Patent Application
20120073638
The invention related to InP-based multi junction semiconductor devices and the photovoltaic and optoelectronic devices comprising the same.
Ultra-high efficiency and very-light-weight solar cells are highly desirable for many defense and commercial applications. Multi junction (MJ) tandem cell design is the only proven approach that has achieved record high conversion efficiencies. Currently, the state-of-the-art GaInP/(In)GaAs/Ge monolithic triple junction solar cells have demonstrated a very impressive conversion efficiency of 33.8% under AM1.5G and 41.1% under AM1.5D 454 suns. The lattice-matched triple junction solar cell design based on Ge substrates is actually current mismatched, which makes overall conversion efficiency lower than the achievable limit. GaInNAs alloys with bandgaps close to 1 eV have been attempted as the bottom junction for better current-matching. But their short minority-carrier lifetime, or diffusion length, actually reduced the solar cell overall conversion efficiency.
Metamorphic layers, such as lattice mismatched InGaAs, have been used to improve the current matching condition. This approach has shown an increased efficiency, as the benefit resulted from the better current matching is greater than the loss through non-radiative recombination caused by the misfit dislocations. However, the efficiency improvement using such an approach is very limited because more non-radiative loss is always associated with these metamorphic layers. Moreover, adding more junctions on the state-of-the-art triple junction design has also been explored to further increase the conversion efficiency. However, the results have not yet shown any efficiency improvement as the GaAs/Ge based material system lacks high-quality, lattice-matched semiconductors with optimal current-matched bandgaps required to realize a real gain in efficiency.
Herein, we describe an approach using lattice-matched II-VI (ZnCdHg)(SeTe) and III-V (InGaAsP) semiconductors grown on InP substrates for MJ solar cells that can reach efficiencies greater than 40% under 1 sun. Lattice-matched quaternary alloys on InP have a very broad range of bandgaps: CdZnSeTe, CdZnHgSe, and InGaAsP quaternary alloys lattice-matched to InP can cover bandgaps from 2.2 eV down to 0.7 eV. Using MBE or MOCVD, the growth of these quaternary alloys can be well controlled as being demonstrated in other optoelectronic devices, such as photodetectors, lasers, and LEDs.
In one aspect, the invention provides semiconductor structures comprising, an InP substrate; an optional InGaAsP building block formed over and lattice matched or pseudomorphically strained to the InP substrate; an InP building block formed over and lattice matched or pseudomorphically strained to either (i) the InGaAsP building block, when present; or (ii) the InP substrate; at least one (ZnCdHg)(SeTe) building block formed over and lattice matched or pseudomorphically strained to the InP building block, wherein, when more than one (ZnCdHg)(SeTe) building block is present, each (ZnCdHg)(SeTe) building block has a different bandgap; and a tunnel diode between each of the building blocks.
In another aspect, the invention provides solar cells comprising a semiconductor structure according to the preceding aspect.
a (top) shows calculated conversion efficiencies (left-hand y-axis) for a two-junction tandem cell as functions of the top junction bandgaps (the x-axes), the lines plotted against the right y-axes give bandgaps for all the subcells under current-matched condition; (bottom) shows an exemplary layer structures and compositions corresponding to the data shown on top.
b (top) shows calculated conversion efficiencies (left-hand y-axis) for a three junction tandem cell as functions of the top junction bandgaps (the x-axes), the lines plotted against the right y-axes give bandgaps for all the subcells under current-matched condition; (bottom) shows an exemplary layer structures and compositions corresponding to the data shown on top.
c (top) shows calculated conversion efficiencies (left-hand y-axis) for a four-junction tandem cell as functions of the top junction bandgaps (the x-axes), the lines plotted against the right y-axes give bandgaps for all the subcells under current-matched condition; (bottom) shows an exemplary layer structures and compositions corresponding to the data shown on top.
a) shows the composition dependent band edges of the CdZnSeTe, CdZnHgSe, and InGaAsP alloys, the alloy mole fractions x and y are chosen to have the alloys perfectly lattice matched to InP; (b) shows a schematic band edge alignment of the two active regions of a two junction solar cell design.
It is the object of the present invention to provide for at least one or more of (a) the use of lattice-matched materials may eliminate misfit dislocations that reduce material quality; (b) the use of direct bandgap materials to maximize the absorption and to minimize the thickness of the junction region to minimize series resistance, material usage and growth time; (c) spontaneous emission coupling between adjacent junctions made of direct bandgap semiconductors needs to be taken into account for the optimal design of the bandgap energy and thickness of each multi-junction building block and may aid in optimizing the overall conversion efficiency of the whole device; (d) minimization of the series resistance of the contacts, the tunnel diodes, contact layers, and the substrate; and/or (e) decrease the efficiency reduction from the loss of solar radiation below the lowest bandgap energy of present devices.
In particular, the instant invention utilizes lattice-matched or pseudomorphically strained InP, (ZnCdHg)(SeTe), and, optionally, InGaAsP semiconductor material systems for multi-junction solar cells that can be grown on InP substrates.
Referring to
Referring to
Each alloy layer can be doped with a dopant as is familiar to those skilled in the art. For example, Table 1 lists n- and p-doped materials which can be used according to the invention, their respective dopants, and doping concentrations [n (cm−3) or p (cm−3)] of the dopant therein.
Each multi junction building block can optionally comprise other additional layers that are either doped at different levels or have different alloy compositions or even different semiconductor materials, where the layers are made of III-V alloys or II-VI alloys.
For example, the invention provides the structure according to first aspect (e.g.,
In certain other embodiments, the invention provides the structure according to first aspect (e.g.,
In any of the preceding embodiments, more than one (ZnCdHg)(SeTe) building block can be present. When more than one is present, each (ZnCdHg)(SeTe) building block has a different bandgap. Each (ZnCdHg)(SeTe) building blocks, can comprise, independently, a binary, ternary, quaternary or higher (ZnCdHg)(SeTe) alloy. In certain embodiments, each (ZnCdHg)(SeTe) building block independently comprises CdZnHgSe, CdZnSeTe, ZnSeTe, CdSeTe, CdSe, ZnSe, HgCdTe, or HgSe. In certain embodiments, each (ZnCdHg)(SeTe) building block independently comprises CdZnHgSe, CdZnSeTe, or ZnSeTe.
In certain other embodiments, a first (ZnCdHg)(SeTe) building block comprises CdZnHgSe (e.g., CdxZnyHg1-x-ySe, wherein x is about 0 to about 0.5 and y is about 0 to about 1, provided that 1-x-y is greater than 0; or wherein x is about 0 to about 0.5 and y is about 0.511 to about 0.519) and a second (ZnCdHg)(SeTe) building block comprises an CdZnSeTe alloy (e.g., CddZn1-dSeeTe1-e, wherein d is about 0 to about 0.5 and e is 0 to 1; or d is about 0 to about 0.5 and e is 0.5 to 1). In certain other embodiments, a first (ZnCdHg)(SeTe) building block comprises an CdZnHgSe alloy (e.g., CdxZnyHg1-x-ySe, wherein x is about 0 to about 0.5 and y is 0 to 1, provided that 1-x-y is greater than 0; or x is about 0 to about 0.5 and y is about 0.5) and a second (ZnCdHg)(SeTe) building block comprises ZnSe1-zTez, wherein z is 0 to 1.
In certain embodiments, each of the multi junction building blocks are lattice matched or pseudomorphically strained to either the substrate or to the block over which it was formed. In certain particular embodiments, the multi junction building blocks are lattice matched or pseudomorphically strained to the substrate. In certain particular embodiments, the multi-junction building blocks are lattice matched to the substrate. In other certain particular embodiments, the multi junction building blocks are pseudomorphically strained to the substrate.
Each alloy layer in a multi junction building block can be chosen such that bandgap energy (Eg) of each of the multi junction building blocks is a value between 0.70-2.20 eV. In certain embodiments, the bandgap of each multi junction building block can be chosen from the group consisting of 0.70-0.90 eV, 0.80-1.00 eV, 0.90-1.10 eV, 1.10-1.30 eV, 1.20-1.40 eV, 1.25-1.45 eV, 1.30-1.50 eV, 1.60-1.80 eV, 1.70-1.90 eV, 1.80-2.00 eV, 1.90-2.10 eV and 2.00-2.20 eV.
For example, referring to the representative embodiment of
In another example, referring to the representative embodiment of
In another example, referring to the representative embodiment of
In certain of the preceding embodiments, each of the layers has a bandgap greater than the bandgap of the multi junction building block it is formed over. In other certain of the preceding embodiments, each of the layers has a bandgap less than the bandgap of the multi-junction building block it is formed over. In other certain of the preceding embodiments, each of the multi junction building blocks is lattice matched or pseudomorphically strained to the substrate. In other certain of the preceding embodiments, each of the multi junction building blocks are lattice matched to the substrate.
The semiconductor structures of first aspect (e.g.,
In yet other embodiments, the structure can further comprise at least one tunnel diode which is formed naturally between any two multi junction building blocks. For example, heterojunction formed by two building blocks and having a type-II or type-III band alignments would not require an additional tunnel diode to be formed between the respective building blocks. In certain embodiments, the tunnel diode which is formed naturally between any two multi-junction building blocks has a type-II band alignment. In certain other embodiments, the tunnel diode which is formed naturally between any two multi junction building blocks has a type-III band alignment.
The semiconductor structures of first aspect can also further comprise, as necessary, a buffer layer between the substrate and the first multi junction building block formed over the substrate (i.e., an InGaAsP building block or an InP building block). Such buffer layers can comprise an appropriate material or multiple layers of materials as known to those skilled in the art, for example, to promote growth of a multi junction building block over the substrate.
Further additional components, which are familiar to those skilled in the art, which can be included in the semiconductor structures of the first aspect include, n- and/or p-contact layers (e.g., ohmic contacts). Such contact layers can be in contact with the substrate or the upper-most layer of the multi junction building blocks formed over the substrate. In certain embodiments, the ohmic contacts can comprise a conductive metal layer; examples of conductive metals include, but are not limited to, gold, silver, platinum, palladium, nickel, calcium, magnesium, tungsten, indium, indium/mercury, tin, gold/tin, mixtures, and multilayers thereof. Further examples of such contacts which can be utilized with various multi junction building blocks and/or substrates are listed in Table 2.
Each of the multi junction building blocks can be prepared, for example via liquid phase epitaxy (LPE), molecular beam epitaxy (MBE) or metal organic chemical vapor deposition (MOCVD), according to methods familiar to those skilled in the art.
Herein, a notation is used to refer to alloys having the form of two sets of elements each within its own set of parenthesis; for example, (ABCD)(EFGH). This notation means that the alloy comprised at least one element selected from A, B, C, and D, and at least one element selected from E, F, G, and H. When this notation is used in combination with the modifiers such as “binary”, “ternary”, “quaternary”, “quinary”, or “senary”, among others, it means that the alloy contains a total of 2, 3, 4, 5, or even 6 elements, respectively, provided that at least one element selected from A, B, C, and D, and at least one element selected from E, F, G, and H. For example, a ternary (ZnCdHg)(TeSe) alloy includes both ZnTeSe and ZnCdTe, among other combinations.
It should be understood that when a layer is referred to as being “on” or “formed over” another layer or substrate, it can be directly on the layer or substrate, or an intervening layer may also be present. It should also be understood that when a layer is referred to as being “on” or “formed over” another layer or substrate, it may cover the entire layer or substrate, or a portion of the layer or substrate.
It should be further understood that when a layer is referred to as being “directly on” another layer or substrate, the two layers are in direct contact with one another with no intervening layer. It should also be understood that when a layer is referred to as being “directly on” another layer or substrate, it may cover the entire layer or substrate, or a portion of the layer or substrate.
The term “bandgap” or “Eg” as used herein means the energy difference between the highest occupied state of the valence band and the lowest unoccupied state of the conduction band of the material. The bandgap for a building block, as used herein, refers to the bandgap of the material that forms the p-n junction.
The term “lattice matched” as used herein means that the two referenced materials have the same or lattice constants differing by up to +/−0.2%. For example, GaAs and AlAs are lattice matched, having lattice constants differing by ˜0.12%.
The term “pseudomorphically strained” as used herein means that layers made of different materials with a lattice parameter difference up to +/−2% can be grown on top of other lattice matched or strained layers without generating misfit dislocations. In certain embodiments, the lattice parameters differ by up to +/−1%. In other certain embodiments, the lattice parameters differ by up to +/−0.5%. In further certain embodiments, the lattice parameters differ by up to +/−0.2%.
The term “building block” as used herein, means a region comprising a p-n junction having at least two layers of similar or dissimilar materials doped n and p type, respectively, where the absorption edge of this p-n junction defines the bandgap of the building block, as defined herein. When a building block is noted as an “(ABCD)(EFGH) building block,” then the building block comprises a p-n junction having at least two layers of similar or dissimilar (ABCD)(EFGH) materials doped n and p type, respectively. Such building blocks can comprise multiple layers. For example, a building block can comprise a p-n junction and a third doped layer to form a Ppn structure, wherein the P region can comprise material that has the same or larger bandgap than that of the p-n region, or a building block can comprise a p-n junction and one additional doped layer on each side of the p-n junction to form a PpnN structure, wherein the P and the N regions can comprise materials that have the same or larger bandgap than that of the p-n junction region.
The term “layer” as used herein, means a continuous region of a material (e.g., an alloy) that can be uniformly or non-uniformly doped and that can have a uniform or a non-uniform composition across the region.
The term “tunnel diode” as used herein, means a region comprising two heavily doped layers with n- and p-type, respectively. Both of these layers can be of the same materials (homojunction) or different materials (heterojunction).
The term “p-doped” as used herein means atoms have been added to the material (e.g., an alloy) to increase the number of free positive charge carriers.
The term “n-doped” as used herein means atoms have been added to the material (e.g., an alloy) to increase the number of free negative charge carriers.
The term “p+-doped” as used herein means atoms have been added to the material (e.g., an alloy) to increase the number of free positive charge carriers such that the material is degenerate, as is known to those skilled in the art.
The term “n+-doped” as used herein means atoms have been added to the material (e.g., alloy) to increase the number of free negative charge carriers such that the material is degenerate, as is known to those skilled in the art.
The term “P-doped” as used herein means the material is p-doped, as defined herein, and the bandgap of the material is the same or greater than the p-doped material of a p-n junction.
The term “N-doped” as used herein means the material is n-doped, as defined herein, and the bandgap of the material is the same or greater than the n-doped material of a p-n junction.
The term “II-VI alloy” as used herein means an alloy where the constituent elements are selected from Groups HA, IIB, and VIA, of the periodic table, wherein at least one constituent element is selected from Groups IIA and/or IIB of the periodic table and at least one constituent element is selected from Group VIA of the periodic table. Examples of II-VI alloys include, but are not limited to (a) binary alloys such as, but not limited to, Cadmium selenide (CdSe), Cadmium sulfide (CdS), Cadmium telluride (CdTe), Zinc oxide (ZnO), Zinc selenide (ZnSe), Zinc sulfide (ZnS), and Zinc telluride (ZnTe); (b) ternary alloy such as, but not limited to, Cadmium zinc telluride (CdZnTe, CZT), Mercury cadmium telluride (HgCdTe), Mercury zinc telluride (HgZnTe), and Mercury zinc selenide (HgZnSe); and (c) quaternary alloys such as, but not limited to, Cadmium mercury selenide telluride (CdHgSeTe) and Cadmium zinc selenide telluride (CdZnSeTe).
The term “III-V alloy” as used herein means an alloy where the constituent elements are selected from Groups IIIA and VA of the periodic table, wherein at least one constituent element is selected from Group IIIA of the periodic table and at least one constituent element is selected from Group VA of the periodic table. Examples of III-V alloys include, but are not limited to (a) binary alloys such as, but not limited to, Aluminum antimonide (AlSb), Aluminum arsenide (AlAs), Aluminum nitride (AlN), Aluminum phosphide (AlP), Boron nitride (BN), Boron phosphide (BP), Boron arsenide (BAs), Gallium antimonide (GaSb), Gallium arsenide (GaAs), Gallium nitride (GaN), Gallium phosphide (GaP), Indium antimonide (InSb), Indium arsenide (InAs), Indium nitride (InN), and Indium phosphide (InP); (b) ternary alloys, but not limited to, Aluminum gallium arsenide (AlGaAs, AlxGa1-xAs), Indium gallium arsenide (InGaAs, InxGa1-xAs), Aluminum indium arsenide (AlInAs), Aluminum indium antimonide (AlInSb), Gallium arsenide nitride (GaAsN), Gallium arsenide phosphide (GaAsP), Aluminum gallium nitride (AlGaN), Aluminum gallium phosphide (AlGaP), Indium gallium nitride (InGaN), Indium arsenide antimonide (InAsSb), and Indium gallium antimonide (InGaSb); (c) quaternary alloys such as, but not limited to, Aluminum gallium indium phosphide (AlGaInP, also InAlGaP, InGaAlP, AlInGaP), Aluminum gallium arsenide phosphide (AlGaAsP), Indium gallium arsenide phosphide (InGaAsP), Aluminum indium arsenide phosphide (AlInAsP), Aluminum gallium arsenide nitride (AlGaAsN), Indium gallium arsenide nitride (InGaAsN), and Indium aluminum arsenide nitride (InAlAsN); and (d) quinary alloys such as, but not limited to, Gallium indium nitride arsenide antimonide (GaInNAsSb). Higher order alloys include, for example, the senary alloy Indium gallium aluminum arsenide antimonide phosphide InGaAlAsSbP.
Three multi junction (MJ) solar cell designs are based on theoretical calculations of optimal subcell bandgaps using our newly developed comprehensive model that takes into account practical material parameters, nonradiative recombination, and spontaneous emission coupling. The detailed modeling results of total conversion efficiencies and the schematic layer structures and compositions of the described designs are shown in
As shown in
The specific efficiencies of the described designs are listed in Table 3. The same model is used to calculate the conversion efficiencies of the state-of-the-art single junction and MJ solar cells. The results are also listed together with the published experimental data in Table 3, which show clearly that our model is able to very accurately predict the actual device performance not only for the single junction Si and GaAs cells but also for the more complicated triple junction tandem cells. It is therefore very reasonable to expect that our predicted efficiencies for the new designs will be realistic and achievable experimentally.
a plots the calculated conduction and valence band edges of the ZnCdTeSe, CdZnHgSe, and InGaAsP quaternary alloys lattice-matched to InP. Using these band edge diagrams, one can determine the band edge alignment between any two given layers of different compositions or of different materials. The band edge alignment for the two active regions of the two junction solar cell design is schematically shown in
Compared with the current state-of-the-art triple junction solar cell designs, our structures have the following advantages:
This provides reduced absorption of IR light, better heat sinking, and very light weight.
The described MJ solar cells can also be used for terrestrial concentrator photovoltaic applications, where high efficiency and low-cost cells are critical to the overall cost for solar electricity generation. For example, HgCdSe on a lattice-matched InAs substrate could provide a material system for IR photodectectors. Together with ZnCdSeTe integrated with GaAlAsSb, the material platform enables the construction of highly desirable monolithically integrated multispectral photodetectors on a single substrate to cover the entire UV to IR spectrum.
The present invention is illustrated by way of the foregoing description and examples. The foregoing description is intended as a non-limiting illustration, since many variations will become apparent to those skilled in the art in view thereof. It is intended that all such variations within the scope and spirit of the appended claims be embraced thereby. Each referenced document herein is incorporated by reference in its entirety for all purposes.
Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims.
This application claims the benefit of U.S. Provisional Application Ser. No. 61/384,951, filed Sep. 21, 2010, which is hereby incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61384951 | Sep 2010 | US |
