光结构和所述第三陷光结构产生的局域表面等离激元分别对应不同的光波响应峰值；
    所述叠层光伏器件具有垂直于所述叠层光伏器件向光面的第一截面，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构在所述第一截面上形成分立的微结构，所述分立的微结构在所述叠层光伏器件向光面上投影的平均尺寸分别为d1、d2、d3，所述微结构间的平均间距分别为w1、w2、w3；
    至少存在一个所述第一截面，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
    Figure PCTCN2021136475-appb-100002
    或，
    Figure PCTCN2021136475-appb-100003
  24. 根据权利要求23所述的叠层光伏器件，其特征在于，所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
    Figure PCTCN2021136475-appb-100004
    或，
    Figure PCTCN2021136475-appb-100005
  25. 根据权利要求23所述的叠层光伏器件，其特征在于，所述第一陷光结构、所述第二陷光结构、所述第三陷光结构选自颗粒状、线状、挖孔结构。
  26. 根据权利要求25所述的叠层光伏器件，其特征在于，所述颗粒的形状为球形、半球形、线状交叉结构、圆柱体、锥体中的一种；所述孔的形状为圆形、近似圆形、多边形中的一种。
  27. 根据权利要求23所述的叠层光伏器件，其特征在于，所述上层电池单元包括第一吸收层；所述下层电池单元包括第二吸收层；所述第一陷光结构至少与所述第一吸收层或所述第二吸收层之间的距离不大于2nm。
  28. 根据权利要求27所述的叠层光伏器件，其特征在于，所述第一吸收层为钙钛矿材料，厚度为50nm-200nm。
  29. 根据权利要求27所述的叠层光伏器件，其特征在于，所述第二吸收层为单晶硅，厚度小于100um。
  30. 根据权利要求23-29中任一所述的叠层光伏器件，其特征在于，所述叠层光伏器件还包括：电介质层；所述电介质层由填充在所述第一陷光结构的间隙中的电介质材料形成；
    所述第一陷光结构的高度大于或等于所述电介质层的高度。
  31. 根据权利要求30所述的叠层光伏器件，其特征在于，所述电介质材料的介电常数为1.2-200；
    所述电介质材料选自氧化硅、氧化铝、氮化硅、氧化钽、氮化铝中的至少一种。
  32. 根据权利要求23-29中任一所述的叠层光伏器件，其特征在于，所述 第一陷光结构的局域表面等离激元的光波响应峰值处在所述下层电池单元的吸收光波长范围内；所述第三陷光结构的局域表面等离激元的光波响应峰值处在所述上层电池单元的吸收光波长范围内。
  33. 根据权利要求23-29中任一所述的叠层光伏器件，其特征在于，对于任意的第一截面，所述d2≤1200nm，d3≤300nm。
  34. 根据权利要求23-29中任一所述的叠层光伏器件，其特征在于，所述金属选自金、银、铝、铜、镓、铟中的至少一种；
    所述半导体材料选自掺铝氧化锌、掺铟氧化锡中的至少一种。
  35. 根据权利要求23所述的叠层光伏器件，其特征在于，所述叠层光伏器件还包括位于所述下层电池单元背光面一侧的第二陷光结构和位于所述上层电池单元向光面一侧的第三陷光结构；
    所述微结构在所述叠层光伏器件向光面上投影的平均尺寸和相邻所述微结构间的平均间距具有如下关系：
    Figure PCTCN2021136475-appb-100006
    和/或，
    Figure PCTCN2021136475-appb-100007
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