WO2018192199A1 - 多结叠层激光光伏电池及其制作方法 - Google Patents

多结叠层激光光伏电池及其制作方法 Download PDF

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WO2018192199A1
WO2018192199A1 PCT/CN2017/106334 CN2017106334W WO2018192199A1 WO 2018192199 A1 WO2018192199 A1 WO 2018192199A1 CN 2017106334 W CN2017106334 W CN 2017106334W WO 2018192199 A1 WO2018192199 A1 WO 2018192199A1
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type
junction
layer
algaas
photovoltaic cell
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PCT/CN2017/106334
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English (en)
French (fr)
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董建荣
赵勇明
孙玉润
黄杰
于淑珍
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中国科学院苏州纳米技术与纳米仿生研究所
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Priority to JP2020505956A priority Critical patent/JP6888859B2/ja
Priority to ES17905938T priority patent/ES2947007T3/es
Priority to EP17905938.1A priority patent/EP3614444B1/en
Priority to US16/500,045 priority patent/US11245046B2/en
Priority to CA3058490A priority patent/CA3058490C/en
Publication of WO2018192199A1 publication Critical patent/WO2018192199A1/zh

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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
    • H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0693—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells the devices including, apart from doping material or other impurities, only AIIIBV compounds, e.g. GaAs or InP solar cells
    • H—ELECTRICITY
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    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0687—Multiple junction or tandem solar cells
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
    • H01L31/1848—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P comprising nitride compounds, e.g. InGaN, InGaAlN
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to a multi-junction photovoltaic cell, and in particular to a multi-junction laminated laser photovoltaic cell using AlGaAs as an absorption layer and a fabrication method thereof.
  • the laser energy supply system is an innovative energy transfer system that uses this system to deliver light from a laser source through a fiber optic to a laser photovoltaic cell to provide a stable power output.
  • the conversion of fiber-conducting light into electricity has more advantages than traditional metal wire and coaxial cable power transmission technology, and can be applied in the case of the need to eliminate electromagnetic interference or to isolate the electronic device from the surrounding environment, in radio communication, industry. Sensors, defense, aviation, medicine, energy and other directions have important applications.
  • Laser photovoltaic cells work similarly to solar cells, but because they are for monochromatic sources, the former can achieve higher conversion efficiencies. Unlike a typical solar cell, the light source uses a 790 nm-850 nm wavelength laser suitable for fiber transmission.
  • GaAs is a III-V compound semiconductor material.
  • the forbidden band width E g at room temperature is 1.428 eV.
  • the GaAs PN junction cell can be used to convert 790-850 nm laser energy into electrical energy for use as a photoelectric conversion in a laser energy supply system. element.
  • the open circuit voltage of GaAs photovoltaic cells is about 1V.
  • GaAs multi-junction laminated laser photovoltaic cells are grown on GaAs or Ge conductive substrates, and the sub-cells are connected by tunneling junctions, so that a higher output voltage can be obtained.
  • the main object of the present application is to provide a multi-junction laminated laser photovoltaic cell and a manufacturing method thereof to overcome the deficiencies in the prior art.
  • the technical solution adopted by the present application includes:
  • the embodiment of the present application provides a multi-junction laminated laser photovoltaic cell, comprising a battery unit laminate and a lower electrode and an upper electrode respectively electrically connected to a bottom and a top of the battery unit stack, wherein the battery unit stack comprises a stacked arrangement.
  • N AlGaAs The PN junction battery has two tunneling junctions between two adjacent sub-cells, N ⁇ 2.
  • the light absorbing layer in the AlGaAs PN junction battery includes a P-type Al x1 Ga 1-x1 As base region and an N-type Al x1 Ga 1-x1 As emitter region, wherein the value of X1 is such that the incident light laser wavelength Less than or equal to the absorption long-wavelength limit of Al x1 Ga 1-x1 As.
  • the bottom of the battery cell stack is electrically connected to the lower electrode via a conductive substrate.
  • a current spreading layer and an ohmic contact layer are sequentially formed on the battery cell stack, and the ohmic contact layer is electrically connected to the upper electrode, and the current spreading layer does not absorb incident laser light.
  • the battery cell stack includes a first tunneling junction, a first AlGaAs subcell, and an Nth tunneling junction, which are sequentially formed on the conductive substrate. And an Nth AlGaAs subcell, wherein the tunneling junction is alternately disposed with the subcell, and neither of the first tunneling junction to the Nth tunneling junction absorbs incident laser light.
  • the battery cell stack includes a first AlGaAs sub-batter sequentially formed on the conductive substrate, and the first tunneling junction is up to (N-1) An AlGaAs subcell, an (N-1) tunneling junction, and an Nth AlGaAs subcell, wherein a tunneling junction is alternately disposed with the subcell, and the first tunneling junction is in the (N-1) tunneling junction Neither of them absorbs the incident laser light.
  • the embodiment of the present application further provides a method for fabricating the multi-junction laminated laser photovoltaic cell, comprising:
  • a lower electrode is formed on the back surface of the conductive substrate.
  • the present application uses AlGaAs as the absorption layer to convert the laser energy of the multi-junction laminate battery, which can effectively increase the open circuit voltage of the photovoltaic cell, thereby greatly improving the conversion efficiency of the photovoltaic cell.
  • FIG. 1 is a schematic cross-sectional view showing an epitaxial wafer of an AlGaAs six-junction laminated laser photovoltaic cell in an exemplary embodiment of the present application.
  • FIG. 2 is a schematic cross-sectional view showing an initial product of an AlGaAs six-junction laminated laser photovoltaic cell in an exemplary embodiment of the present application.
  • FIG 3 is a top plan view of a finished AlGaAs hexa-junction laser photovoltaic cell in an exemplary embodiment of the present application.
  • An aspect of an embodiment of the present application first provides a multi-junction laminated laser photovoltaic cell comprising a battery cell stack and a lower electrode and an upper electrode electrically connected to a bottom and a top of the battery cell stack, respectively, and the battery cell stack
  • the N AlGaAs PN junction cells are arranged in a stack, and the adjacent two of the sub-cells are connected in series via a tunneling junction, N ⁇ 2.
  • the light absorbing layer in the AlGaAs PN junction battery includes a P-type Al x1 Ga 1-x1 As base region and an N-type Al x1 Ga 1-x1 As emitter region, wherein the value of X1 is such that the incident light laser wavelength The absorption long-wavelength of less than or equal to Al x1 Ga 1-x1 As, especially close to and less than the absorption long-wavelength limit of Al x1 Ga 1-x1 As. More specifically, the design of x1 in Al x1 Ga 1-x1 As varies with the incident laser wavelength, that is, the specific composition of Al x1 Ga 1-x1 As can be adjusted according to the incident laser wavelength to satisfy the above requirements. . For example, when the incident wavelength is 830-650 nm, then x1 can be 0.02-0.38.
  • the AlGaAs sub-battery includes a P-type back field layer, a P-type Al x1 Ga 1-x1 As base region, an N-type Al x1 Ga 1-x1 As emitter region, and an N-type window sequentially disposed in a set direction.
  • the multijunction stacked laser photovoltaic cell comprises a conductive single crystal substrate, a plurality of AlGaAs subcells, a tunnel junction between each subcell, a current spreading layer, and an ohmic contact layer. Each sub-cell is connected in series by a tunneling junction.
  • the bottom of the battery cell stack is electrically connected to the lower electrode via a conductive substrate.
  • the conductive substrate is selected from a conductive single crystal substrate.
  • the material of the conductive single crystal substrate includes, but is not limited to, GaAs or Ge.
  • the battery cell stack is formed on a conductive substrate, and the AlGaAs sub-cell includes P-type Al x2 Ga 1-x2 As or P-type Ga 0.52 In 0.48 disposed in a direction away from the conductive substrate.
  • a P back field layer a P-type Al x1 Ga 1-x1 As base region, an N-type Al x1 Ga 1-x1 As emitter region, an N-type Al x3 Ga 1-x3 As or an N-type Ga 0.52 In 0.48 P window layer, wherein
  • the values of x2 and x3 should be such that Al x2 Ga 1-x2 As and Al x3 Ga 1-x3 As do not absorb incident laser light.
  • x2, x3 can be adjusted depending on the incident laser wavelength, thereby changing the specific composition of Al x2 Ga 1-x2 As and Al x3 Ga 1-x3 As to satisfy the foregoing requirements.
  • a current spreading layer and an ohmic contact layer are sequentially formed on the battery cell stack, and the ohmic contact layer is electrically connected to the upper electrode, and the current spreading layer does not absorb incident laser light.
  • the material of the ohmic contact layer includes, but is not limited to, GaAs.
  • the conductive substrate employs an N-type substrate including a first tunneling junction, a first AlGaAs subcell, and an Nth tunneling junction, which are sequentially formed on the conductive substrate. And an Nth AlGaAs subcell, wherein the tunneling junction is alternately disposed with the subcell, and neither of the first tunneling junction to the Nth tunneling junction absorbs incident laser light.
  • the first tunneling junction includes an N + -type Ga 0.52 In 0.48 P or N + -type (Al) GaAs layer and a P + -type (Al) GaAs layer disposed in a direction away from the conductive substrate
  • the Any of the two tunneling junctions to the Nth tunneling junction includes an N + -type Ga 0.51 In 0.49 P or N + -type Al x4 Ga 1-x4 As (x4>x1) layer disposed in a direction away from the conductive substrate.
  • x4, x5 can be adjusted depending on the incident laser wavelength, thereby changing the specific composition of Al x4 Ga 1-x4 As and Al x5 Ga 1-x5 As to satisfy the foregoing requirements.
  • composition of matter of the second tunneling junction to the Nth tunneling junction may be identical.
  • an N-type Ga 0.51 In 0.49 P or an N-type Al x6 Ga 1-x6 As current spreading layer and an N + -type GaAs ohmic contact layer are sequentially formed on the Nth AlGaAs sub-battery, wherein the value of x6 is further
  • the current spreading layer should be such that the incident laser light is not absorbed.
  • x6 can be adjusted depending on the incident laser wavelength, thereby changing the specific composition of Al x6 Ga 1-x6 As to satisfy the aforementioned requirements.
  • the conductive substrate employs a P-type substrate including a first AlGaAs sub-cell sequentially formed on a conductive substrate, a first tunneling junction up to (N-1) An AlGaAs subcell, an (N-1) tunneling junction, and an Nth AlGaAs subcell, wherein a tunneling junction is alternately disposed with the subcell, and the first tunneling junction is in the (N-1) tunneling junction Neither of them absorbs the incident laser light.
  • any one of the first tunneling junction to the (N-1) tunneling junction includes N + -type Ga 0.52 In 0.48 P or N + -type Al x4 Ga disposed in a direction away from the conductive substrate.
  • the Nth AlGaAs subcell is further formed with an N-type Ga 0.52 In 0.48 P or an N-type Al x6 Ga 1-x6 As current spreading layer and an N + -type GaAs ohmic contact layer, x6>x1, and
  • the value of x6 should be such that the current spreading layer does not absorb incident laser light. That is, x6 can be adjusted according to the incident laser wavelength, thereby changing the specific composition of Al x6 Ga 1-x6 As to satisfy the foregoing requirements.
  • each of the AlGaAs PN junction cells in the battery cell stack is such that the photocurrent generated by each of the AlGaAs PN junction cells when sufficiently absorbing the incident laser light energy is the same.
  • the thickness of the absorption layer of each AlGaAs sub-cell should ensure sufficient absorption of the incident laser light energy and the photocurrent generated in each AlGaAs sub-cell is the same.
  • an anti-reflection film is further disposed on the light-receiving surface of the multi-junction laminated laser photovoltaic cell.
  • the light receiving surface is distributed on a top end surface of the multi-junction laminated laser photovoltaic cell.
  • the multi-junction laminated laser photovoltaic cell described in the present application can utilize the incident most widely by adopting a multi-junction AlGaAs laminated structure and a band gap of the absorption layer Al x1 Ga 1-x1 As or the like, or slightly smaller than the wavelength of the incident laser light.
  • the energy of the photon to get the maximum output voltage can be at least about 8% higher (relative lift ratio) than a battery of similar structure using GaAs as the absorber layer.
  • Another aspect of the embodiments of the present application further provides a method of fabricating the multi-junction laminated laser photovoltaic cell, comprising: forming a battery cell stack on a front surface of a conductive substrate;
  • a lower electrode is formed on the back surface of the conductive substrate.
  • the fabrication method comprises: sequentially growing a plurality of AlGaAs PN junction cells on a conductive single crystal substrate, tunneling junctions for electrical connection between the sub-cells, current spreading layer, and top re-doping An ohmic contact layer is formed, and then an upper electrode, a lower electrode, and an anti-reflection film including a gate electrode are separately formed to form a target device.
  • the absorption layer of each of the sub-cells is AlGaAs.
  • the manufacturing method may include: forming the battery cell stack by at least one of MOCVD and MBE.
  • the N-type dopant atoms used include Si, Se, S or Te.
  • the P-type dopant atoms used include Be, Zn, Mg or C.
  • the manufacturing method may further include: first performing a thinning process on the back surface of the conductive substrate, and then forming a lower electrode on the back surface of the conductive substrate.
  • the manufacturing method may further include: forming an ohmic contact between the upper electrode and the ohmic contact layer at least by rapid annealing.
  • the manufacturing method may further include: forming an anti-reflection film on the light-receiving surface of the formed multi-junction laminated laser photovoltaic cell.
  • the manufacturing method may include the following steps:
  • the N-type dopant atom is Si, Se, S or Te
  • the P-type dopant atom is Zn, Mg or C
  • each layer of material is sequentially grown by an MBE method on a conductive single crystal substrate
  • the N-type dopant atoms are Si, Se, S or Te
  • the P-type dopant atoms are Be, Mg or C
  • a back surface of the substrate is formed by electron beam evaporation, thermal evaporation or magnetron sputtering of one or more layers of metal;
  • the anti-reflection film is removed by wire bonding at a wire bonding place other than the circular light-receiving surface, and the metal is exposed for bonding wires.
  • an AlGaAs six junction stacked laser photovoltaic cell fabricated on an N-type GaAs substrate is described.
  • the manufacturing method of the laser photovoltaic cell comprises the following specific steps:
  • tunneling junction comprising N + -type Ga 0.52 In 0.48 P or N + -type (Al) GaAs layers arranged in a direction away from the substrate, P + type (Al) GaAs layer;
  • the tunneling junction comprising N + -type Ga 0.52 In 0.48 P or N + -type Al x4 Ga 1-x4 As disposed in a direction away from the substrate a layer of x4>x1), a layer of P + -type Al x5 Ga 1-x5 As(x5>x1), and the arrangement of x4 and x5 is such that Al x4 Ga 1-x4 As and Al x5 Ga 1-x5 As do not absorb incident light;
  • the contact layer, used as an ohmic contact, is arranged such that the current wide expansion layer does not absorb incident light.
  • Each structural layer in the epitaxial wafer of the six-junction GaAs laser photovoltaic cell is grown by MOCVD or MBE; if the MOCVD method is used, the N-type dopant atom is Si, Se, S or Te, P-type dopant atom It is Zn, Mg or C; if the MBE method is used, the N-type dopant atoms are Si, Se, S, Sn or Te, and the P-type dopant atoms are Be, Mg or C.
  • the back side of the substrate is fabricated by electron beam evaporation, thermal evaporation or magnetron sputtering of one or more layers of metal (N-type GaAs substrate using AuGe/Ni/Au, P-type GaAs substrate using Ti/Pd/Au).
  • Planar electrode N-type GaAs substrate using AuGe/Ni/Au, P-type GaAs substrate using Ti/Pd/Au.
  • An anti-reflection film is formed on the light-receiving surface.
  • the anti-reflection film is removed by wire bonding at a wire bonding place other than the circular light-receiving surface, and the metal is exposed for bonding wires.
  • Al x1 Ga 1-x1 As is used as an absorption layer to convert laser energy, and the Al composition of AlGaAs is adjusted so that the wavelength of the incident laser light is less than or equal to the absorption long wavelength limit of AlGaAs.
  • the thermal relaxation loss during the photon energy conversion process is minimized.
  • the incident laser as a laser with a wavelength of about 808 nm
  • the open circuit voltage of the Al 0.07 Ga 0.93 As laser photovoltaic cell can be improved by about 8 compared with the GaAs laser photovoltaic cell. %, which can greatly improve the conversion efficiency of laser photovoltaic cells.
  • a six-junction AlGaAs laminated laser photovoltaic cell for converting an 808 nm laser may include a GaAs substrate 01 and a first tunneling junction 02.
  • the first to fourth AlGaAs sub-cells to the sixth AlGaAs sub-cells 03, 05, 07, 09, 11 and 13 comprise an AlGaAs or GaInP back field layer 30, an AlGaAs base region 31, an AlGaAs emitter region 32, an AlGaAs or GaInP window layer 33
  • the first tunneling junction 02 includes (Al)GaAs or GaInP 20 and (Al)GaAs layers 21;
  • the second tunneling junctions to the sixth tunneling junctions 04, 06, 08, 10 and 12 include (Al)GaAs or GaInP 40 and AlGaAs layer 41.
  • the manufacturing method of the six-junction AlGaAs laminated laser photovoltaic cell specifically comprises the following steps:
  • a first tunneling junction 02 is grown on an N-type GaAs substrate (1-2 ⁇ 10 18 cm -3 , thickness 350 ⁇ m) 01, and N + -type GaAs is doped with a concentration of Si of 1 ⁇ 10 19 cm -3 by 20 nm.
  • the growth of the epitaxial wafer is completed, and the structure thereof can be referred to FIG.
  • the photoresist is evenly distributed on the front side of the wafer, and the gate line pattern on the photolithographic mask is transferred into the previously prepared circle by photoresist exposure and development to expose a portion of the N + GaAs contact layer to form a gate line electrode.
  • an upper electrode including a gate line having a width of 6 ⁇ m and a pitch of 250 ⁇ m in a circular light-receiving surface having a diameter of 2 mm was produced.
  • N + -type GaAs contact layer of the uncovered portion of the gate electrode in the circular light-receiving region is etched by a wet method until the window layer Ga 0.52 In 0.48 P 14 of the sixth AlGaAs sub-cell is exposed.
  • Annealing was performed between the metal and the N-type GaAs by rapid annealing in an N2 atmosphere at 420 ° C for 90 seconds.
  • a 43 nm TiO 2 /102 nm SiO 2 double-layer anti-reflection film 52 was deposited on the light-receiving surface by an optical coater.
  • the anti-reflection film is removed by wire bonding at a wire bonding place other than the circular light-receiving surface, and the metal is exposed for bonding wires.
  • the laser photovoltaic cell process is completed by cleavage and separation of the laser photovoltaic cell chip, and the structure of the finished product of the AlGaAs six-junction laminated laser photovoltaic cell device can be referred to FIG.

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Abstract

本申请公开了一种多结叠层激光光伏电池，其包括电池单元层叠体以及分别与电池单元层叠体底部、顶部电连接的下电极、上电极，所述电池单元层叠体包括层叠设置的N个AlGaAs PN结子电池，相邻两个所述的子电池之间经隧穿结串联，N≥2。所述AlGaAs PN结子电池采用AlGaAs吸收层。本申请还公开了制作所述多结叠层激光光伏电池的方法。本申请采用AlGaAs作为多结叠层电池的吸收层转换激光能量，可以有效提高光伏电池的开路电压，进而可以大幅提升光伏电池的转换效率。

Description

多结叠层激光光伏电池及其制作方法 技术领域
本申请涉及一种多结光伏电池，具体涉及一种采用AlGaAs作吸收层的多结叠层激光光伏电池及其制作方法。
背景技术
激光供能系统是一个创新的能量传递系统，凭借这个系统，将激光光源发出的光通过光纤输送到激光光伏电池上，可以提供稳定的电源输出。通过光纤传导光转化为电比传统的金属线和同轴电缆电力传输技术有更多的优点，可以应用在需要消除电磁干扰或需要将电子器件与周围环境隔离的情况下，在无线电通信，工业传感器，国防，航空，医药、能源等方向有重要应用。激光光伏电池的工作原理与太阳电池类似，但由于是针对单色光源，前者可以获得更高的转换效率。与一般太阳电池不同的是，光源采用适合光纤传输的790nm-850nm波长的激光。
GaAs是III-V族化合物半导体材料，室温下的禁带宽度Eg是1.428eV，GaAs PN结电池可以用于将790-850nm的激光能量转换为电能，用作激光供能系统中的光电转换元件。GaAs光伏电池的开路电压约为1V,在GaAs或Ge导电衬底上生长GaAs多结叠层激光光伏电池，各子电池间通过隧穿结连接，这样可以获得较高的输出电压。然而对于比较成熟且应用较广的808nm(光子能量1.5346eV)激光，由于光子能量比GaAs的禁带宽度大0.1066eV，采用GaAs作吸收层吸收808nm激光时，每个光子从价带激发到导带的电子将通过热弛豫损失0.1066eV的能量，占光子能量的6.9％，而占到转换到电能的10％以上。
发明内容
本申请的主要目的在于提供一种多结叠层激光光伏电池及其制作方法，以克服现有技术中的不足。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种多结叠层激光光伏电池，包括电池单元层叠体以及分别与电池单元层叠体底部、顶部电连接的下电极、上电极，所述电池单元层叠体包括层叠设置的N个AlGaAs  PN结子电池，相邻两个所述的子电池之间经隧穿结串联，N≥2。
进一步地，所述AlGaAs PN结子电池中的光吸收层包括P型Alx1Ga1-x1As基区和N型Alx1Ga1-x1As发射区，其中X1的取值应使入射光激光波长小于或等于Alx1Ga1-x1As的吸收长波限。
进一步地，所述电池单元层叠体底部经导电衬底与所述下电极电连接。
更进一步地，所述电池单元层叠体上还依次形成有电流扩展层和欧姆接触层，所述欧姆接触层与所述上电极电连接，所述电流扩展层不吸收入射激光。
更进一步地，若所述导电衬底采用N型衬底，则所述电池单元层叠体包括依次形成在导电衬底上的第一隧穿结、第一AlGaAs子电池、直至第N隧穿结和第N AlGaAs子电池，其中隧穿结与子电池交替设置，且所述第一隧穿结至第N隧穿结中的任一者均不吸收入射激光。更进一步地，若所述导电衬底采用P型衬底，则所述电池单元层叠体包括依次形成在导电衬底上的第一AlGaAs子电池、第一隧穿结直至第(N-1)AlGaAs子电池、第(N-1)隧穿结和第N AlGaAs子电池，其中隧穿结与子电池交替设置，且所述第一隧穿结至第(N-1)隧穿结中的任一者均不吸收入射激光。
本申请实施例还提供了一种制作所述多结叠层激光光伏电池的方法，包括：
在导电衬底正面生长形成所述电池单元层叠体；
在所述电池单元层叠体上形成介质膜，并在所述介质膜上加工出窗口，使所述电池单元层叠体的欧姆接触层的至少局部区域从所述窗口中露出；
在从所述窗口中暴露出的欧姆接触层上制作上电极；
刻蚀从所述窗口中暴露出的欧姆接触层的未被上电极覆盖的区域，直至露出所述电池单元层叠体的电流扩展层；
在导电衬底背面制作下电极。
与现有技术相比，本申请采用AlGaAs作为多结叠层电池的吸收层转换激光能量，可以有效提高光伏电池的开路电压，进而可以大幅提升光伏电池的转换效率。
附图说明
图1是本申请一典型实施例中一种AlGaAs六结叠层激光光伏电池外延晶片的剖面结构示意图。
图2是本申请一典型实施例中一种AlGaAs六结叠层激光光伏电池初成品的剖面示意图。
图3是本申请一典型实施例中一种AlGaAs六结叠层激光光伏电池成品的俯视图。
具体实施方式
针对现有技术中的不足，本案发明人经长期研究和实践，提出了本申请的技术方案，以下予以详细说明。
本申请实施例的一个方面首先提供了一种多结叠层激光光伏电池，包括电池单元层叠体以及分别与电池单元层叠体底部、顶部电连接的下电极、上电极，所述电池单元层叠体包括层叠设置的N个AlGaAs PN结子电池，相邻两个所述的子电池之间经隧穿结串联，N≥2。
进一步地，所述AlGaAs PN结子电池中的光吸收层包括P型Alx1Ga1-x1As基区和N型Alx1Ga1-x1As发射区，其中X1的取值应使入射光激光波长小于或等于Alx1Ga1-x1As的吸收长波限，尤其是接近且小于Alx1Ga1-x1As的吸收长波限。更确切的说，Alx1Ga1-x1As中的x1的设计随入射激光波长而改变，亦即，可以依据入射激光波长而调整Alx1Ga1-x1As的具体组成，使之满足前述要求。例如，当入射波长为830-650nm时，则x1可以为0.02-0.38。
更进一步地，所述AlGaAs子电池包含沿设定方向依次设置的P型背场层、P型Alx1Ga1-x1As基区、N型Alx1Ga1-x1As发射区、N型窗口层，其中P型背场层和N型窗口层均不吸收入射激光。
在一些实施方案中，所述多结叠层激光光伏电池包括导电单晶衬底、多个AlGaAs子电池、各子电池间的隧穿结、电流扩展层和欧姆接触层。各子电池间通过隧穿结串联。
更进一步地，所述电池单元层叠体底部经导电衬底与所述下电极电连接。
优选的，所述导电衬底选自导电单晶衬底。
优选的，所述导电单晶衬底的材质包括但不限于GaAs或Ge。
更进一步地，所述电池单元层叠体形成在导电衬底上，且所述AlGaAs子电池包含沿远离导电衬底的方向依次设置的P型Alx2Ga1-x2As或P型Ga0.52In0.48P背场层、P型Alx1Ga1-x1As基区、N型Alx1Ga1-x1As发射区、N型Alx3Ga1-x3As或N型Ga0.52In0.48P窗口层，其中x2和x3的取值应使Alx2Ga1-x2As和Alx3Ga1-x3As不吸收入射激光。换言之，可以依据入射激光波长而调整x2、x3，从而改变Alx2Ga1-x2As和Alx3Ga1-x3As的具体组成，使之满足前述要求。
更进一步地，所述电池单元层叠体上还依次形成有电流扩展层和欧姆接触层，所述欧姆接触层与所述上电极电连接，所述电流扩展层不吸收入射激光。
优选的，所述欧姆接触层的材质包括但不限于GaAs。
在一些实施方案中，所述导电衬底采用N型衬底，所述电池单元层叠体包括依次形成在导电衬底上的第一隧穿结、第一AlGaAs子电池、直至第N隧穿结和第N AlGaAs子电池，其中 隧穿结与子电池交替设置，且所述第一隧穿结至第N隧穿结中的任一者均不吸收入射激光。进一步地，所述第一隧穿结包含沿远离导电衬底方向依次设置的N+型Ga0.52In0.48P或N+型(Al)GaAs层和P+型(Al)GaAs层，所述第二隧穿结至第N隧穿结中的任一者包含沿远离导电衬底方向依次设置的N+型Ga0.51In0.49P或N+型Alx4Ga1-x4As(x4>x1)层和P+型Alx5Ga1-x5As(x5>x1)层，其中x4、x5的取值应使Alx4Ga1-x4As和Alx5Ga1-x5As不吸收入射激光。换言之，可以依据入射激光波长而调整x4、x5，从而改变Alx4Ga1-x4As和Alx5Ga1-x5As的具体组成，使之满足前述要求。
更进一步地，其中第二隧穿结至第N隧穿结的物质组成可以是完全相同的。
更进一步地，所述第N AlGaAs子电池上还依次形成有N型Ga0.51In0.49P或N型Alx6Ga1-x6As电流扩展层和N+型GaAs欧姆接触层，其中x6的取值应使所述电流扩展层不吸收入射激光。换言之，可以依据入射激光波长而调整x6，从而改变Alx6Ga1-x6As的具体组成，使之满足前述要求。
在一些实施方案中，所述导电衬底采用P型衬底，所述电池单元层叠体包括依次形成在导电衬底上的第一AlGaAs子电池、第一隧穿结直至第(N-1)AlGaAs子电池、第(N-1)隧穿结和第N AlGaAs子电池，其中隧穿结与子电池交替设置，且所述第一隧穿结至第(N-1)隧穿结中的任一者均不吸收入射激光。
进一步地，所述第一隧穿结至第(N-1)隧穿结中的任一者包含沿远离导电衬底方向依次设置的N+型Ga0.52In0.48P或N+型Alx4Ga1-x4As层和P+型Alx5Ga1-x5As层，其中x4>x1，x5>x1，且x4、x5的取值应使Alx4Ga1-x4As和Alx5Ga1-x5As不吸收入射激光。亦即，可以依据入射激光波长而调整x4、x5，从而改变Alx4Ga1-x4As和Alx5Ga1-x5As的具体组成，使之满足前述要求。更进一步地，其中第一隧穿结至第(N-1)隧穿结的物质组成可以是完全相同的。
更进一步地，所述第N AlGaAs子电池上还依次形成有N型Ga0.52In0.48P或N型Alx6Ga1-x6As电流扩展层和N+型GaAs欧姆接触层，x6>x1，且x6的取值应使所述电流扩展层不吸收入射激光。亦即，可以依据入射激光波长而调整x6，从而改变Alx6Ga1-x6As的具体组成，使之满足前述要求。
更进一步地，所述电池单元层叠体中各AlGaAs PN结子电池的厚度应使各AlGaAs PN结子电池在充分吸收入射激光光能时产生的光电流相同。
更进一步地，各AlGaAs子电池吸收层的厚度应保证入射激光光能的充分吸收且各AlGaAs子电池中产生的光电流相同。
更进一步地，所述多结叠层激光光伏电池的受光面上还设有减反射膜。
例如，所述受光面分布在所述多结叠层激光光伏电池的顶端面上。
本申请所述的多结叠层激光光伏电池通过采用多结AlGaAs叠层结构、且吸收层Alx1Ga1-x1As的带隙等或略小于入射激光的波长，最可以大限度地利用入射光子的能量，从而获得最大的输出电压。例如，与采用GaAs作吸收层的类似结构的电池相比，以808nm入射激光为例，本申请多结叠层激光光伏电池的效率可至少高出约8％(相对提升比例)。
本申请实施例的另一个方面还提供了一种制作所述多结叠层激光光伏电池的方法，包括：在导电衬底正面生长形成所述电池单元层叠体；
在所述电池单元层叠体上形成介质膜，并在所述介质膜上加工出窗口，使所述电池单元层叠体的欧姆接触层的至少局部区域从所述窗口中露出；
在从所述窗口中暴露出的欧姆接触层上制作上电极；
刻蚀从所述窗口中暴露出的欧姆接触层的未被上电极覆盖的区域，直至露出所述电池单元层叠体的电流扩展层；
在导电衬底背面制作下电极。
在一些实施方案中，所述制作方法包括：在导电单晶衬底上依次生长形成若干个AlGaAs PN结子电池、用于各子电池间电学连接的隧穿结、电流扩展层和顶部重掺的欧姆接触层，而后分别制作包含栅电极的上电极、下电极及增透膜，形成目标器件。其中各子电池的吸收层为AlGaAs。
进一步地，所述的制作方法可以包括：至少采用MOCVD、MBE中的任一种方式生长形成所述电池单元层叠体。
优选的，在生长形成所述电池单元层叠体的过程中，采用的N型掺杂原子包括Si、Se、S或Te。
优选的，在生长形成所述电池单元层叠体的过程中，采用的P型掺杂原子包括Be、Zn、Mg或C。
进一步地，所述的制作方法还可包括：先对所述导电衬底背面进行减薄处理，之后在导电衬底背面制作下电极。
进一步地，所述的制作方法还可包括：至少通过快速退火方式使上电极与所述欧姆接触层之间形成欧姆接触。
进一步地，所述的制作方法还可包括：在所形成的多结叠层激光光伏电池的受光面上制作减反膜。
在本申请的一些较为具体的实施方案中，所述的制作方法可以包括如下步骤：
(1)在导电单晶衬底上由MOCVD方法依次生长各层材料，N型掺杂原子为Si、Se、S或Te；P型掺杂原子为Zn、Mg或C；
或者，在导电单晶衬底上由MBE方法依次生长各层材料，N型掺杂原子为Si、Se、S或Te；P型掺杂原子为Be、Mg或C；
(2)在上述外延生长好的多结叠层电池晶片(电池单元层叠体)正面(N+GaAs接触层)沉积一层介质膜，然后采用光刻和腐蚀的方法在该层介质膜上制作圆形窗口，露出N+GaAs接触层；
(3)通过匀胶、光刻、电子束蒸发(热蒸发或磁控溅射)一层或多层金属、金属剥工艺步骤，制作包含圆形受光区域中栅电极的上电极；
(4)采用湿法方法腐蚀圆形受光区域内栅电极未覆盖部分的N+型GaAs接触层，直至露出电流扩展层；
(5)通过机械抛光减薄衬底；
(6)衬底背面以电子束蒸发、热蒸发或磁控溅射一层或多层金属制作平面电极；
(7)采用快速退火在金属与半导体间形成欧姆接触。
(8)在受光面制作减反膜。
(9)通过光刻的方法在圆形受光面以外引线键合处去掉减反射膜，露出金属用于键合引线。
(10)解理或切割分离激光光伏电池芯片，完成激光光伏电池工艺。
在本申请的一些更为具体的实施方案中涉及一种在N型GaAs衬底上制作的AlGaAs六结叠层激光光伏电池。该激光光伏电池的制作方法包括如下具体步骤：
(一)六结AlGaAs叠层激光光伏电池外延晶片(电池单元层叠体)的生长
(1)在N型GaAs衬底上生长第一隧穿结，隧穿结包括沿远离衬底方向依次设置的N+型Ga0.52In0.48P或N+型(Al)GaAs层，P+型(Al)GaAs层；
(2)在上述第二隧穿结上生长P型Alx2Ga1-x2As(x2>x1)或P型Ga0.52In0.48P背场层、P型Alx1Ga1-x1As基区、N型Alx1Ga1-x1As发射区、N型Alx3Ga1-x3As(x3>x1)或N型Ga0.52In0.48P(与GaAs晶格匹配)窗口层，形成第一AlGaAs子电池；
(2)在上述第一AlGaAs子电池上生长第二隧穿结，隧穿结包括沿远离衬底方向依次设置的N+型Ga0.52In0.48P或N+型Alx4Ga1-x4As(x4>x1)层，P+型Alx5Ga1-x5As(x5>x1)层，x4和x5的设置使得Alx4Ga1-x4As和Alx5Ga1-x5As不吸收入射光；
(3)然后依次交替生长隧穿结(与第一隧穿结结构相同)和AlGaAs子电池，直至第六AlGaAs子电池；
(4)在第六AlGaAs子电池的N型Alx6Ga1-x6As(x6>x1)或N型Ga0.52In0.48P窗口层上生长N+型(大于4×1018cm-3)GaAs接触层，用作欧姆接触，x6的设置使得电流宽扩展层不吸收入射光。
所述六结GaAs激光光伏电池外延晶片中的各结构层均采用MOCVD或MBE法生长而成；若采用MOCVD法，则N型掺杂原子为Si、Se、S或Te，P型掺杂原子为Zn、Mg或C；若采用MBE法，则N型掺杂原子为Si、Se、S、Sn或Te，P型掺杂原子为Be、Mg或C。
(二)器件(多结叠层激光光伏电池)的制作
(1)采用PECVD在上述外延生长好的AlGaAs六结叠层电池外延晶片正面(N+GaAs接触层)沉积一层SiO2介质膜，然后采用光刻和腐蚀的方法在该层SiO2上制作圆形窗口，露出N+GaAs接触层；
(2)通过匀胶、光刻、电子束蒸发(热蒸发或磁控溅射)AuGe/Ni/Au、金属剥离工艺步骤，制作包含圆形受光区域中栅电极的上电极；
(3)采用湿法方法腐蚀圆形受光区域内栅电极未覆盖部分的N+型GaAs接触层，直至露出电流扩展层；
(4)通过机械抛光将衬底减薄到约100μm；
(5)衬底背面以电子束蒸发、热蒸发或磁控溅射一层或多层金属(N型GaAs衬底采用AuGe/Ni/Au，P型GaAs衬底采用Ti/Pd/Au)制作平面电极；
(6)采用快速退火在金属与半导体间形成欧姆接触。
(7)在受光面制作减反膜。
(8)通过光刻的方法在圆形受光面以外引线键合处去掉减反射膜，露出金属用于键合引线。
(9)解理或切割分离激光光伏电池芯片，完成激光光伏电池工艺。
本申请的多结叠层激光光伏电池中采用Alx1Ga1-x1As作为吸收层来转换激光能量，通过调整AlGaAs的Al组分使得入射激光的波长小于或等于AlGaAs的吸收长波限，这样可将光子能量转换过程中的热弛豫损失减到最小，以入射激光为波长约808nm的激光为例，与GaAs激光光伏电池相比，Al0.07Ga0.93As激光光伏电池的开路电压可提高约8％，从而能够大幅提高激光光伏电池的转换效率。
以下结合附图及实施例对本申请的技术方案进行更为详尽的解释说明。
参见图1、图2、图3所示是本申请一典型实施例涉及的一种转换808nm激光的六结AlGaAs叠层激光光伏电池，其可以包含GaAs衬底01，第一隧穿结02，第一AlGaAs子电池03，第二隧穿结04，第二AlGaAs子电池05，第三隧穿结06，第三AlGaAs子电池07，第四隧穿结 08，第四AlGaAs子电池09，第五隧穿结10，第五AlGaAs子电池11，第六隧穿结12，第六AlGaAs子电池13，电流扩展层14，GaAs欧姆接触层15，正电极50，负电极51，减反膜52，引线键合点61，受光面62和电极栅线63等。其中，第一AlGaAs子电池到第六AlGaAs子电池03、05、07、09、11和13层包含AlGaAs或GaInP背场层30、AlGaAs基区31、AlGaAs发射区32、AlGaAs或GaInP窗口层33；第一隧穿结02包括(Al)GaAs或GaInP 20和(Al)GaAs层21；第二隧穿结至第六隧穿结04、06、08、10和12包括(Al)GaAs或GaInP 40和AlGaAs层41。
该六结AlGaAs叠层激光光伏电池的制作方法具体包括如下步骤：
一、用MOCVD方法生长AlGaAs六结叠层激光光伏电池外延晶片
(1)在N型GaAs衬底(1-2×1018cm-3，厚度350μm)01上生长第一隧穿结02，由20nm掺Si浓度1×1019cm-3的N+型GaAs层20和20nm掺C浓度4×1019cm-3的P+型Al0.3Ga0.7As层21组成；
(2)生长30nm掺C浓度为1×1018cm-3的P型Al0.2Ga0.8As 30，作为第一AlGaAs子电池03的背场，然后生长2090nm掺C杂浓度为4×1017cm-3的Al0.07Ga0.93As 31作为第一子电池03的基区，再生长200nm掺Si浓度约为1×1018cm-3的Al0.07Ga0.93As 32作为第一子电池03的发射区，接着生长40nm掺Si浓度为1×1018cm-3的Al0.2Ga0.8As 33作为第一子电池03的窗口层。
(3)生长20nm掺Si浓度为1×1019cm-3的Al0.15Ga0.85As 40作为第二隧穿结04的N+层、20nm掺C浓度4×1019cm-3的Al0.3Ga0.7As层41作为第二隧穿结04的P+层；
(4)按照上述方法依次交替生长其他AlGaAs子电池(05、07、09、11和13)和隧穿结(06、08、10和12)，直至第六AlGaAs子电池13。为保证器件吸收入射到电池中光的99％并满足各AlGaAs子电池中产生的光电流相同，各子电池吸收层的厚度如表1所示。
表1 AlGaAs子电池吸收层的近似厚度(nm)
Figure PCTCN2017106334-appb-000001
(5)在第六AlGaAs子电池13的窗口层上生长1000nm掺Si浓度1×1018cm-3Ga0.52In0.48P 14、100nm掺Si浓度6×1018cm-3的GaAs欧姆接触层15，完成外延晶片的生长，其结构可以参阅图1。
二、六结AlGaAs叠层激光光伏电池的制备工艺
(1)采用PECVD在外延生长好的AlGaAs叠层多结电池外延晶片正面(N+GaAs接触层15)沉积一层200nm SiO2，然后在该层SiO2上匀光刻胶，采用光刻胶曝光、显影把光刻掩模板上的图形转移到光刻胶上，暴露出SiO2表面；接着以光刻胶作掩膜采用HF缓冲腐蚀液在SiO2上腐蚀出直径为2.2mm的圆形窗口，露出N+GaAs接触层。
(2)随后在晶片正面匀光刻胶，采用光刻胶曝光、显影把光刻掩模上的栅线图形转移到前面制作好的圆内，露出部分N+GaAs接触层制作栅线电极。
(3)通过电子束蒸发方法在晶片正面依次沉积AuGe/Ni/Au(35/10/100nm)、Ag 1000nm、Au 100nm金属层作为正(上)电极50，采用剥离的方法去掉不需要区域的金属，制作出包含直径为2mm的圆形受光面中宽度6μm、间距为250μm栅线的上电极。
(4)采用湿法方法腐蚀圆形受光区域内栅电极未覆盖部分的N+型GaAs接触层，直至露出第六AlGaAs子电池的窗口层Ga0.52In0.48P 14。
(5)通过机械抛光减薄GaAs衬底01到约110μm，
(6)在晶片背面GaAs衬底01上用电子束次蒸发依次沉积AuGe/Ni/Au(35/10/100nm)形成下电极层51，此时所获AlGaAs六结叠层激光光伏电池器件初成品的结构请参阅图2；
(7)采用快速退火在N2气氛和420℃下退火90秒，金属与N型GaAs之间形成欧姆接触。
(8)采用光学镀膜机在受光面蒸镀43nm TiO2/102nm SiO2双层减反射膜52。
(9)通过光刻的方法在圆形受光面以外引线键合处去掉减反射膜，露出金属用于键合引线。
(10)通过解理分离激光光伏电池芯片，完成激光光伏电池工艺，该AlGaAs六结叠层激光光伏电池器件成品的结构可参阅图3。
应当理解，以上仅是本申请的较佳应用范例，对本申请的保护范围不构成任何限制。凡采用等同变换或者等效替换而形成的技术方案，均应落在本申请权利保护范围之内。

Claims (19)

  1. 一种多结叠层激光光伏电池，包括电池单元层叠体以及分别与电池单元层叠体底部、顶部电连接的下电极、上电极，其特征在于：所述电池单元层叠体包括层叠设置的N个AlGaAs PN结子电池，相邻两个所述的子电池之间经隧穿结串联，N≥2。
  2. 根据权利要求1所述的多结叠层激光光伏电池，其特征在于：所述AlGaAs PN结子电池中的光吸收层包括P型Alx1Ga1-x1As基区和N型Alx1Ga1-x1As发射区，其中X1的取值应使入射光激光波长小于或等于Alx1Ga1-x1As的吸收长波限。
  3. 根据权利要求2所述的多结叠层激光光伏电池，其特征在于：所述AlGaAs子电池包含沿设定方向依次设置的P型背场层、P型Alx1Ga1-x1As基区、N型Alx1Ga1-x1As发射区和N型窗口层，其中P型背场层和N型窗口层均不吸收入射激光。
  4. 根据权利要求2所述的多结叠层激光光伏电池，其特征在于：所述电池单元层叠体底部经导电衬底与所述下电极电连接；优选的，所述导电衬底选自导电单晶衬底；优选的，所述导电单晶衬底的材质包括GaAs或Ge。
  5. 根据权利要求4所述的多结叠层激光光伏电池，其特征在于：所述电池单元层叠体形成在导电衬底上，且所述AlGaAs子电池包含沿远离导电衬底的方向依次设置的P型Alx2Ga1-x2As或P型Ga0.52In0.48P背场层、P型Alx1Ga1-x1As基区、N型Alx1Ga1-x1As发射区、N型Alx3Ga1-x3As或N型Ga0.52In0.48P窗口层，其中x2和x3的取值应使Alx2Ga1-x2As和Alx3Ga1-x3As不吸收入射激光。
  6. 根据权利要求5所述的多结叠层激光光伏电池，其特征在于：所述导电衬底采用GaAs导电单晶衬底，并且所述背场层中P型Alx2Ga1-x2As或P型Ga0.52In0.48P与GaAs晶格匹配。
  7. 根据权利要求5所述的多结叠层激光光伏电池，其特征在于：所述电池单元层叠体上还依次设置有电流扩展层和欧姆接触层，所述欧姆接触层与所述上电极电连接，所述电流扩展层不吸收入射激光；优选的，所述欧姆接触层的材质包括GaAs。
  8. 根据权利要求4-7中任一项所述的多结叠层激光光伏电池，其特征在于：所述导电衬底采用N型衬底，所述电池单元层叠体包括依次形成在导电衬底上的第一隧穿结、第一AlGaAs子电池、直至第N隧穿结和第NAlGaAs子电池，其中隧穿结与子电池交替设置，且所述第一隧穿结至第N隧穿结中的任一者均不吸收入射激光。
  9. 根据权利要求8所述的多结叠层激光光伏电池，其特征在于：所述第一隧穿结包含沿远离导电衬底方向依次设置的N+型Ga0.52In0.48P或N+型(Al)GaAs层和P+型(Al)GaAs层，所述第二 隧穿结至第N隧穿结中的任一者包含沿远离导电衬底方向依次设置的N+型Ga0.51In0.49P或N+型Alx4Ga1-x4As(x4>x1)层和P+型Alx5Ga1-x5As(x5>x1)层，其中x4、x5的取值应使Alx4Ga1-x4As和Alx5Ga1-x5As不吸收入射激光。
  10. 根据权利要求8所述的多结叠层激光光伏电池，其特征在于：所述第NAlGaAs子电池上还依次形成有N型Ga0.51In0.49P或N型Alx6Ga1-x6As电流扩展层和N+型GaAs欧姆接触层，其中x6的取值应使所述电流扩展层不吸收入射激光。
  11. 根据权利要求4-7中任一项所述的多结叠层激光光伏电池，其特征在于：所述导电衬底采用P型衬底，所述电池单元层叠体包括依次形成在导电衬底上的第一AlGaAs子电池、第一隧穿结直至第(N-1)AlGaAs子电池、第(N-1)隧穿结和第NAlGaAs子电池，其中隧穿结与子电池交替设置，且所述第一隧穿结至第(N-1)隧穿结中的任一者均不吸收入射激光。
  12. 根据权利要求11所述的多结叠层激光光伏电池，其特征在于：所述第一隧穿结至第(N-1)隧穿结中的任一者包含沿远离导电衬底方向依次设置的N+型Ga0.52In0.48P或N+型Alx4Ga1-x4As层和P+型Alx5Ga1-x5As层，其中x4>x1，x5>x1，且x4、x5的取值应使Alx4Ga1-x4As和Alx5Ga1-x5As不吸收入射激光。
  13. 根据权利要求11所述的多结叠层激光光伏电池，其特征在于：所述第NAlGaAs子电池上还依次形成有N型Ga0.52In0.48P或N型Alx6Ga1-x6As电流扩展层和N+型GaAs欧姆接触层，x6>x1，且x6的取值应使所述电流扩展层不吸收入射激光。
  14. 根据权利要求1、2、3、4、5、6、7、9、10、12、13中任一者所述的多结叠层激光光伏电池，其特征在于：所述电池单元层叠体中各AlGaAs PN结子电池的厚度应使各AlGaAs PN结子电池在充分吸收入射激光光能时产生的光电流相同。
  15. 根据权利要求1所述的多结叠层激光光伏电池，其特征在于：所述多结叠层激光光伏电池的受光面上还设有减反射膜；优选的，所述受光面分布在所述多结叠层激光光伏电池的顶端面上。
  16. 权利要求1-15中任一项所述多结叠层激光光伏电池的制作方法，其特征在于包括：
    在导电衬底正面生长形成所述电池单元层叠体；
    在所述电池单元层叠体上形成介质膜，并在所述介质膜上加工出窗口，使所述电池单元层叠体的欧姆接触层的至少局部区域从所述窗口中露出；
    在从所述窗口中暴露出的欧姆接触层上制作上电极；
    刻蚀从所述窗口中暴露出的欧姆接触层的未被上电极覆盖的区域，直至露出所述电池单元层叠体的电流扩展层；
    在导电衬底背面制作下电极；
    以及，在所形成的多结叠层激光光伏电池的受光面上制作减反膜。
  17. 根据权利要求16所述的制作方法，其特征在于包括：至少采用MOCVD、MBE中的任一种方式生长形成所述电池单元层叠体；优选的，在生长形成所述电池单元层叠体的过程中，采用的N型掺杂原子包括Si、Se、S或Te；优选的，在生长形成所述电池单元层叠体的过程中，采用的P型掺杂原子包括Be、Zn、Mg或C。
  18. 权利要求16所述的制作方法，其特征在于还包括：先对所述导电衬底背面进行减薄处理，之后在导电衬底背面制作下电极。
  19. 权利要求16所述的制作方法，其特征在于还包括：至少通过快速退火方式使上电极与所述欧姆接触层之间形成欧姆接触。
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