GB2117174A - Multilayer photovoltaic solar cell - Google Patents
Multilayer photovoltaic solar cell Download PDFInfo
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- GB2117174A GB2117174A GB8205618A GB8205618A GB2117174A GB 2117174 A GB2117174 A GB 2117174A GB 8205618 A GB8205618 A GB 8205618A GB 8205618 A GB8205618 A GB 8205618A GB 2117174 A GB2117174 A GB 2117174A
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- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 29
- 230000003595 spectral effect Effects 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 130
- 239000004065 semiconductor Substances 0.000 claims description 51
- 239000013078 crystal Substances 0.000 claims description 21
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052732 germanium Inorganic materials 0.000 claims description 16
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000005641 tunneling Effects 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000003667 anti-reflective effect Effects 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000151 deposition Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000002800 charge carrier Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910005540 GaP Inorganic materials 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910000756 V alloy Inorganic materials 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXNLCSXBJCPWGL-UHFFFAOYSA-N [Ga].[As].[In] Chemical compound [Ga].[As].[In] KXNLCSXBJCPWGL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- GUSAMWMYRQHFMI-UHFFFAOYSA-N dioxoantimony Chemical compound O=[Sb]=O GUSAMWMYRQHFMI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000003094 perturbing effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- H01L31/04—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
-
- 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
- H01L31/04—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
- H01L31/072—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 heterojunction type
- H01L31/0735—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 heterojunction type comprising only AIIIBV compound semiconductors, e.g. GaAs/AlGaAs or InP/GaInAs solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/544—Solar cells from Group III-V materials
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- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Sustainable Energy (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Development (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Photovoltaic Devices (AREA)
Abstract
A multilayer multijunction photovoltaic solar cell for use with a light concentrating lens 21 comprises a plurality of successive homogeneous layers 31, 32, 33, of mutually different composition on a substrate 11, there being solar energy sensitive pn homojunctions within each layer, and tunnelling shorting heterojunctions between adjacent layers. The layers are lattice matched, and each has the same lattice constant as the substrate to within +/-1%. Each layer absorbs solar spectral energy at a different wavelength. The substrate has no internal solar energy sensitive junction. Preferred materials are Ga0 &cirf& 35 In0.12. As for the substrate and the first layer 31, Ga0.69 In0.31 As0 &cirf& 5 P0.5 for the second layer 32 and In0.5 Ga0.5 P for the third layer 33. Other suitable materials are listed and transparent antireflective surface coating 20 is provided. <IMAGE>
Description
SPECIFICATION
Multilayer photovoltaic solar cell
This invention relates to a multilayer
photovoltaic solar cell for the conversion of solar
energy to electrical energy and particularly to a
multilayer photovoltaic cell of high efficiency for
such conversion.
Several forms of photovoltaic cells have been
developed for converting solar energy to electrical
energy; however, the efficiency of known systems
is low and, when efficiencies are improved through the use of more efficient converters, the
cost of the converters is high. It has been
proposed to increase the conversion efficiency by
concentrating the solar energy, through the use of
optical systems, onto the converters. With such
systems the effiency of conversion can be further
increased. Cost consideration on each of the
several components of a conversion system
indicates that, with light concentrators, more
expensive photovoltaic converters may be
employed, however, there are economic cost
limits on the concentrator system.Further, as the
concentration of light onto the converter becomes
more intense, there is a need for dissipating the
heat derived from the concentrated light because
the efficiency of some converters drops as the
heat of the converter increases.
From a study of the above recited considerations, it can be shown that, with the use of concentrator systems that can decrease the cost of energy conversion by increasing conversion efficiency, the emphasis can shift from converter cell cost to cell efficiency. Thus, if the cell efficiency can be made great enough, a concentrator system can produce electricity more cheaply than the same area of a lower cost array.
These observations lead to the consideration of high efficiency stacked multijunction solar cells with each cell responsive to a different energy band of solar energy and with a concentrator for concentrating the energy and tracking the cell toward the source of energy.
Multilayer photovoltaic cells have been suggested as a means for converting solar energy to electrical energy. One form for such a cell is described in U.S. Patent No. 4,017,332 to L. W.
James issued April 12, 1977. This patent suggests a multilayer cell composed of stacks of heterojunction cells. As distinguished from the
James disclosure, the present invention is directed to a multilayer photovoltaic cell composed of stacks of homojunction cells.
The prior art multilayer photovoltaic cells have also suggested producing the successive layers of semiconductor materials responsive to different energy bandgaps (see the above-mentioned U.S.
patent). In the cell disclosed herein the several layers are selected to be responsive to different bandgaps all at substantially the same current level with a specific avoidance of the bandgap for light energy effected by fluctuations in humidity and air mass.
Prior art multilayer photovoltaic cells have been constructed on substrate materials that have been lattice matched to the semiconductor layers of the cell and such substrates have been developed with separate junctions for contributing to the conversion of the overall cell (again see U.S. Patent 4,017,332). In the cell disclosed in the present application a relatively inexpensive substrate material is proposed that is specifically lattice matched with the semicoriductor layers and specifically designed without an internal junction so as to avoid sensitivity for the cell to the fluctuation in the infrared absorption in the solar spectrum caused by OH vibration bands associated with water vapor. The solar cell proposed herein will g therefore be less sensitive to fluctuations in humidity and air mass.
In a prior art publication by the present inventor and R. C. Knechtli at the Thirteenth IEEE
Photovoltaic Specialists Conference~1978, June 5-8, 1978, Washington, D.C. a multilayer photovoltaic cell was described having efficiencies of the desired order. The photovoltaic cell disclosed in the present application is distinguished from the prior art disclosure by the specific absence of a junction in the substrate and by the further production of layers lattice matched to the substrate and containing homojunctions to produce the desired electrical conversion with the desired efficiency.
The idea of obtaining very high energy conversion efficiencies by optically stacking solar cells with different bandgaps is known. There is, however, increasing motivation to consider fabricating such a stack of solar cells monolithically on a single wafer. This follows for space applications because a single wafer is lighter than a multiple wafer stack, and for terrestrial applications using concentrator systems, because a single wafer is likely to be cheaper, simpler, and more easily cooled than is a multiple wafer stack. There are, however, major constraints on the design and fabrication of such a high efficiency monolithic stacked multijunction solar cell.Two design constraints are, first, that the different semiconductor materials making up the stack be nearly lattice matched so that crystal integrity can be maintained, and second, if the light sensitive junctions are to be series connected, that the material bandgaps be such that the light generated current be distributed approximately equally between the multiple junctions. A corrolary problem is that of providing the desired series connection of the active junctions without suffering unacceptable voltage losses at inactive junctions, in the stacked structures to be considered.
In accordance with the foregoing, we propose a multijunction photovoltaic cell comprising layers of indium gallium phosphide and indium gallium arsenide on a germanium substrate. The successive layers include junctions in different adsorption bands while the substrate and successive layers are lattice matched to less than + 1% variation. With a concentrator, contacts the
cell provides an efficient means for converting solar energy to electrical energy.
Thus in accordance with the present invention there is provided a high efficiency, multijunction
photovoltaic solar cell for use with a light
concentrating element, said cell comprising
(a) a single crystal, single element substrate
without an internal solar energy sensitive
junction, said substrate capable of lattice
matching to within +1% to a Ga68In12As semiconductor material responsive in the solar
spectral range,
(b) a first homogeneous layer of semiconductor
material deposited on said substrate, lattice
matched thereto and having about Ga.88ln.12As composition with a semiconductor bandgap of
1.25 ev., and absorbing solar spectral energy at a
first wavelength,
(c) a second homogeneous layer of
semiconductor material deposited on said first
layer lattice matched to said first homogeneous
layer and having about Ga.6#ln.31As.5P.5 composition with a semiconductor bandgap of
1.5 ev., and absorbing solar spectral energy at a
second wavelength,
(d) a third homogeneous layer of
semiconductor material deposited on said second
layer lattice matched to said second
homogeneous layer and having about In.5Ga.5P
composition with a semiconductor bandgap of
1.85 ev., and absorbing solar spectral energy at a third wavelength,
(e) said first, second and third layer each having essentially the same lattice constant as said single crystal substrate to within +1%,
(f) said first, second and third layer each containing a solar energy sensitive p/n homojunction and each layer having a tunneling, shorting heterojunction with the layer immediately above and below it, and
(g) said first, second and third layers each developing essentially the same zero voltage solar energy generated current as the other layers.
For a better understanding of the invention and to show how the same may be carried into effect, reference will now be made, by way of example, to the accompanying drawings in which:~
Figure 1 is a two-junction cell not in accordance with the present invention and included herein by way of comparison;
Figure 2 is a threejunction cell in accordance with the present invention;
Figure 3 is a plot of current vs. voltage for several photovoltaic cells;
Figure 4 is a plot of solar cell efficiency vs. the number of stacked cells;
Figure 5 is a plot of the sun's spectral irradiance vs. wavelength and photon energy; and
Fig. 6 is a schematic diagram of a growth chamber of fabrication of the photovoltaic cells of the present invention.
Definitions
Dopant:
A semiconductor can carry current by means of either positively charged or negatively charged carriers. Such carriers are added to the semiconductor via trace chemical impurities called dopants. If the dopants add negative charge carriers to the semiconductor, they are said to dope the semiconductor n-type. If the dopants add positive charge carriers, they are said to dope the semiconductor p-type. When the semiconductor is doped strongly with high concentrations of negative charge such that the semiconductor becomes semimetallic, it is doped n+.
Similarly, high densities of positive charged carriers dope a semiconductor p+. A dopant is distinct from a major chemical component forming the semiconductor in that it is present at < 1% in atomic composition and in that it adds charge carriers to the semiconductor.
Junction:
A junction in a semiconductor device is a planar region on one side of which the carriers are positively charged and on the other side of which the carriers are negatively charged.
Homojunction:
A homojunction is a junction for which the semiconductor material on either side of a junction is the same or homogeneous. In other words, the only chemical difference on either side of the junction is the choice of dopants which are present in trace amounts. The major chemical components forming the semiconductor on either side of the junction are identical.
Heterojunction:
A heterojunction is a junction for which the semiconductor materials on either side of the junction not only differ in carrier type but also in major component compositions. The chemical composition on either side of the junction is heterogeneous. In other words, the semiconductor with positively charged carriers is substantially different chemically from the semiconductor with negatively charged carriers. On occasion, substantial alloying can occur when forming a heterojunction such that the change in carrier type does not occur exactly at the heterogeneous interface. However, herein such a junction is still referred to as a heterojunction.
Bandgap energy:
A semiconductor absorbs light with photon energies above a certain energy and it transmits light with photon energies less than that energy.
The energy for onset of absorption is called the semiconductor bandgap energy. Changes in semiconductor chemical composition lead to changes in this bandgap energy.
Lattice match:
The atoms in a crystal are separated by certain spacings and relative angles. The sites on which atoms are found form a crystal lattice. It is
possible in some cases to change the atoms in going from one material to another without changing the crystal lattice appreciably. For example, an AlAs crystal has the same crystal lattice as a GaAs crystal. One simply replaces an
Al atom with a Ga atom. When two crystals have the same lattice and when the atomic spacings are the same, there is a good lattice match and one crystal can be grown as an extension of the other.
Fig. 1 is a schematic cross-sectional representation of a multilayer photovoltaic solar cell.
The layers of the cell are not to scale either vertically or horizontally except that, in the vertical dimension, the layers are shown in somewhat relative thicknesses. As illustrated, a germanium substrate 11 is provided with a contact surface
12 at one side and is joined to a first semiconductor cell 13 at the other side. The germanium substrate is preferably a single crystal, a single element substrate with a crystalline structure that is capable of being lattice matched to a Ga.881n,,2As semiconductor material responsive in the visible, or near visible, light range.The substrate does not contain a light responsive junction but it is intentionally grown as a germanium crystal because of the lattice structure that permits the match to the first layer of a multilayer cell that is capable of producing light generated current in a range that can be desirably distributed among other layers of a multilayer cell.
The cell 13 is preferably constructed of gallium, indium, and arsenic, having the composition of Ga.8#ln.12As and an energy bandgap of 1.25 ev. A junction 14 is illustrated in the first layer 13. The first cell 13 is lattice matched to the substrate and is capable of absorbing visible, or near visible, light with photon energies above the preferred 1.225 ev. and capable of generating a current compatible with the desired distribution within the multilayer cell.
A second cell 15 is shown in contact with the first cell 13. The cell 15 is preferably constructed of gallium, indium, and phosphorous, having the composition of Ga.43ln.57P and an energy bandgap of 1.75 ev. The second cell 15 is lattice matched to the first cell and is capable of absorbing visible, or near visible, light with photon energies above the preferred 1.75 ev. and is also capable of generating a current compatible with the desired distribution within the multilayer cell.
Deposited on the other surface of the second cell 15 is a conductive and transparent layer 16 of indium tin oxide or antimony tin oxide. The composition of indium tin oxide and antimony tin oxide are mixtures of two oxides; indium oxide (In203) and tin oxide (SnO2) in the first composition and antimony oxide (SbO2) and tin oxide in the second. These mixtures may be in any
ratio of the two oxides, but in general there is from 80 to 90 mole percent indium oxide in the first composition and from 10 to 30 mole percent
antimony oxide in the second composition. These
compositions are conventionally indicated by the
chemical formulae In203/SnO2 or SnO/SbO2.
- One or more contacts 17 is attached to the
outer surface of layer 16. Electrically conductive
wires 18 and 19 are attached to the contacts 12
and 1 7, respectively. A transparent antireflective
outer surface coating 20 is applied over the
surface layer 16 and contacts 17.
As illustrated in Fig. 1, a concentrator 21, here
shown as a concentrating lens, is positioned
above the cell in a position to concentrate light from a source 22, here illustrated as the sun.
Fig. 2 illustrates a multilayer cell wherein three
layers 31, 32 and 33 are assembled between the
substrate 1 1 and the conductive layer 16. The
composition of these three layers in the preferred form are:
layer 31, Ga.88ín.,2As with bandgap 1.25 ev.
layer 32, Ga.69ln.3lAs.sp.s with bandgap 1.50
ev.
layer 33, In5Ga.5P with bandgap 1.85 ev.
In the multilayer cell of Fig. 2, the substrate is
preferably single crystal, single element
germanium with a lattice structure capable of
being lattice matched to Ga,881n.,2As but does not
contain a junction and therefore is not responsive
to photons passing to or through it. The lattice
structure of the germanium substrate makes it
particularly suited to the construction of the
three-layer cell of the above composition in that
both the desired crystal lattice match may be
accomplished throughout the three-layer cell and the desired light generated current will be distributed substantially equally between the
multiple junctions permitting series connection of the junctions.
The layers are preferably deposited on the substrate 11 by metal organic chemical vapor deposition processes in a manner to establish a layer of the desired thickness and composition.
The three-junction cell of Fig. 2 has a higher solar energy conversion efficiency that the two-junction cell of Fig. 1 (refer to Fig. 4). A three-layer cell has a theoretical conversion efficiency of 50% at
1000 suns concentration, whereas the two-layer cell has a theoretical efficiency of 44% at 1000 suns.
Although the three-junction cell resembles the cell of Fig. 1, it differs in that the second junction
layer 32 and the third junction layer 33 compositions are unobvious. These layers are chosen to contain In, Ga, As and P so that the same metal organic chemical vapor deposition system can be used in a single process sequence to prepare either the device of Fig. 1 or the device of Fig. 2. The compositions are specifically chosen so that lattice matching within 1% is observed for all three layers. Furthermore, the bandgap positions determined by the compositions allow equal currents to be generated in all three layers.
This equal current requirement produces the apparently small but very significant compositions shift from In.57Ga.43P in layer 1 5 (Fig.1) to ln.6Ga.5P in layer 33 (Fig. 2). A failure to observe this shift would drop the three-layer cell efficiency by approximately 10 percentage points.
The composition of the second layer 32 of Fig.
2, i.e., Ga ##In.31As.6 P.5, does not follow by perturbing either layer of Fig. 1 and is therefore unobvious from the cell of Fig. 1. This composition follows from a consideration of bandgap and crystal lattice spacing data for the
InGaAsP quarternary metallurgical system as well as a consideration of solar cell current requirements as explained above.
A preferred method for constructing the threelayer cell of the invention is to start with a single crystal substrate, for example, a germanium wafer. The germanium wafer substrate does not include a light sensitive junction by preference; firstly, because a substrate with a junction becomes more costly to construct because the purity of the germanium wafer with a functional light sensitive junction is of the order of < 1 ppm whereas the wafer without a junction requires purity control of only < 1000 ppm; and secondly, because to junction in the germanium wafer would be responsive to the light bandgap which is most severely effected by fluctuations in humidity and air mass. A further advantage of the germanium substrate is that it is an elemental semiconductor like silicon and it can be grown as a ribbon, thus contributing to its lower cost.
Further, germanium is lattice matched to layers 13 and 15 or 31,32 and 33 listed above to < 1% and should therefore permit the efficiency of the cell, proposed herein, to more nearly approach the theoretical limit.
In the preferred form of the cell described herein, the substrate germanium layer is between 200 and 300 micrometers thick and preferably 250 micrometers. The power limit on thickness is determined both by operating conditions which establish the conduction characteristics of the substrate and the physical strength of the substrate in its function as the base of the multilayer cell. The upper limit for the dimension of the substrate is mainly economic in that thicker substrates are more costly to make and include more volume of an expensive material.
We propose a growth method which will allow in sequence Ill-V alloy layer depositions over large substrate areas. This type of deposition is known having been described in U.S. Patent No.
4,128,733, issued December 5, 1978 to L. M.
Fraas et al. Fig. 6 shows a growth chamber for such a method, called low pressure metal organic chemical vapor deposition (MO-CVD). In this method, one introduces trialkyl gallium or trialkyl indium, or a mixture thereof and phosphine or arsine, or a mixture thereof into a pyrolysis chamber. These compounds react on the germanium substrate to form the required ínGaAs or InGaP alloys. One example of the reaction is:
(1 -x)Ga(C2H5)3+xln(C2H5)3+AsH3 6000C #Ga (1-x) ln#As +By-products wherein x has a value in the range of > 0 to < 1.
The product is a semiconductor film deposited on the germanium substrate.
The semiconductor is doped p-type by adding
dialkyl zinc, dialkyl cadmium, or dialkylberylium trimethylamine vapors and n-type by adding hydrogen sulfide, tetralkyl tin or dialkyl telluride vapors. All Ill-V alloy layers with the prescribed composition are grown in sequence by using a programmable gas flow controller.
In fabricating the comparison cell of Fig. 1,
lattice matched homojunction cells are stacked together by placing shorting tunnel junctions at the heterofaces. Starting with a germanium substrate with a dopant type p+, the next layer of the cell is formed by the epitaxial deposition of a p+ type layer of gallium indium arsenide preferably with an alloy composition Ga.88ín.,2As.
During the course of the deposition of this semiconductor layer, the concentration of the dopant is reduced to produce a p-type layer and eventually the dopant is changed to produce a p/n junction and transition to n-type layer. Continued deposition increases the thickness of the first layer and a finishing portion is deposited with a dopant concentration such as to produce an n+ layer at the boundary of the first layer.
A second semiconductor layer is then
epitaxially deposited on the outside surface of the first layer initially with a dopant material and concentration to produce a p+ layer at the interface. The second semiconductor layer is an indium gallium phosphide material with a
preferred alloy composition of ln.51Ga.43P. During the course of the deposition of this semiconductor layer, the concentration of the dopant is reduced to produce a p-type layer and eventually the depant is changed to produce a p/n junction and transition to n-type layer. Continued deposition increases the thickness of the second layer with a transition of dopant composition such as to produce an n+ layer at the boundary of the second layer.
An outer conductive layer is then deposited on the outer surface of the second layer to complete the two-layer photovoltaic cell. The conductive layer may also be an anti-reflective coating.
Preferably, the conductive layer has an alloy composition of indium tin oxide (In203/SnO2) conventionally abbreviated as ITO.
To complete the photovoltaic cell, a pair of conductors are attached one to each outer surface of the substrate and ITO layers.
In fabricating the cell of Fig. 2, the substrate is produced as described with respect to Fig. 1 cell, then the first layer of lattice matched composition Ga.881n.,2As is epitaxially deposited, then the second layer of Ga.691n.31As.5 P.5, then the third layer of In# Ga In.5Ga.5P, and then the outer conductive layer with non-reflective coating. In this three-layer cell, the individual layers are controlled in composition to accomplish the desired lattice match while developing essentially the same zero voltage light generated current to produce a high efficiency, multijunction
photovoltaic solar cell. Each layer contains a light sensitive p/n homojunction and each has a tunneling, shorting heterojunction with the layer immediately above and below it.
It should be noted that the junctions within the
photovoltaic cell are homojunctions and that the
stacked layers are lattice matched. Further, there
are tunnel junctions at the heterofaces between the cells. With this method of construction, more effective tunnel junctions are provided. Since the magnitude of the tunneling currents through a barrier depends on the barrier height as well as the barrier width, placing a tunnel junction at a
heteroface provides a barrier height equal to that of the lower bandgap material comprising the heteroface.
In the multilayer photovoltaic cell just
described, the first layer has a bandgap of 1.25
ev. and the second layer has a bandgap of 1.75
ev. With the homojunction construction here
described, the tunneling barrier height will be
1.25 ev.
In the preferred embodiment here described,
the thickness of each deposited semiconductor
layer is between 2 and 6 micrometers thick and
preferably about 4 micrometers thick. The highly
doped tunnel junction layer on the low bandgap
side for the homojunction cell must be thin
enough not to absorb an appreciable amount of light, i.e., < 1000 . This criterion is not difficult to meet, since the absorption length is longer just
above but near the bandgap of a semiconductor,
i.e., the region of interest for a multijunction cell.
This layer must also be thick enough not to be
completely depleted, i.e., > 100A.
A form of apparatus for depositing the layers of the photovoltaic cell of the present invention is shown in Fig. 6. The apparatus is shown in schematic diagram form of a pyrolytic chemical vapor deposition system. The system includes a chamber 61 generally enclosed within the dotted lines 60. The chamber is evacuated by pump 62 to provide a vacuum within the chamber. A substrate support plate 63 is mounted within the chamber in proximity to a heater element 64.
Power is supplied to the heater element 64 from source 65 through controller 66. A thermocouple 67 senses the temperature within the chamber 61.
Metal organic materials in gaseous form are supplied through inlet line 68 to the chamber 61.
A second inlet line 69 supplies hydride materials in gaseous form to the chamber 61. The various gases react at the temperature and pressure within the chamber to deposit the desired semiconductor alloy composition with the desired type of dopant to produce the epitaxial growth of a lattice matched photovoltaic cell. A chemical vapor deposition process is described in U.S.
Patent No. 4,128,733 and in Journal of Vacuum
Science Technology, Vol. 15, No. 1, Jan./Feb., 1978, pages 119~122.
After the successive layers of the multilayer photovoltaic cell have been deposited, a transparent layer of conductive material is deposited. A preferred form for the transparent conductive layer is indium tin oxide, while other combination materials, such as antimony tin oxide may be deposited with the satisfaction of conditions that the layer be both conductive and transparent to the light energy passing to the active layers of the cell.
The transparent conductive layer of the multilayer cell is preferably between 0.2 and 2.0 micrometers thick with about 1 micrometer thickness being most desirable. The lower limit for the outer conductive layer thickness is determined by its operating characteristics while the upper limit is based on economics of the material and deposition costs.
In a preferred form, a transparent, antireflective outer surface coating 20 is applied over the conductive layer. This antireflective layer reduces the losses due to reflection of the light energy and thus increases the efficiency of the cell. The material for this coating is chosen from compounds such as silicon monoxide, tantalum oxide or titanium oxide.
Each layer of the multilayer cell is lattice matched to its neighor layer with a maximum lattice constant variation of +1.0%. This matching being important because with poor lattice matching or nonmatching, crystallinity of the cell system degrades and forms a structure having a high density of crystal dislocations, and in the worse cases, even forms grain boundaries. Such dislocations then become sites for recombination of the light generated charge carriers, thus reducing the amount of current produced. These dislocations also provide shunting current paths which further reduce open circuit voltages.
Lattice matching is accomplished by the proper choice of the composition and relative amounts of the materials in the different layers. The method of growth, with special control of the temperature is also important to the formation of high-quality, single crystal layers.
The layers of the preferred multilayer cell deposited on the germanium substrate are all lattice matched to the germanium lattice constant of 5.66A to within +1.0%.
In the Fig. 3 plot of current vs. voltages, the performance of several different photovoltaic cells is illustrated. The curves illustrate at one end the maximum voltage generated at substantially zero current and at the other end the maximum current at substantially zero voltage or "shortcircuit" condition. The preferred operation of a single cell, as cell A, is the maximum power point or the place along the performance curve where the current line 41 and the voltage line 42 are at a maximum as at point 43. In the multilayer cell herein described, the series interconnection requires that the current generated by each separate layer be substantially equal. It follows from this constraint that the optimum design of a multijunction cell with a maximum efficiency will require the cells in the stack to generate substantially the same short circuit currents. Fig.
3 illustrates this point by illustrating performance curves for cells A, B and C.
In accordance with the foregoing, a multilayer cell involving a cell having the performance curve
A and a cell having the performance curve B would be operating in a series additive sense at a current level where the two curves intersect at 44. In the same respect, cells with performance curves B and C would be most efficient at the current level where the curves have the same current as at point 45. In this figure, the multijunction cell composed of cells B and C substantially outperforms a cell composed of cells
A and B. [Reference: SolarEnergy, Vol. 22, pp.
383 (1979)1.
Fig. 4 represents the limits of increasing the number of cells of a multilayer cell in an effort to increase the efficiency. In "Thirteenth IEEE
Photovoltaic Specialists Conference~1978," page 868 ff, A. Bennett and L. L. Olsen, a calculation method is described indicating a maximum efficiency.for 100 suns of about 60% with 6 active junctions in the multilayer cell.
With the multilayer cell constructed in accordance with the present invention it is predicted that a multilayer structure incorporating two junctions, one at 1.8 ev. in InGaP and one at 1.2 ev. in GalnAs, will have a theoretical efficiency of about 40% and, because the Ge,
GalnAs and InGaP layers are lattice matched to < 1%, the practical efficiency can be expected to approach the theoretical limit.
Fig. 5 is a plot of spectral irradiance of the sun vs. wavelength and photon energy, illustrating the solar spectral range including wavelengths from the visible range to the infrared range. In the photovoltaic cell of the present invention, it is preferred to operate the indivudal cells in the wavelengths where the maximum energy is available from the sunlight spectrum. The sun's spectrum of wavelengths ranges from about 0.3 to about 2.5 micrometers with a maximum at about 0.45 micrometers. The photon number energy of sun light ranges from 4.0 to 0.65 ev., with a maximum energy at 2.5 ev. The plot of Fig.
5 is for air mass of 1 representing spectral irradiance with the sun directly overhead.
The elements employed in the various layers of
Figure 2 are all found in Columns IIIA and VA of the Periodic Table and are preferred for use according to the invention. However, other semiconductive materials can be used. For example, compounds formed of elements in
Columns IIB and VIA such as CdS and CdTe could be used; also IB-IIIA-VIA compounds such as
CulnS or variations thereof where, i.e., Se is substituted for S or Ga for In; also IIB-IVA-VA compounds such as ZnSnP. Also, other IIIA-VA compounds can be used in lieu of the mostpreferred IIIA-VA compounds previously discussed.
Claims (11)
1. A high efficiency, multijunction photovoltaic solar cell for use with a light concentrating element, said cell comprising:
(a) a single crystal, single element substrate without an internal solar energy sensitive junction, said substrate capable of lattice matching to within +1 % to a Ga.881n.12As semiconductor material responsive in the solar spectral range,
(b) a first homogeneous layer of semiconductor material deposited on said substrate, lattice matched thereto and having about Ga.88In.12As composition with a semiconductor bandgap of 1.25 ev., and absorbing solar spectral energy at a first wavelength,
(c) a second homogeneous layer of semiconductor material deposited on said first layer lattice matched to said first homogeneous layer and having about Ga.691n.3,As.5P.5 composition with a semiconductor bandgap of 1.5 ev., and absorbing solar spectral energy at a second wavelength,
(d) a third homogeneous layer of semiconductor material deposited on said second layer lattice matched to said second homogeneous layer and having about In.5 Ga .5 P composition with a semiconductor bandgap of 1.85 ev., and absorbing solar spectral energy at a third wavelength,
(e) said first, second and third layer each having essentially the same lattice constant at said single crystal substrate to within + 1 %, (f) said first, second and third layer each containing a solar energy sensitive p/n homojunction and each layer having a tunneling, shorting heterojunction with the layer
immediately above and below it, and
(g) said first, second and third layers each developing essentially the same zero voltage solar
energy generated current as the other layers.
2. A photovoltaic solar cell as claimed in Claim
1, wherein said substrate layer is germanium.
3. A photovoltaic solar cell as claimed in Claim
1 1 or 2, with the addition of an outer surface layer of indium tin oxide deposited on the last
deposited semiconductor layer.
4. A photovoltaic solar cell as claimed in Claim
3, wherein said outer surface layer is between 0.2
and 2.0 micrometers thick.
5. A photovoltaic solar cell as claimed in Claim
4, wherein said outer surface layer is about 1
micrometer thick.
6. A photovoltaic solar cell as claimed in any
preceding claim, wherein the substrate layer is
between 200 and 300 micrometers thick.
7. A photovoltaic solar cell as claimed in Claim
6, wherein the substrate layer is about 250
micrometers thick.
8. A photovoltaic solar cell as claimed in any
preceding claim, wherein each of said deposited
semiconductor layers is between 2 and 6
micrometers thick.
9. A photovoltaic solar cell as claimed in Claim 8, wherein each of said deposited semiconductor layers is about 4 micrometers thick.
10. A photovoltaic cell as claimed in any preceding claim, wherein the layers are all lattice matched to the germanium lattice constant of 5.66A to within +1.0%.
11. A multilayer photovoltaic solar cell, substantially as hereinbefore described with reference to, and as shown in, Figure 2 of the accompanying drawings.
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GB8205618A GB2117174B (en) | 1982-02-25 | 1982-02-25 | Multilayer photovoltaic solar cell |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2255227A (en) * | 1991-04-23 | 1992-10-28 | Us Energy | Monolithic tandem solar cells |
EP0796508A1 (en) * | 1994-12-08 | 1997-09-24 | Pacific Solar Pty Ltd | Multilayer solar cells with bypass diode protection |
DE10106491B4 (en) * | 2000-02-14 | 2010-08-12 | Sharp K.K. | Photoelectric converter with a first and a second pn junction of III-V compound semiconductors |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1549040A (en) * | 1975-07-28 | 1979-08-01 | Philips Electronic Associated | Semiconductor devices and photocouplers |
GB2067012A (en) * | 1979-12-31 | 1981-07-15 | Chevron Res | Photovoltaic solar cell |
-
1982
- 1982-02-25 GB GB8205618A patent/GB2117174B/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1549040A (en) * | 1975-07-28 | 1979-08-01 | Philips Electronic Associated | Semiconductor devices and photocouplers |
GB2067012A (en) * | 1979-12-31 | 1981-07-15 | Chevron Res | Photovoltaic solar cell |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2255227A (en) * | 1991-04-23 | 1992-10-28 | Us Energy | Monolithic tandem solar cells |
GB2255227B (en) * | 1991-04-23 | 1995-04-05 | Us Energy | Monolithic tandem solar cell |
EP0796508A1 (en) * | 1994-12-08 | 1997-09-24 | Pacific Solar Pty Ltd | Multilayer solar cells with bypass diode protection |
EP0796508A4 (en) * | 1994-12-08 | 1998-06-03 | Pacific Solar Pty Ltd | Multilayer solar cells with bypass diode protection |
US5990415A (en) * | 1994-12-08 | 1999-11-23 | Pacific Solar Pty Ltd | Multilayer solar cells with bypass diode protection |
DE10106491B4 (en) * | 2000-02-14 | 2010-08-12 | Sharp K.K. | Photoelectric converter with a first and a second pn junction of III-V compound semiconductors |
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GB2117174B (en) | 1985-09-25 |
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