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WO2014012442A1 - 一种高效多结太阳能电池的制备方法 - Google Patents

一种高效多结太阳能电池的制备方法 Download PDF

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WO2014012442A1
WO2014012442A1 PCT/CN2013/078965 CN2013078965W WO2014012442A1 WO 2014012442 A1 WO2014012442 A1 WO 2014012442A1 CN 2013078965 W CN2013078965 W CN 2013078965W WO 2014012442 A1 WO2014012442 A1 WO 2014012442A1
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sub
cell
band gap
solar cell
subcell
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French (fr)
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毕京锋
林桂江
刘建庆
丁杰
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Xiamen Sanan Optoelectronics Technology Co Ltd
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Xiamen Sanan Optoelectronics Technology Co Ltd
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    • H—ELECTRICITY
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    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/161—Photovoltaic cells having only PN heterojunction potential barriers comprising multiple PN heterojunctions, e.g. tandem cells
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    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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    • 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
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    • 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
    • H10F10/1425—Inverted metamorphic multi-junction [IMM] photovoltaic cells
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    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/163—Photovoltaic cells having only PN heterojunction potential barriers comprising only Group III-V materials, e.g. GaAs/AlGaAs or InP/GaInAs photovoltaic cells
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    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/127—The active layers comprising only Group III-V materials, e.g. GaAs or InP
    • H10F71/1272—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising at least three elements, e.g. GaAlAs or InGaAsP
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    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/127—The active layers comprising only Group III-V materials, e.g. GaAs or InP
    • H10F71/1272—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising at least three elements, e.g. GaAlAs or InGaAsP
    • H10F71/1274—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising at least three elements, e.g. GaAlAs or InGaAsP comprising nitrides, e.g. InGaN or InGaAlN
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    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/127—The active layers comprising only Group III-V materials, e.g. GaAs or InP
    • H10F71/1276—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising growth substrates not made of Group III-V materials
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    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/124—Active materials comprising only Group III-V materials, e.g. GaAs
    • H10F77/1248—Active materials comprising only Group III-V materials, e.g. GaAs having three or more elements, e.g. GaAlAs, InGaAs or InGaAsP
    • H—ELECTRICITY
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    • 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
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/124—Active materials comprising only Group III-V materials, e.g. GaAs
    • H10F77/1248—Active materials comprising only Group III-V materials, e.g. GaAs having three or more elements, e.g. GaAlAs, InGaAs or InGaAsP
    • H10F77/12485—Active materials comprising only Group III-V materials, e.g. GaAs having three or more elements, e.g. GaAlAs, InGaAs or InGaAsP comprising nitride compounds, e.g. InGaN
    • 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 invention relates to a preparation method of an efficient multi-junction solar cell, belonging to the technical field of semiconductor materials.
  • solar cells have attracted more and more attention as a practical new energy source. It is a semiconductor device that uses photovoltaic effect to convert solar energy into electrical energy, which greatly reduces the dependence of people's production and life on coal, oil and natural gas, and becomes one of the most effective ways to use green energy.
  • solar energy is one of the most ideal renewable energy sources, and fully exploiting solar energy has become a sustainable energy strategy decision for governments around the world.
  • concentrating multi-junction compound solar cells which are the third generation photovoltaic power generation technology, have attracted much attention due to their high photoelectric conversion efficiency.
  • GaInP/GaAs/Ge triple junction solar cells have achieved more than 41.8% under concentrating conditions. Photoelectric conversion efficiency.
  • the Ge bottom cell absorbs too much low-energy photons, it does not match the short-circuit current of the top cells in InGaP and GaAs, so the conventional GaInP/GaAs/Ge
  • the triple junction solar cell structure is not an optimal combination of efficiency.
  • you can find a material with a band gap of 1 eV instead of Ge you can achieve three-junction battery current matching.
  • In 0.3 Ga 0.7 As has a band gap of 1eV, which is one of the choices, but there is 2.14% between it and GaAs. The lattice mismatch, and after the flip-chip growth is completed, the process is complicated and the cost is relatively expensive.
  • a method of fabricating an efficient multi-junction solar cell comprising the steps of:
  • a fourth subcell is formed over the third subcell to have a fourth bandgap greater than the third bandgap, the lattice constant of which matches the first, second, and third subcells.
  • a solar cell epitaxial growth system comprising: a MOCVD reaction chamber, MBE The reaction chamber and the pretreatment chamber, wherein the MOCVDE reaction chamber and the MBE reaction chamber share the pretreatment chamber and are connected by a channel in which a transfer device is located.
  • the invention is designed to be MOCVD and MBE
  • the combination of two crystal growth methods, in-situ growth of the required solar cell structure in different growth chambers, ensures the cleanliness of the sample surface and improves the crystal quality.
  • Figure 1 is a plot of band gap and lattice constant for 1eV GaInNAsSb.
  • FIG. 2 is a schematic diagram of an epitaxial growth apparatus of a solar cell according to an embodiment of the present invention.
  • FIG. 3 is a diagram showing a band gap distribution of an efficient five-junction solar cell according to an embodiment of the present invention.
  • Figure 4 is a flow chart of the preparation of the embodiment 2 of the present invention.
  • FIG. 5 is a flow chart showing epitaxial growth of a second subcell according to an embodiment of the present invention.
  • FIG. 6 is a schematic structural view of a multi-junction solar cell according to Embodiment 2 of the present invention.
  • Figure 7 is a flow chart of the preparation of the embodiment 3 of the present invention.
  • Figure 8 is a schematic view showing the structure of a multi-junction solar cell according to Embodiment 3 of the present invention.
  • 201, 211 a second sub-battery back field layer
  • 303, 313 a third sub-cell emitting area
  • Figure 1 is a plot of band gap and lattice constant for 1eV GaInNAsSb. As can be seen from the figure, it can be in the tradition GaInNAs(Sb) sub-cells with 1eV inserted into a GaInP/GaAs/Ge triple junction solar cell form a four-junction solar cell for cell current matching and GaInNAs(Sb) The lattice is matched to GaAs to improve the photoelectric conversion efficiency of the multi-junction solar cell.
  • the following embodiment proposes an epitaxial growth system for a multi-junction solar cell, which integrates MOCVD in the same pre-processing chamber (Load-lock).
  • the system and the MBE system are connected by a vacuum channel, and a transfer device is arranged in the vacuum channel for epitaxial wafers in the MOCVD system and MBE during epitaxial growth. Transfer between systems.
  • Each of the embodiments disclosed below utilizes the epitaxial growth system described above to prepare an efficient multi-junction solar cell.
  • a four junction solar cell is fabricated using the epitaxial growth system described above, the specific steps of which include.
  • the Ge substrate serves as a base region to constitute a first subcell having a first band gap (0.65 to 0.70 eV).
  • the third subcell is grown by MOCVD to have a third band gap greater than the second band gap (1. 35 ⁇ 1.45 eV ) and match the lattice of the first and second subcells.
  • a fourth sub-cell is grown by the MOCVD method over the third sub-cell to have a fourth band gap greater than the third band gap 1.86 ⁇ 1.95 eV), whose lattice constant matches the first, second and third sub-cells.
  • a highly doped cap layer is formed over the fourth subcell.
  • a five-junction solar cell is fabricated using the epitaxial growth system described above, the specific steps of which include.
  • the Ge substrate serves as a base region to constitute a first subcell having a first band gap (0.67 to 0.70 eV).
  • the third sub-cell is grown by MOCVD to have a third band gap greater than the second band gap ( 1.40 ⁇ 1.42 eV) and match the lattice of the first and second subcells.
  • a fourth sub-cell is grown by the MOCVD method over the third sub-cell to have a fourth band gap greater than the third band gap ( 1.60 ⁇ 1.70 eV), whose lattice constant matches the first, second and third sub-cells.
  • the fourth sub-cell grown by MOCVD Al x Ga y In 1-xy P fifth sub-cell having a fifth band gap greater than the fourth band gap ( 1.90 ⁇ 2.10 eV), whose lattice constant matches the first, second, third and fourth sub-cells.
  • a highly doped cap layer is formed over the fifth subcell.
  • the GaInNAs (Sb) second subcell can be grown in the following manner: a MOCVD growth method, forming a back field layer over the first subcell; forming a GaInNAs (Sb) base region and an emitter region in the back field layer by MBE growth method; using MOCVD In the growth method, a window layer is formed over the emitter region to form a second subcell.
  • Figure 2 discloses an epitaxial growth system 800 for a multi-junction solar cell.
  • the epitaxial growth system 800 is provided with an MOCVD system, a MBE system, and a pretreatment chamber 830 in which the MOCVD reaction chamber 810 and the MBE reaction chamber 820 share a pretreatment chamber 830.
  • the vacuum channel 840 is connected to the MOCVD reaction chamber 810 and the MBE reaction chamber 820, and the vacuum is maintained below 1 ⁇ 10 -6 Pa.
  • a transfer device is disposed in the vacuum channel for transferring the epitaxial wafer between the MOCVD system and the MBE system during the epitaxial growth process.
  • the MOCVD reaction chamber 810 and the MBE reaction chamber 820 are disposed in the same pretreatment chamber, and a transfer device is disposed, so that only the program control can be realized in the same pretreatment chamber during the epitaxial growth process. Switch between MOCVD growth and MBE growth.
  • the combination of MOCVD and MBE crystal growth methods is realized, and the required solar cell structure is grown in situ in different growth chambers, preventing surface oxidation and adsorption pollution of the sample surface, and ensuring the cleanliness of the sample surface.
  • Figure 4 discloses a flow chart of a method of preparing a four junction solar cell.
  • Step S11 providing a Ge substrate.
  • Step S12 forming a first sub-cell 100 with a Ge substrate as a base region.
  • n-type GaAs is epitaxially grown on the surface of the above substrate 101, and the doping concentration is 2 ⁇ 10 18 Cm -3 , thickness is 100 nm as the first sub-cell emitter region 102, epitaxially grown on the n-type GaAs layer 102 with a thickness of 25 nm, doped at 1 ⁇ 10 18 Cm -3 InGaP material layer as window layer 102, p-type Ge
  • the substrate itself serves as a base region to constitute a first subcell.
  • Step S13 forming a GaInNAs (Sb) second sub-cell 200 above the tunneling junction 601 .
  • FIG. 5 includes five steps of steps S13a to S13e.
  • S13a in the MOCVD growth chamber 810, a p-type InGaP is grown over the tunnel junction 601 As the back field layer 201, the thickness is 50 nm, and the doping concentration is 1 ⁇ 10 18 Cm -3 about.
  • S13b The growing sample is passed through the pretreatment chamber 830 and the vacuum channel 840 to the MBE growth chamber 820.
  • the base region 202 In the MBE growth chamber 820, in the back field layer 201 is formed above Ga 0.92 In 0.08 N 0.02 As 0.97 Sb 0.01
  • the base region 202 preferably has a thickness of 3000 nm and a doping concentration of 5 ⁇ 10 17 Cm -3
  • the emitter region 203 has a thickness of 200 nm and a doping concentration of 2 ⁇ 10 18 Cm -3 .
  • S13d The grown sample is passed through the pretreatment chamber 830 and the vacuum channel 840, and the track is sent back.
  • S13e In the MOCVD growth chamber, an n-type InGaP window layer 204 is grown on the emitter region 203 with a thickness of 25 nm. , doping concentration is 1 ⁇ 10 18 Cm -3 about.
  • Step S14 Forming a third sub-battery 300 over the second sub-cell by MOCVD.
  • MOCVD In the growth chamber, a thickness of 50 nm is grown above the tunnel junction 602, and the doping concentration is 1 ⁇ 2 ⁇ 10 18 Cm -3 of The p+-InGaP material layer is used as the back field layer 301; the thickness is 2 microns above the back field layer 301, and the doping concentration is 1 ⁇ 5 ⁇ 10 17 Cm -3
  • the n-type GaAs material layer is used as the second sub-cell base 302; and the thickness is 100 on the base 302.
  • doping concentration is about 2 ⁇ 10 18 Cm -3
  • the n+-Ga(In)As material layer acts as the emitter region 303; in the emitter region 303 is grown on the n-type InGaP window layer 304 with a thickness of 25 nm and a doping concentration of 1 ⁇ 10 18 Cm -3 about.
  • Step S15 Forming a fourth sub-battery 400 over the third sub-cell by MOCVD.
  • MOCVD In the growth chamber, the epitaxial growth thickness is 100 nm above the tunneling junction 603, and the doping concentration is 1 ⁇ 2 ⁇ 10 18 Cm -3 of
  • the p-AlGaInP material layer is used as the back field layer 401; the thickness of the back field layer 401 is 1000 nm, and the doping concentration is 5 ⁇ , respectively. 10 17 Cm -3
  • the p+-GaInP material layer is used as the base region 402; the growth thickness is 100 nm on the base region 402.
  • Doping concentration is 2 ⁇ 10 18 Cm -3
  • the n+-GaInP material layer serves as the emitter region 403; in the emitter region 403 An n-type AlGaInP window layer 504 having a thickness of 25 nm and a doping concentration of 1 ⁇ 10 18 Cm -3 Left and right.
  • a heavily doped n++-GaAs material layer is grown on top of the fourth subcell as a capping layer in the MOCVD growth chamber 700, thickness 500 nm, doping concentration 1 ⁇ 10 19 Cm -3 .
  • a method for preparing a highly efficient five-junction solar cell can be obtained by the following steps:
  • Step S21 providing a Ge substrate.
  • a Ge substrate 111 having a p-type thickness of 140 ⁇ m is selected, and its doping concentration is 2 ⁇ 10 17 cm -3 - 5 ⁇ 10 17 cm -3 .
  • Step S22 forming a first sub-cell 110 with a Ge substrate as a base region.
  • the doping concentration on the surface of the substrate 111 is 2 ⁇ 10 18 Cm -3 N-type with a thickness of 100 nm
  • the GaAs material layer is used as the first subcell emitting region 112, and the epitaxial growth thickness is 25 nm on the n-type GaAs layer 112, and the doping is concentrated at 1 ⁇ 10 18 Cm -3 InGaP material layer as window layer 113, p-type Ge
  • the substrate itself serves as a base region to constitute a first subcell.
  • a heavily doped p++/n++-GaAs tunneling junction is grown over the first subcell 611 , its thickness is 50 nm, and the doping concentration is up to 2 ⁇ 10 19 Cm -3 .
  • Step S23 forming a GaInNAs (Sb) second sub-cell 210 above the tunneling junction 611 .
  • a p-type InGaP is grown as a back-field layer 211 over the tunnel junction 611 with a thickness of 50 nm and a doping concentration of 1 ⁇ 10 18 Cm -3 about.
  • the growing sample is passed through the pretreatment chamber 830 and the vacuum channel 840 to the MBE growth chamber. 820.
  • the base region 212 In the MBE growth chamber 820, formed above the back field layer 211 Ga 0.92 In 0.08 N 0.02 As 0.97 Sb 0.01
  • the second subcell the base region 212 preferably has a thickness of 3000 nm and a doping concentration of 5 ⁇ 10 17 Cm -3
  • the emitter region 213 has a thickness of 200 nm and a doping concentration of 2 ⁇ 10 18 Cm -3 .
  • the grown sample is passed through pretreatment chamber 830 and vacuum channel 840, and the track is transferred back to MOCVD. Growth room.
  • an n-type InGaP window layer 214 is grown on the emitter region 213 with a thickness of 25 nm and a doping concentration of 1 ⁇ 10 18 Cm -3 about.
  • Step S24 Forming a third sub-battery 310 over the second sub-cell by MOCVD.
  • MOCVD In the growth chamber, a thickness of 50 nm is grown above the tunneling junction 612, and the doping concentration is 1 ⁇ 2 ⁇ 10 18 Cm -3 of The p+-InGaP material layer is used as the back field layer 311; the thickness is 2 microns above the back field layer 301, and the doping concentration is 1 ⁇ 5 ⁇ 10 17 Cm -3
  • the n-type Ga ( In ) As material layer is used as the base region 312; and the thickness is grown on the base region 312.
  • an n-type InGaP window layer 314 is grown on the emitter region 313, the thickness of which is 25 nm, and the doping concentration is 1 ⁇ 10 18 Cm -3 about.
  • Step S25 Forming a fourth sub-battery 400 over the third sub-cell by MOCVD.
  • MOCVD In the growth chamber, the epitaxial growth thickness is 100 nm above the tunneling junction 613, and the doping concentration is 1 ⁇ 2 ⁇ 10 18 Cm -3 of The p-AlGaInP material layer is used as the back field layer 411; the thickness of the back field layer 411 is 1000 nm, and the doping concentration is 5 ⁇ , respectively.
  • heavily doped is grown between the fourth sub-cell and the fifth sub-cell p++/n++-AlGaAs tunneling junction 614 with a thickness of 50 nm and a doping concentration of up to 2 ⁇ 10 19 Cm -3 .
  • Step S26 Forming a fifth sub-battery 500 over the fourth sub-cell by MOCVD.
  • MOCVD In the growth chamber, the epitaxial growth thickness is 100 nm and the doping concentration is 1 ⁇ 2 ⁇ 10 above the tunnel junction 614.
  • the p-AlGaAs material layer is used as the back field layer 511; the epitaxial growth thickness is 500 nm on the back field layer 511, and the doping concentration is 1 ⁇ 5 ⁇ 10 17 Cm -3 of p+-Al x Ga y In 1-xy
  • the P material layer serves as the base region 512; the growth thickness on the base region 512 is 50 nm with a doping concentration of approximately 2 ⁇ 10 18 Cm -3 of n+-Al x Ga y In 1-xy
  • the P material layer acts as the emitter region 513; grows above the emitter region 513 N-type AlGaAs window layer 903 with a thickness of 25 nm and a doping concentration of 1 ⁇ 10 18 Cm -3 Left and right.
  • a heavily doped n++-GaAs material layer is grown on top of the fourth subcell as a capping layer in the MOCVD growth chamber 710, thickness 500 nm, doping concentration 1 ⁇ 10 19 Cm -3 .
  • Ge/GaInNAs (Sb) is formed.
  • /InGaAs/AlGaAs/AlGaInP five-junction solar cell its band gap distribution is shown in Figure 3. Shown.
  • the five-junction solar cell refines the absorption spectrum, current matching is easier to achieve, and the spectral absorption range is wider and more efficient.

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Description

一种高效多结太阳能电池的制备方法
本申请主 张如下优先权：中国发明专利申请号 201210249856.3 ，题为 ' 一种高效多结太阳能电池的制备方法 ' ，于 2012 年 7 月 19日 提交。 上述申请的全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种高效多结太阳能电池的制备方法，属半导体材料技术领域。
背景技术
在最近几年，太阳电池作为实用的新能源，吸引了越来越多的关注。它是一种利用光生伏打效应，将太阳能转化成电能的半导体器件，这在很大程度上减少了人们生产生活对煤炭、石油及天然气的依赖，成为利用绿色能源的最有效方式之一。在所有新能源中，太阳能是最为理想的再生能源之一，充分开发利用太阳能成为世界各国政府可持续发展的能源战略决策。近些年来，作为第三代光伏发电技术的聚光多结化合物太阳电池，因其高光电转换效率而倍受关注。
目前，GaInP/GaAs/Ge 三结太阳电池在聚光条件下已获得超过 41.8% 光电转换效率。但是由于 Ge 底电池过多的吸收了低能光子，因而与 InGaP 和 GaAs 中顶电池的短路电流不匹配，所以传统的 GaInP/GaAs/Ge 三结太阳电池结构并不是效率最优化的组合。理想状况下，如果能够寻找禁带宽度为 1 eV 的材料替代 Ge ，就能够实现三结电池电流匹配。 In0.3Ga0.7As 具有 1eV 的禁带宽度，是选择之一，但其与 GaAs 之间存在 2.14% 的晶格失配，而且倒装生长完成后，工艺过程复杂，成本相对昂贵。
发明内容
根据本发明的第一个方面，提供了一种高效多结太阳能电池的制备方法，其包括步骤：
（ 1 ）提供一 Ge 衬底，用于半导体外延生长；
（ 2 ）以 Ge 衬底为基区，在所述 Ge 衬底上生长发射区，构成第一子电池，其具有一第一带隙；
（ 3 ）采用 MBE 生长方法，在所述第一子电池上方形成第二子电池，使其具有大于第一带隙的一第二带隙，且晶格与第一子电池晶格匹配；
（ 4 ）采用 MOCVD 生长方法，在所述第二子电池上方形成第三子电池，使其具有大于第二带隙的第三带隙，并且与第一、二子电池晶格匹配；
（ 5 ）采用 MOCVD 生长方法，在所述第三子电池上方形成第四子电池，使其具有大于第三带隙的第四带隙，其晶格常数与第一、二、三子电池匹配。
根据本发明的第二个方面，一种太阳能电池外延生长系统，包括： MOCVD 反应腔、 MBE 反应腔和预处理室，其中 MOCVDE 反应腔和 MBE 反应腔共用所述预处理室并通过一通道连接，一传送装置位于所述通道内。
本发明通过设计，将 MOCVD 和 MBE 两种晶体生长方法联合，在不同的生长室中原位生长所需的太阳能电池结构，保证了样品表面的洁净度，提高了晶体质量。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。此外，附图数据是描述概要，非按比例绘制。
图 1 为 1eV GaInNAsSb 的带隙和晶格常数关系图。
图 2 为根据本发明实施的太阳能电池的外延生长设备示意图。
图 3 为根据本发明实施的一种高效五结太阳能电池带隙分布图。
图 4 为本发明实施 2 的制备流程图。
图 5 为本根据本发明实施的第二子电池的外延生长流程图。
图 6 为本发明实施 2 的多结太阳能电池结构简图。
图 7 为本发明实施 3 的制备流程图。
图 8 为本发明实施 3 的多结太阳能电池结构简图。
图中各标号表示
100 、 110 ：第一子电池；
101 、 111 ： p 型 Ge 衬底；
102 、 112 ：第一子电池发射区；
103 、 113 ：第一子电池窗口层；
200 、 210 ：第二子电池；
201 、 211 ：第二子电池背场层；
202 、 212 ：第二子电池基区；
203 、 213 ：第二子电池发射区；
204 、 214 ：第二子电池窗口层；
300 、 310 ：第三子电池；
301 、 311 ：第三子电池背场层；
302 、 312 ：第三子电池基区；
303 、 313 ：第三子电池发射区；
304 、 314 ：第三子电池窗口层；
400 、 410 ：第四子电池；
401 、 411 ：第四子电池背场层；
402 、 412 ：第四子电池基区；
403 、 413 ：第四子电池发射区；
404 、 414 ：第四子电池窗口层；
510 ：第五子电池；
511 ：第五子电池背场层；
512 ：第五子电池基区；
513 ：第五子电池发射区；
514 ：第五子电池窗口层；
611 ：第一、二子电池之间的隧穿结；
612 ：第二、三子电池之间的隧穿结；
613 ：第三、四子电池之间的隧穿结；
614 ：第四、五子电池之间的隧穿结；
700 、 710 ：盖帽层；
800 ：设备系统；
810 ： MOCVD 反应腔；
820 ： MEB 反应腔；
830 ：预处理室；
840 ：真空通道。
具体实施方式
图 1 为 1eV GaInNAsSb 的带隙和晶格常数关系图。从图中可看出，可在传统 GaInP/GaAs/Ge 三结太阳电池中插入 1eV 的 GaInNAs(Sb) 子电池构成四结太阳能电池，实现电池电流匹配，且其 GaInNAs(Sb) 的晶格与 GaAs 匹配，从而提高多结太阳能电池的光电转换效率。
在目前的外延生长工艺中，高晶格质量的 GaInNAs(Sb) 材料需 MBE 方法生长获得。然而， MBE 外延生长方法要求高真空、低温生长，因此很多材料源并不适合采用 MBE （如硫、磷等），且其生长速度很慢。针对此问题，下面实施例提出了一种多结太阳能电池的外延生长系统，其在同一预处理室（ Load-lock ）中集成了 MOCVD 系统和 MBE 系统，之间通过真空通道连接，且在真空通道中配置了传送装置，用于在外延生长过程中，可将外延片在 MOCVD 系统和 MBE 系统之间传送。
下面公开的各实施例利用上述外延生长系统，制备高效的多结太阳能电池。
在一些实施例中，采用上述外延生长系统制备了四结太阳能电池，其具体步骤包括。
在 p 型 Ge 衬底上，在分子束外延（ MBE ）生长室中生长 n 型 GaAs 作为发射区， Ge 衬底作为基区，构成第一子电池，使其具有第一带隙（ 0.65~0.70 eV ）。
在第一子电池上方，利用 MBE 的方法外延生长 GaInNAs （ Sb ）第二子电池，使其具有大于第一带隙的第二带隙（ 0.95 ~1.05 eV ）并且与第一子电池晶格匹配。
将生长好的第一、二子电池，通过传送装置传送至金属有机化合物化学气相沉淀（ MOCVD ）系统的生长室，进行后续生长。
在第二子电池上方，利用 MOCVD 生长第三子电池，使其具有大于第二带隙的第三带隙（ 1. 35 ~1.45 eV ）并且与第一、二子电池晶格匹配。
在所述第三子电池上方，利用 MOCVD 方法生长第四子电池，使其具有大于第三带隙的第四带隙 1.86~1.95 eV ），其晶格常数与第一、二、三子电池匹配。
在所述第四子电池上方形成高掺杂盖帽层。
在一些实施例中，采用上述外延生长系统制备了五结太阳能电池，其具体步骤包括。
在 p 型 Ge 衬底上，在分子束外延（ MBE ）生长室中生长 n 型 GaAs 作为发射区， Ge 衬底作为基区，构成第一子电池，使其具有第一带隙（ 0.67~0.70 eV ）。
在第一子电池上方，利用 MBE 的方法外延生长 GaInNAs （ Sb ）第二子电池，使其具有大于第一带隙的第二带隙（ 0.95 ~1.05 eV ）并且与第一子电池晶格匹配。
将生长好的第一、二子电池，通过传送装置传送至金属有机化合物化学气相沉淀（ MOCVD ）系统的生长室，进行后续生长。
在第二子电池上方，利用 MOCVD 生长第三子电池，使其具有大于第二带隙的第三带隙（ 1.40 ~1.42 eV ）并且与第一、二子电池晶格匹配。
在所述第三子电池上方，利用 MOCVD 方法生长第四子电池，使其具有大于第三带隙的第四带隙（ 1.60~1.70 eV ），其晶格常数与第一、二、三子电池匹配。
在所述第四子电池上方，利用 MOCVD 方法生长 AlxGayIn1-x-yP 第五子电池，使其具有大于第四带隙的第五带隙 （ 1.90~2.10 eV ），其晶格常数与第一、二、三、四子电池匹配。
在所述第五子电池上方形成高掺杂盖帽层。
更具体地，在一些实施例中， GaInNAs （ Sb ）第二子电池可采用下面方式生长：采用 MOCVD 生长方法，在第一子电池上方形成背场层；采用 MBE 生长方法，在所述背场层形成 GaInNAs （ Sb ）基区和发射区；采用 MOCVD 生长方法，在所述发射区上方形成窗口层，构成第二子电池。
对于本发明的更多细节，可参考下面实施 1~ 实施 3 。
实施例 1
图 2 公开了一种多结太阳能电池的外延生长系统 800 。外延生长系统 800 设有 MOCVD 系统、 MBE 系统和预处理室 830 ，其中 MOCVD 反应腔 810 和 MBE 反应腔 820 共用预处理室 830 。真空通道 840 连接 MOCVD 反应腔 810 和 MBE 反应腔 820 ，其真空度维持在 1 × 10-6 Pa 以下。且在真空通道中配置了传送装置，用于在外延生长过程中，可将外延片在 MOCVD 系统和 MBE 系统之间传送。
在本外延生长系统中，将 MOCVD 反应腔 810 和 MBE 反应腔 820 设置在同一预处理室中，并设置了传送装置，使得在外延生长过程中只需通过程序控制即可实现在同一预处理室进行 MOCVD 生长和 MBE 生长之间转换。一方面实现了 MOCVD 和 MBE 两种晶体生长方法联合，在不同的生长室中原位生长所需的太阳能电池结构，防止了样品表面氧化和吸附性污染，保证了样品表面的洁净度。
实施例 2
图 4 公开了一种四结太阳能电池的制备方法的流程图。
步骤 S11 ：提供一 Ge 衬底。选用 p 型厚度为 140 微米的 Ge 衬底 101 ，其掺杂浓度为在 2 × 1017cm-3 -- 5 × 1017cm-3 。
步骤 S12 ：以 Ge 衬底为基区，形成第一子电池 100 。在 MOCVD 生长室中，在上述衬底 101 表面外延生长 n 型 GaAs ，掺杂浓度为 2 × 1018cm-3 ，厚度为 100 nm ，作为第一子电池发射区 102 ，在 n 型 GaAs 层 102 上外延生长厚度为 25 nm 、掺杂浓构在 1 × 1018cm-3 的 InGaP 材料层作为窗口层 102 ，以 p 型 Ge 衬底本身作为基区，构成第一子电池。
在 MOCVD 生长室中，在第一子电池上方生长重掺杂的 p++/n++-GaAs 隧穿结 601 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S13 ：在隧穿结 601 上方形成 GaInNAs （ Sb ）第二子电池 200 。请参看图 5 ，其包括步骤 S13a~S13e 五个步骤。 S13a ：在 MOCVD 生长室内 810 ，在隧穿结 601 上方生长 p 型 InGaP 作为背场层 201 ，其厚度为 50 nm ，掺杂浓度在 1 × 1018cm-3 左右。 S13b ：将生长完成的样品通过预处理室 830 和真空通道 840 ，轨道传送至 MBE 生长室 820 。 S13c: 在 MBE 生长室 820 内，在背场层 201 上方形成 Ga0.92In0.08N0.02As 0.97Sb0.01 第二子电池，基区 202 厚度优选值为 3000 nm ，掺杂浓度为在 5 × 1017cm-3 ；发射区 203 厚度为 200 nm ，掺杂浓度为在 2 × 1018cm-3 。 S13d ：将生长完成的样品通过预处理室 830 和真空通道 840 ，轨道传送回 MOCVD 生长室。 S13e ：在 MOCVD 生长室内，在发射区 203 上面生长 n 型 InGaP 窗口层 204 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第二子电池上方生长重掺杂的 p++/n++-GaAs 隧穿结 602 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S14 ：采用 MOCVD 在第二子电池上方形成第三子电池 300 。在 MOCVD 生长室内，在隧穿结 602 上方生长厚度为 50 nm 、掺杂浓度为 1~2 × 1018cm-3 的 p+-InGaP 材料层作为背场层 301 ；在背场层 301 上方生长厚度为 2 微米、掺杂浓度为 1~5 × 1017cm-3 的 n 型 GaAs 材料层作第二子电池基区 302 ；在基区 302 上生长厚度为 100 nm 、掺杂浓度大约 2 × 1018cm-3 的 n+-Ga(In)As 材料层作为发射区 303 ；在发射区 303 上面生长 n 型 InGaP 窗口层 304 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第三子电池上生长重掺杂的 p++/n++-InGaP 隧穿结 603 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S15 ：采用 MOCVD 在第三子电池上方形成第四子电池 400 。在 MOCVD 生长室内，在隧穿结 603 上方外延生长厚度为 100 nm 、掺杂浓度为 1~2 × 1018cm-3 的 p-AlGaInP 材料层作为背场层 401 ；在背场层 401 上生长厚度为 1000 nm 、掺杂浓度分别为 5 × 1017cm-3 的 p+-GaInP 材料层作为基区 402 ；在基区 402 上生长生长厚度为 100nm 、掺杂浓度分别为 2 × 1018cm-3 的 n+-GaInP 材料层作为发射区 403 ；在发射区 403 上面生长 n 型 AlGaInP 窗口层 504 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第四子电池的顶部生长重掺杂 n++-GaAs 材料层作为盖帽层 700 ，厚度为 500 nm ，掺杂浓度为 1 × 1019cm-3 。
最后，在样品表面进行减反膜蒸镀，金属电极的制备等后期工艺，完成所需要的太阳能电池，其结构剖面图如图 6 所示。
实施例 3
一种高效五结太阳能电池的制备方法，可以选择如下步骤获得：
步骤 S21 ：提供一 Ge 衬底。选用 p 型厚度为 140 微米的 Ge 衬底 111 ，其掺杂浓度为在 2 × 1017cm-3 -- 5 × 1017cm-3 。
步骤 S22 ：以 Ge 衬底为基区，形成第一子电池 110 。在 MOCVD 生长室中，在上述衬底 111 表面外延生长掺杂浓度为 2 × 1018cm-3 、厚度为 100 nm 的 n 型 GaAs 材料层作为第一子电池发射区 112 ，在 n 型 GaAs 层 112 上外延生长厚度为 25 nm 、掺杂浓构在 1 × 1018cm-3 的 InGaP 材料层作为窗口层 113 ，以 p 型 Ge 衬底本身作为基区，构成第一子电池。
MOCVD 生长室中，在第一子电池上方生长重掺杂的 p++/n++-GaAs 隧穿结 611 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S23 ：在隧穿结 611 上方形成 GaInNAs （ Sb ）第二子电池 210 。在 MOCVD 生长室内 810 ，在隧穿结 611 上方生长 p 型 InGaP 作为背场层 211 ，其厚度为 50 nm ，掺杂浓度在 1 × 1018cm-3 左右。将生长完成的样品通过预处理室 830 和真空通道 840 ，轨道传送至 MBE 生长室 820 。在 MBE 生长室 820 内，在背场层 211 上方形成 Ga0.92In0.08N0.02As 0.97Sb0.01 第二子电池，基区 212 厚度优选值为 3000 nm ，掺杂浓度为在 5 × 1017cm-3 ；发射区 213 厚度为 200 nm ，掺杂浓度为在 2 × 1018cm-3 。将生长完成的样品通过过预处理室 830 和真空通道 840 ，轨道传送回 MOCVD 生长室。在 MOCVD 生长室内，在发射区 213 上面生长 n 型 InGaP 窗口层 214 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第二子电池上方生长重掺杂的 p++/n++-GaAs 隧穿结 612 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S24 ：采用 MOCVD 在第二子电池上方形成第三子电池 310 。在 MOCVD 生长室内，在隧穿结 612 上方生长厚度为 50 nm 、掺杂浓度为 1~2 × 1018cm-3 的 p+-InGaP 材料层作为背场层 311 ；在背场层 301 上方生长厚度为 2 微米、掺杂浓度为 1~5 × 1017cm-3 的 n 型 Ga （ In ） As 材料层作基区 312 ；在基区 312 上生长厚度为 100 nm 、掺杂浓度大约 2 × 1018cm-3 的 n+-Ga （ In ） As 材料层作为发射区 313 ；在发射区 313 上面生长 n 型 InGaP 窗口层 314 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第三子电池上生长重掺杂的 p++/n++-InGaP 隧穿结 613 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S25 ：采用 MOCVD 在第三子电池上方形成第四子电池 400 。在 MOCVD 生长室内，在隧穿结 613 上方外延生长厚度为 100 nm 、掺杂浓度为 1~2 × 1018cm-3 的 p-AlGaInP 材料层作为背场层 411 ；在背场层 411 上生长厚度为 1000 nm 、掺杂浓度分别为 5 × 1017cm-3 的 p+-AlxGa1-xAs 材料层作为基区 402 ；在基区 402 上生长生长厚度为 100nm 、掺杂浓度分别为 2 × 1018cm-3 的 n+-AlxGa1-xAs 材料层作为发射区 413 ；在发射区 413 上面生长 n 型 AlGaInP 窗口层 414 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第四子电池和第五子电池中间生长重掺杂的 p++/n++-AlGaAs 隧穿结 614 ，其厚度是 50 nm ，掺杂浓度高达 2 × 1019cm-3 。
步骤 S26 ：采用 MOCVD 在第四子电池上方形成第五子电池 500 。在 MOCVD 生长室内，在隧穿结 614 上方外延生长厚度为 100 nm 、掺杂浓度为 1~2 × 1018cm-3 的 p-AlGaAs 材料层作为背场层 511 ；在背场层 511 上外延生长厚度为 500nm 、掺杂浓度为 1~5 × 1017cm-3 的 p+-AlxGayIn1-x-yP 材料层作基区 512 ；在基区 512 上生长厚度为 50 nm 、掺杂浓度大约 2 × 1018cm-3 的 n+-AlxGayIn1-x-yP 材料层作为发射区 513 ；在发射区 513 上面生长 n 型 AlGaAs 窗口层 903 ，其厚度为 25 nm ，掺杂浓度在 1 × 1018cm-3 左右。
在 MOCVD 生长室内，在第四子电池的顶部生长重掺杂 n++-GaAs 材料层作为盖帽层 710 ，厚度为 500 nm ，掺杂浓度为 1 × 1019cm-3 。
最后，在样品表面进行减反膜蒸镀，金属电极的制备等后期工艺，完成所需要的太阳能电池，其结构剖面图如图 7 所示。
在本实施例中，形成了 Ge/ GaInNAs （ Sb ） /InGaAs/AlGaAs/AlGaInP 五结太阳能电池，其带隙分布如图 3 所示。对于四结太阳能电池，此五结太阳能电池细化了吸收光谱，电流匹配更容易实现，光谱吸收范围更广且效率更高。

Claims (11)

  1. 一种高效多结太阳能电池的制备方法，其具体步骤包括：
    （ 1 ）提供一 Ge 衬底，用于半导体外延生长；
    （ 2 ）以 Ge 衬底为基区，在所述 Ge 衬底上生长发射区，构成第一子电池，其具有一第一带隙；
    （ 3 ）采用 MBE 生长方法，在所述第一子电池上方形成第二子电池，使其具有大于第一带隙的一第二带隙，且晶格与第一子电池晶格匹配；
    （ 4 ）采用 MOCVD 生长方法，在所述第二子电池上方形成第三子电池，使其具有大于第二带隙的第三带隙，并且与第一、二子电池晶格匹配；
    （ 5 ）采用 MOCVD 生长方法，在所述第三子电池上方形成第四子电池，使其具有大于第三带隙的第四带隙，其晶格常数与第一、二、三子电池匹配。
  2. 根据权利要求 1 所述的太阳能电池的制备方法，其特征在于：所述第二子电池为 GaInNAs （ Sb ）电池。
  3. 根据权利要求 2 所述的太阳能电池的制备方法，其特征在于：所述第二子电池的制备步骤包括：
    采用 MOCVD 生长方法，在第一子电池上方形成背场层；
    采用 MBE 生长方法，在所述背场层形成 GaInNAs （ Sb ）基区和发射区；
    采用 MOCVD 生长方法，在所述发射区上方形成窗口层，构成第二子电池。
  4. 根据权利要求 2 所述的太阳能电池的制备方法，其特征在于：所述形成的太阳能电池包括四结子电池，其中第一子电池的带隙为 0.65~0.70 eV ，第二子电池的带隙为 0.95~1.05 eV ，第三子电池的带隙为 1.35~1.45 eV ，第四子电池的带隙为 1.86~1.95 eV 。
  5. 根据权利要求 4 所述的太阳能电池的制备方法，其特征在于：所述第三子电池为 Ga(In)As 电池，第四子电池为 GaInP 电池。
  6. 根据权利要求 2 所述的太阳能电池的制备方法，其还包括步骤（ 6 ）：采用 MOCVD 生长方法，在所述第四子电池上方形成第五子电池，使其具有大于第四带隙的第五带隙，其晶格常数与第一、二、三、四子电池匹配，构成五结太阳能电池。
  7. 根据权利要求 6 所述的太阳能电池的制备方法，其特征在于：所述第一子电池的带隙为 0.67~0.70 eV ， 第二子电池的带隙为 0.95~1.05 eV ，第三子电池的带隙为 1.40 ~1.42 eV ，第四子电池的带隙为 1.60~1.70 eV ，第五子电池的带隙为 1.90~2.10 eV 。
  8. 根据权利要求 7 所述的太阳能电池的制备方法，其特征在于：所述第三子电池为 Ga(In)As 电池；所述第四子电池为 AlGaAs 电池；所述第五子电池为 AlGaInP 电池。
  9. 根据权利要求 8 所述的太阳能电池的制备方法，其特征在于：所述第五子电池的材料为四元化合物 AlxGayIn1-x-yP ，通过组分 x ， y 的调节，在带隙满足的条件下，实现与其它所有子电池晶格匹。
  10. 一种用于前述任意一项权利要求所述制备方法的太阳能电池外延生长系统，包括： MOCVD 反应腔、 MBE 反应腔和预处理室，其中 MOCVDE 反应腔和 MBE 反应腔共用所述预处理室并通过一通道连接，一传送装置位于所述通道内。
  11. 根据权利要求 10 所述的太阳能电池外延生长系统，其特征在于：所述通道为真空通道，其真空度维持在 1 × 10-6 Pa 以下。
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