Patent Application
20120090672
1. Field of the Invention
The invention relates to a semiconductor based structure for a device for converting radiation to electrical energy comprising various combinations of rare-earths and Group IV, III-V, and II-VI semiconductors and alloys thereof enabling enhanced performance including high radiation conversion efficiency.
2. Description of Related Art
Prior art is found in U.S. Pat. No. 5,548,128, U.S. Pat. No. 4,834,501, U.S. Pat. Nos. 7,598,513, 7,589,003 2007/0020891, U.S. 2008/0277647 and U.S. 2008/0187768; all included herein in their entirety by reference. Additional art is found in App. Phy. Lett., 86, 191912 (2005); App. Phy. Letters, 88, 252112, 2006; App. Phy. Letters, 89, 231924, 2006; Kouvetakis, John “Independently tunable electronic and structural parameters in ternary Group IV semiconductors for optoelectronic applications”; all included herein in their entirety by reference.
Crystalline Si has enjoyed spectacular success in the solar cell industry for various reasons including the ability to benefit from technological breakthroughs in the microelectronics industry and the close proximity of the 1.1 eV band gap value of Si to the optimal theoretical 1.3 eV band gap value for which the thermodynamically limited single-cell efficiency reaches a maximum value. Since modern single-cell crystal solar technology appears to be approaching the maximum expected efficiency, efforts to increase the competitiveness of these cells have focused on decreasing the cell thickness and thereby reducing silicon consumption. Still, ultra-thin Si cells face a fundamental limitation. The lowest energy direct optical transition in this material occurs at 3.5 eV, and therefore, its absorption below this threshold is very low because only phonon-assisted transitions are possible. On the other hand, thinner films have certain advantages because the ratio of carrier diffusion length to thickness is larger, thereby increasing the collection efficiency of minority carriers. The ideal compromise for maximum efficiency is estimated to be approximately 150 μm. Consequently, the industry is also approaching a fundamental limit when it comes to savings by reducing the Si thickness.
Researchers at Arizona State University have developed a method to fabricate Si/GeSn and/or Si/Ge tandem cells that take advantage of chemical vapor deposition (CVD) techniques allowing growth of Ge and GeSn on silicon substrates. The resulting potential efficiencies substantially exceed that of traditional Si solar cells and represent the most promising approach to advance Si-cell technology. Increased Efficiency—traditional Si cells offer maximum thermodynamic efficiency of ≈35% (requires thick Si) compared to ≈40% efficiency offered by new method for ultra-thin Si; traditional Si operates at ≈21% for actual commercial values and down to ≈15% at a 25 μm thickness. Allows Dramatic Reductions in Material Thickness—GeSn/Ge thicknesses below 10 μm and even below 1 μm for certain applications sufficient for 90% light absorption compared to the optimal 150 μm value needed for traditional Si solar cells. Eliminates Need for Light Trapping Features—traditional methods require special texturing or rear surface reflectors; significance of advantage increases as thickness decreases.
Doped and intrinsic Ge1-x-ySixSny alloys are synthesized directly on Si(100) using simple deposition chemistries and their optical and electrical properties are determined. Tuning the Si/Sn ratio at ˜4 yields strain-free films with Ge-like cell dimensions, while variation of the ratio around this value produces compressively strained, tetragonal structures with an in-plane lattice constant “pinned” to a value close to that of pure Ge (5.658 Å). First-principles calculations show that mixing entropy thermodynamically stabilizes SiGeSn in contrast to GeSn analogs with the same Sn content. GeSn and SiGeSn are predicted to become metastable for 2% and 12% Sn, respectively, in good agreement with experiment.
The optical properties of Ge1-ySny alloys (y˜0.02) grown by chemical vapor deposition on Si substrates have been studied using spectroscopic ellipsometry and photocurrent spectroscopy. The system shows a 10-fold increase in optical absorption, relative to pure Ge, at wavelengths corresponding to the C-telecommunication band (1550 nm) and a 20-fold increase at wavelengths corresponding to the L-band (1620 nm). Measurements on a series of samples with different thicknesses reveal nearly identical dielectric functions, from which the composition reproducibility of the growth method is estimated to be as good as 0.1%. It is shown that a model that includes excitonic effects reproduces the measured onset of absorption using the direct band gap E0 as essentially the only adjustable parameter of the fit.
Group-IV semiconductors, including alloys incorporating Sn, have been grown on dimensionally dissimilar Si substrates using novel molecular hydride chemistries with tunable reactivities that enable low temperature, CMOS compatible integration via engineering of the interface microstructure. Here we focus on properties of three such Ge-based systems including: (1) device quality Ge layers with thicknesses>5 μm possessing dislocation densities <105/cm2 are formed using molecular mixtures of Ge2H6 and highly reactive (GeH3)2CH2 organometallic additives circumventing the classical Stranski-Krastanov growth mechanism, (2) metastable GeSn alloys are grown on Si via reactions of Ge2H6 and SnD4, and (3) ternary SiGeSn analogs are produced lattice-matched to Ge-buffered Si using admixtures of SiGeH6, SiGe2H8, SnD4, Ge2H6, and Si3H8. Optical experiments and prototype device fabrication demonstrate that the ternary SiGeSn system represents the first group-IV alloy with a tunable electronic structure at fixed lattice constant, effectively decoupling band gap and strain and eliminating the most important limitation in device designs based on group-IV materials. Doping at levels higher than 1019 cm−3 (both p and n-type) is achieved for all the above semiconductor systems using a similar precursor chemistry approach. Electrical and infrared optical experiments demonstrate that doped GeSn and SiGeSn have mobilities that compare or exceed that of bulk Ge.
Ternary GeSiSn alloys have been demonstrated on Ge- and GeSn-buffered Si substrates. These alloys, with a two-dimensional compositional space, make it possible to decouple lattice constant and electronic structure for the first time in a group-IV system. A Kouvetakis and Menendez paper, in Thin Solid Films, reviews the basic properties of the GeSiSn alloy, presents some new results on its optical properties, and discusses the approach that has been followed to model heterostructures containing GeSiSn layers for applications in modulators, quantum cascade lasers, and photovoltaics.
As used herein a rare earth, [RE1, RE2, . . . REn], is chosen from the lanthanide series of rare earths from the periodic table of elements {57La, 58Ce, 59Pr, 60Nd, 61Pm, 62Sm, 63Eu, 64Gd, 65Tb, 66Dy, 67Ho, 68Er, 69Tm, 70Yb and 71Lu} plus yttrium, 39Y, and scandium, 21Sc, are included as well for the invention disclosed. “REO” is used generically to refer to rare earth oxide, rare earth nitride, rare earth phosphide and mixtures thereof compounds; “RE” may refer to one or more than one rare earth in combination.
In some embodiments a photovoltaic structure, optionally a solar cell comprising one or more active junction layers, comprises a plurality of layers wherein an active junction layer is optionally Group IV based, optionally Group III-V based and/or optionally Group II-VI based. Frequently various active junctions are designed to operate in tandem such that a wide range of incident radiation, optionally solar radiation, is absorbed. Separating the one or more active junction layers from a substrate are transition layers designed to transition between a substrate of first composition and first lattice constant to a first active junction layer of second composition and second lattice constant. The transition layers comprise, optionally, a rare earth based layer(s) and, optionally, a Group IV based layer(s). Rare earth based layers comprise at least one rare earth in combination with at least one of oxygen, nitrogen and phosphorous. Group IV based layers comprise at least one of germanium and silicon; optionally, Group IV based layers comprise at least one of other Group IV materials such as carbon, tin and/or lead. In this manner a multi-junction solar cell is constructed on a substrate with one or more rare earth based layers and optionally one or more Group IV based layers between a multi-junction solar cell and a substrate. As used herein a multi-junction solar cell comprises one or more active junction layers comprising either Group IV, group III-V and/or Group II-VI based layers. In one embodiment a rare earth based layer and a Group IV based layer separate an active junction layer from a substrate.
Rare earth base layers are of a composition defined by [RE1]x[RE2]y[RE3]z[J1]u[J2]v[J3]w wherein 0<x, u≦5 and 0≦v, w, y, z≦5 and J is one of oxygen, nitrogen or phosphorus. Group IV based layers are of a composition defined by SiuGevCwSnxPby wherein at least one of u or v is greater than zero and 0≦w, x, y, (v or u)≦5. Rare earth base layers and Group IV based layers may be single crystal, polycrystalline, microcrystalline, nano crystals, quantum dots or amorphous. In some embodiments rare earth based layers and Group IV based layers form an interleaved structure as in
The present invention relates to semiconductor devices suitable for electronic, optoelectronic and energy conversion applications. In a particular form, the present invention relates to the fabrication of an energy conversion device through the combination of crystalline or amorphous semiconductors, insulators, rare-earth based compounds and substrates.
Triple junction materials are generally chosen from Group III-V materials, such as In, Ga, Al, As, P with the exact combinations tailored to specific energies but with restriction imposed by the choice of a germanium substrate or Ge support layer. By removing the restrictions of a germanium substrate, or support layer, new combinations of III-V alloys, and II-VI materials, are enabled. A lattice matched and/or engineered strained substrate or support layer with better current match and better band gap match to a broad selection of triple junction cell materials enables a higher efficiency multi-junction solar cell.
The instant invention discloses the use a substrate, optionally silicon, modified by the addition of various rare earth based layers and, optionally, Group IV based layers producing a multilayer, virtual substrate whose upper surface is lattice matched or, optionally, lattice-in-strain matched to a desired multi-junction solar cell or other photovoltaic device comprising material combinations from Groups III-V and/or II-VI and/or Group IV.
a and 5b multiple rare earths and how composition may vary with layer thickness.
a, b and c show various embodiments for substrate and rare earth based layer and Group IV based layer.
a, b and c show different example of strain balanced and lattice matched structures.
a and b shows an exemplary embodiment with graded rare earth composition between two Group IV based layers.
The instant invention discloses a structure to transition from a substrate of first composition to a semiconductor material of second composition, optionally, operable as a solar cell. A transition structure as defined herein comprises at least first rare earth based layer of third composition at a first surface and of fourth composition at a second surface; positioned such that the first surface is in contact with the substrate and the second surface is in contact with the semiconductor material; optionally, a Group IV based layer is between the rare earth based layer second surface and the semiconductor material. In some embodiments there are a plurality of rare earth based layers interleaved with Group IV based layers between a substrate and a semiconductor material of second composition.
a and 5b show exemplary embodiments of how multiple rare earth compositions may vary with layer thickness; other variations are also disclosed in the references. A binary rare earth compound may vary in RE1 and RE2 content; optionally, oxygen, nitrogen and phosphorus content may vary; Group IV specie, C, Si, Ge, Sn, Pb content may vary. The intent being to achieve a lattice constant/inherent lattice strain combination optimum for a specific solar cell composition based upon a starting substrate composition.
a and b show various embodiments for Group IV based substrates, rare earth based layers and Group IV based layers. In some embodiments only one rare earth based layer in combination with one Group IV based layer is required to transition between a substrate or support layer and a multi-junction structure; in some embodiments multiple layers are required as shown in
a, b and c show examples of strain balanced and lattice matched structures. Note that the GexSn1-x layer shown is exemplary and may be of different composition or not needed depending on the composition of a solar cell structure to be added to the structure shown.
a and b show an exemplary embodiment with graded rare earth composition between two Group IV based layers producing a layer with compressive strain on one surface and tensile strain on the other. The embodiments of
In some embodiments a structure within a solid state device comprises a first region of first composition, a second region of second composition and a third region of third composition separated from the first region by the second region; wherein the second region comprises a first and second rare-earth compound such that the lattice spacing of the first compound is different from the lattice spacing of the second compound and the third composition is different from the first composition; optionally, a solid state device comprises a first and third region comprising substantially elements only from Group IV; optionally, a solid state device further comprises a fourth region comprising substantially elements only from Groups III and V; optionally, a solid state device further comprises a fourth region comprising substantially elements only from Groups II and VI; optionally, a solid state device comprises a second region described by [RE1]u[RE2]v[RE3]w[J1]x[J2]y[J2]z wherein [RE] is chosen from a rare earth; [J1], [J2] and [J3] are chosen from a group consisting of Oxygen (O), Nitrogen (N), and Phosphorus (P), and 0≦v, w, y, z≦5, and 0<u, x≦5; optionally, a solid state device comprises a second region comprising a first portion of fourth composition adjacent said first region; a second portion of fifth composition; and a third portion of sixth composition separated from the first portion by the second portion and adjacent said third region wherein the fifth composition is different from the fourth and sixth compositions; optionally, a solid state device comprises a second portion comprising a first surface adjacent said first portion and a second surface adjacent said third portion and said fifth composition varies from the first surface to the second surface; optionally a solid state device comprises a second portion comprising a first surface adjacent said first portion and a second surface adjacent said third portion and comprises a superlattice with a structure comprising two layers of different composition which repeat at least once; optionally a solid state device comprises a first portion in a first state of stress and a third portion in a second state of stress different from the first state of stress.
In some embodiments a solid state device comprises first and second semiconductor layers separated by a rare earth layer wherein the first semiconductor layer is of composition X(1-m)Ym; the second semiconductor layer is of composition XnYoZp and the rare earth layer is of a composition described by [RE1]n[RE2]v[RE3]w[J1]x[J2]y[J2]z wherein [RE] is chosen from a rare earth; [J1], [J2] and [J3] are chosen from a group consisting of Oxygen (O), Nitrogen (N), and Phosphorus (P), and 0≦v, w, y, z≦5, and 0<u, x≦5; and X, Y and Z are chosen from Group IV elements such that 0≦m≦1, 0≦o, p≦5, and n>0; optionally, a device comprises a rare earth layer comprising a first and second rare earth layer such that the composition of the first layer is different from the composition of the second layer and the lattice spacing of the first layer is different from the lattice spacing of the second layer.
In some embodiments a solid state device comprises a first semiconductor layer; a second semiconductor layer; and a rare earth layer comprising regions of different composition separating the first semiconductor layer from the second semiconductor layer; wherein the rare earth layer is of a composition described by [RE1]u[RE2]v[RE3]w[J1]x[J2]y[J2]z wherein [RE] is chosen from a rare earth; [J1], [J2] and [J3] are chosen from a group consisting of Oxygen (O), Nitrogen (N), and Phosphorus (P), and 0≦v, w, y, z≦5, and 0<u, x≦5 such that the composition of the rare earth layer adjacent the first semiconductor layer is different from the composition of the rare earth layer adjacent the second semiconductor layer; optionally, a device comprises first and second semiconductor materials chosen from one or more Group IV elements or alloys; optionally, a device comprises a rare earth layer comprising a first region adjacent said first semiconductor layer, a second region adjacent said second semiconductor layer and a third region separating the first region from the second region such that the composition of the third region is different from the first region and the second region.
In some embodiments a solid state device for converting incident radiation into electrical energy comprises a first semiconductor layer consisting of one or more Group IV elements; a second semiconductor layer consisting of one or more Group IV elements; a rare earth layer comprising regions of different composition separating the first semiconductor layer from the second semiconductor layer; wherein the rare earth layer is of a composition described by [RE1]u[RE2]v[RE3]w[J1]x[J2]y[J2]z wherein [RE] is chosen from a rare earth; [J1], [J2] and [J3] are chosen from a group consisting of Oxygen (O), Nitrogen (N), and Phosphorus (P), and 0≦v, w, y, z≦5, and 0<u, x≦5 such that the composition of the rare earth layer in contact with the first semiconductor layer is different from the composition of the rare earth layer in contact with the second semiconductor layer; and a third semiconductor layer comprising at least one active layer for converting incident radiation into electrical energy in contact with the second semiconductor layer; optionally, a solid state device wherein the rare earth layer composition in contact with the first semiconductor layer is such that the lattice constant of the first semiconductor layer is about the same as the lattice constant of the rare earth layer composition in contact with the first semiconductor layer; optionally, a solid state device wherein the rare earth layer composition in contact with the first semiconductor layer is such that there exists biaxial compressive strain between the rare earth layer and the first semiconductor layer; optionally, a solid state device wherein the rare earth layer composition in contact with the second semiconductor layer is such that the lattice constant of the second semiconductor layer is about the same as the lattice constant of the rare earth layer composition in contact with the second semiconductor layer; optionally, a solid state device wherein the rare earth layer composition in contact with the second semiconductor layer is such that there exists biaxial tensile strain between the rare earth layer and the second semiconductor layer; optionally, a solid state device wherein at least one of the Group IV elements of the second semiconductor layer composition is tin; optionally, a solid state device wherein the composition of the third semiconductor layer is chosen from either Group IV elements or Group III-V elements or Group II-VI elements such that incident radiation is converted into electrical energy.
It will be understood that when an element as a layer, region or substrate is referred to as being “on” or “over” or “adjacent” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” or “directly over” or “in contact with” another element, there are no intervening elements present. It will also be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. As used herein a stratum, or, in the plural, strata, is a layer of material, optionally, one of a number of parallel layers one upon another
Foregoing described embodiments of the invention are provided as illustrations and descriptions. They are not intended to limit the invention to precise form described. In particular, it is contemplated that functional implementation of invention described herein may be implemented equivalently. Alternative construction techniques and processes are apparent to one knowledgeable with integrated circuit, light emitting device, solar cell, flexible circuit and MEMS technologies. Other variations and embodiments are possible in light of above teachings, and it is thus intended that the scope of invention not be limited by this Detailed Description, but rather by Claims following. All references to published material including patents and applications are included herein in their entirety by reference.
This application claims priority from U.S. Provisional Application 61/301,597 filed on Feb. 4, 2010 and is a continuation-in-part of Ser. Nos. 12/408,297, filed on Mar. 20, 2009, 12/510,977, filed on Jul. 28, 2009, and 12/619,637, 12/619,621, 12/619,549, all filed on Nov. 16, 2009 and claims priority from these applications, all included herein in their entirety by reference. applications and patents Ser. Nos. 11/025,693, U.S. 20050166834, 11/257,517, 11/257,597, 11/393,629, 11/472,087, 11/559,690, 11/599,691, 11/788,153, 11/828,964, 11/858,838, 11/873,387, 11/960,418, 11/961,938, 12/119,387, 60/820,438, 61/089,786, 12/029,443, 12/046,139, 12/111,568, 12/119,387, 12/171,200, 12/408,297, 12/510,977, 12/619,621, 12/619,549, 12/619,637, 12/632,741, 12/651,419, 12/890,537, 61/301,597, 61/312,061, U.S. Pat. No. 6,734,453, U.S. Pat. No. 6,858,864, U.S. Pat. No. 7,018,484, U.S. Pat. No. 7,023,011 U.S. Pat. No. 7,037,806, U.S. Pat. No. 7,135,699, U.S. Pat. No. 7,199,015, U.S. Pat. No. 7,211,821, U.S. Pat. No. 7,217,636, U.S. Pat. No. 7,273,657, U.S. Pat. No. 7,253,080, U.S. Pat. No. 7,323,737, U.S. Pat. No. 7,351,993, U.S. Pat. No. 7,355,269, U.S. Pat. No. 7,364,974, U.S. Pat. No. 7,384,481, U.S. Pat. No. 7,416,959, U.S. Pat. No. 7,432,569, U.S. Pat. No. 7,476,600, U.S. Pat. No. 7,498,229, U.S. Pat. No. 7,586,177, U.S. Pat. No. 7,599,623, U.S. Pat. No. 7,655,327, U.S. Pat. No. 7,645,517, all held by the same assignee, contain information relevant to the instant invention and are incorporated herein in their entirety by reference. References, noted in the specification and Information Disclosure Statement, are included herein in their entirety by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61301597 | Feb 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12619621 | Nov 2009 | US |
| Child | 12619637 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12408297 | Mar 2009 | US |
| Child | 13020766 | US | |
| Parent | 12510977 | Jul 2009 | US |
| Child | 12408297 | US | |
| Parent | 12619637 | Nov 2009 | US |
| Child | 12510977 | US | |
| Parent | 12619549 | Nov 2009 | US |
| Child | 12619621 | US |
