WO2008052067A2

WO2008052067A2 - Semiconductor grain and oxide layer for photovoltaic cells

Info

Publication number: WO2008052067A2
Application number: PCT/US2007/082405
Authority: WO
Inventors: Mariana R. Munteanu; Erol Girt
Original assignee: Applied Quantum Technology Llc
Priority date: 2006-10-24
Filing date: 2007-10-24
Publication date: 2008-05-02
Also published as: WO2008052067A3

Abstract

Photovoltaic structures for the conversion of solar irradiance into electrical free energy. In a particular implementation, a photovoltaic cell includes a granular semiconductor and oxide layer with nanometer-size absorber semiconductor grains surrounded by a matrix of oxide. The semiconductor and oxide layer is disposed between electron and hole conducting layers. In some implementations, multiple semiconductor and oxide layers can be deposited.

Description

Semiconductor Grain and Oxide Layer for Photovoltaic Cells

CROSS-REFERENCE TO RELATED APPUCATION(S)

[0001] The present application claims priority to the following U.S. Provisional

Applications:

1) Provisional Appl. Ser. No. 60/854,226, filed October 24, 2006;

2) Provisional Appl. Ser. No. 60/857,967, filed November 10, 2006; and

3) Provisional Appl. Ser. No. 60/859,593, filed November 17, 2006.

TECHNICAL FIELD

[0002] The present disclosure generally relates to photovoltaics.

BACKGROUND

[0003] The maximum thermodynamic efficiency for the conversion of non- concentrated solar irradiance into electrical free energy for a single-band semiconductor absorber is approximately 31 percent [W. Shockley, H. J. Queisser, J., Appl. Phys., 32, 510 (1961)]. This efficiency is attainable in semiconductors with band gap energies ranging from 1.25 to 1.45 electronvolts (eV). For semiconductors, band gap generally refers to the energy difference between the top of the valence band and the bottom of the conduction band. The solar spectrum, however, contains photons with energies ranging from about 0.5 to about 3.5 eV. Photons with energies below the semiconductor band gap are not absorbed. On the other hand, photons with energies above the band gap create charge carriers with a total excess kinetic energy, Ek(excess) = hv - E_g, where hv is the photon energy. A significant factor limiting the conversion efficiency to 31% is that the excess kinetic energy (absorbed photon energy above the semiconductor band gap) Ek(excess) is lost as heat through electron-phonon scattering. "Hot" electrons and holes that are created by absorption of solar photons with energies larger than the band gap will relax to their respective band edges.

[0004] For a single-band-gap semiconductor absorber there are two ways to extract energy from hot carriers before they relax to the band edge. One method produces an enhanced photovoltage, and the other method produces an enhanced photocurrent. The former method involves extraction of hot carriers from a semiconductor absorber before they relax to their respective band edges. Extracting energy from hot carriers, before they relax to the band edge, is possible if the relaxation rate of hot carriers to their respective band edges is slowed. In the latter method, hot carriers produce two or more electron-hole pairs — so-called impact ionization.

[0005] P-n junction solar cells are the most common solar cells, including a layer of n-type semiconductor in direct contact with a layer of p-type semiconductor. If a p- type semiconductor is placed in intimate contact with a n-type semiconductor, then a diffusion of electrons occurs from the region of high electron concentration (the n- type side of the junction) into the region of low electron concentration (p-type side of the junction). The diffusion of carriers does not happen indefinitely, however, because of an opposing electric field created by this charge imbalance. The electric field established across the p-n junction induces separation of charge carriers that are created as result of photon absorption.

[0006] Dye-sensitized solar cells and quantum dot-sensitized solar cells are two next generation solar technologies. In dye-sensitized solar cells, dye molecules are chemisorbed onto the surface of 10 to 30 nanometer (nm) size titanium oxide (TiCte) particles that have been sintered into high porous nanocrystalline 10 to 20 μm thick Tiθ2 films. Upon the photo excitation of dye molecules, electrons are injected from the excited state of dye into the conducting band of the Tiθ2 creating a charge separation and producing photovoltaic effect. The original state of the dye is subsequently restored by electron donation from the electrolyte, usually an organic solvent containing redox system, such as the iodide/triiodide couple. It is generally accepted that, in dye-sensitized solar cells, the electron transport through the oxide is predominantly governed by diffusion, because the highly conductive electrolyte screens the interior of the cells from any applied electric field. [0007] In quantum dot-sensitized solar cells, semiconductor particles with sizes below 10 nm (so-called quantum dots) take the role of the dye molecules as absorbers. In these solar cells, the hot carriers may produce two or more electron- hole pairs, so-called impact ionization, increasing efficiency of these solar cells. Quantum dot-sensitized solar cells offer several other advantages. The band gaps and thereby the absorption ranges are adjustable through quantum dot size or composition. Furthermore, compared to organic dyes, quantum dot sensitization offers improved stability, since the surface of the semiconductor quantum dot can be modified to improve its photostability.

[0008] A noted drawback of both dye-sensitized and quantum dot-sensitized solar cells is long term stability due to the presence of electrolyte. In order to improve stability of quantum dot-sensitized solar cells, the redox electrolyte in these cells can be replaced with a solid hole-conducting material, such as spiro-OMeTAD, or a p-type semiconductor. The former is called a solid state dye-sensitized solar cell, if an absorber is a dye molecule, or a solid state quantum dot-sensitized solar cell, if an absorber is a quantum dot. The latter solar cell, including a p-type semiconductor, is called an extremely thin absorber (ETA) solar cell. In this solar cell, a porous nanocrystalline TiCb film is covered with a p-type semiconductor absorber using an atomic layer deposition technique, or using electrochemical deposition. These techniques enable a conform al deposition of a semiconductor on top of TiCV A p-type semiconductor first fills up the pores of porous TiCte film and then tops the whole structure with a layer about 10 to 200 nm thick. Because of the rough Tiθ2 surface and a conformal deposition of a p-type semiconductor, the interface area between a p-type semiconductor and an oxide layer increases more than 10 times in comparison to that for a flat Tiθ2 film covered by a p-type semiconductor layer. [0009] To decrease the relaxation rate of charge carriers, an absorber semiconductor can be inserted between TiOa (n-type semiconductor) and the solid hole conductor material. In this structure, the n-type semiconductor (oxide, example: T1O2) has a porous structure and the absorber semiconductor is adsorbed at the surface of n-type semiconductor forming individual quantum dots. The average size of the absorber semiconductor quantum dots is below 10 nm to utilize the confinement effect and reduce the relaxation rate of hot carriers increasing efficiency of these solar cells. In the existing fabrication processes of solid state sensitized solar cells porous or rough TiOs layer is filled (using-electrochemical deposition techniques) with absorber semiconductor grains and covered with p-type semiconductor (using atomic layer deposition or electrochemical deposition techniques) or a different hole conducting inorganic material (using for example spin coating of a solution of hole conductor and chlorobenzene (See J. Kruger, U. Bach, R. Plass, M. Piccerelli, L. Cevey, M. Graetzel, Mat. Res. Soc. Symp. Proc, 708, BB9.1.1 (2002)).

[0010] The hole conductor may be an organic transport material. This organic charge transport material may be a polymer, like polytiophen or polyarylamin. The hole conductor may be an organic hole conductor such as spiro- and hetero spiro compounds of the general formula (l)

Kl <P K2

where φ is one of C, Si, Ge or Sn, and Kl and K2 are, independently one of the other conjugated systems. One example organic hole conductor is spiro-OMeTAD (2,2',7,7'-tretakis(N,N-di-p-methoxyphenyl- amine)-9-9'-spirobifluorene). The conductivity of pure spiro-OMeTAD is low. Therefore the material cannot be used, without some modification, in solar cells. Rather, partial oxidation of spiro- OMeTAD by N(PhBr)SSbCk can be used to control the dopant level and to increase the conductivity of the hole conducting layer. A second additive IifCFsSCteJaN can also be added, since Li+ ions have been shown to increase the current output and overall efficiency of the device. The hole conductor matrix can be applied by spin- coating of a solution of the hole conductor in chlorobenzene. MEH-PPV [ρoly[2- methoxy-[5-(2'-ethyl)hexyl)oxy-p-phenylenevmylene]] and PEDOT:PSS [ρoly(3,4- ethylenedioxythiophene) poly(styrenesulfonate)] can also be used as hole conductor materials. To increase its conductivity PEDOTrPSS can be mixed with glycerin, N- methylpyrrolidone, and isopropanol.

SUMMARY

[OO 11] The present invention provides methods, apparatuses and systems directed to novel photovoltaic structures for the conversion of solar irradiance into electrical free energy. In particular implementations, the novel photovoltaic structures can be fabricated using low cost and scalable processes, such as magnetron sputtering. In a particular implementation, a photovoltaic cell includes a photoactive conversion layer comprising one or more granular semiconductor and oxide layers with nanometer -size semiconductor grains surrounded by a matrix of oxide. The semiconductor and oxide layer can be a disposed between electrode layers. In a particular implementation, a photovoltaic cell includes a granular semiconductor and oxide layer with nanometer-size absorber semiconductor grains surrounded by a matrix of oxide. The semiconductor and oxide layer is disposed between electron and hole conducting layers. In some implementations, multiple semiconductor and oxide layers can be deposited. These so-called semiconductor and oxide layers absorb sun light and convert solar irradiance into electrical free energy. Upon illumination with solar irradiance, the nanometer size semiconductor grains inject electrons into the conducting band of oxide, creating charge separation and producing photovoltaic effect. Following charge separation, electrodes extract electrons and holes to produce current. The charge carriers created as a result of photon absorption in the nanometer-size semiconductor grains can be also separated by an electric field formed by the presence of p- and n-type semiconductor layers adjacent to the absorber semiconductor and oxide layer. [0012] The properties of the semiconductor grains can be controlled, and in some instances varied, to achieve a variety of effects and advantages. For example, the size of the semiconductor grains can be configured to facilitate extraction of charge carriers before they can relax to the band edge, increasing the efficiency of the photon conversion in nanometer sized semiconductor absorbers. In addition, the size and/or composition of the semiconductor grains in multiple semiconductor and oxide layers can be varied to match the band gaps of the semiconductor grains to the solar energy spectrum. This can further reduce the energy loss due to the relaxation of carriers to their respective band edges.

DESCRIPTION OF THE DRAWINGS

[0013] Figures Ia to If illustrate example photovoltaic cell structures according to various implementations of the invention.

[0014] Figures Ig, Ih and Ii illustrate the microstructure configuration of a semiconductor and oxide layer according to an implementation of the invention.

[0015] Figure Ij is a diagram illustrating how semiconductor grain diameter may be determined according to one possible implementation of the invention.

[0016] Figures 2a to 2d provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0017] Figures 3a to 3d provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0018] Figures 4a to 4j provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0019] Figures 5a to 5c provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0020] Figures 6a to 6d provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[002 IJ Figures 7a to 7b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0022] Figure 8 is a schematic diagram illustrating an example sputter deposition process.

[0023] Figure 9 is a diagram illustrating the deposition of adatoms on a substrate in a high-pressure, low mobility sputter deposition process.

[0024] Figures 10a to 1Od provide example composite layer configurations, including seed layers and interlayers, that may be used in photovoltaic cells of the present invention.

[0025] Figure 11 illustrates a photovoltaic cell configuration according to one possible implementation of the invention.

[0026] Figures 12a to 12d provide additional example composite layer configurations that that may be used in photovoltaic cells of the present invention.

[0027] Figures 13a to 13h illustrate example photovoltaic cell structures according to various implementations of the invention.

[0028] Figures 14a and 14b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0029] Figures 15a and 15e provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0030] Figures 16a and 16b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0031] Figures 17a to 17e provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0032] Figures 18a and 18b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0033] Figures 19a and 19b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0034] Figures 20a and 20b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

[0035] Figures 21a and 21b provide example composite photoactive layers that may be used in photovoltaic cells of the present invention.

DESCRIPTION OF PREFERRED EMBODIMENT(S) A. Overview

[0036] Figures Ia to If illustrate example structures and configurations of solar cells according to several possible implementations of the invention. As Figure Ia illustrates, a solar cell 100 may comprise (in overlying sequence) a glass substrate 8000, a transparent conductive layer 7000, an electron conducting material layer 1000, a semiconductor and oxide layer 2100, a hole conducting material layer 3000. This layer structure is covered with a second transparent conductive layer 7000 and a second glass layer 8000. In a particular implementation, the transparent conductive layer 7000 may be indium oxide doped with tin oxide. Electron conducting material layer 1000 may be an oxide material or n-type semiconductor material. Hole conducting material layer 3000 may be a p-type semiconductor or other hole conducting material (such as spiro-OMeTAD). Semiconductor and oxide layer 2100 may include an oxide dispersed at grain boundaries of an intrinsic semiconductor.

[0037] In other implementations, solar cell 101, as Figure Ib shows, may comprise (in overlying sequence) glass substrate 8000, transparent conductive layer 7000, electron conducting material layer 1000, semiconductor and oxide layer 2100, hole conducting material layer 3000, second transparent conductive layer 7000, and a non-transparent protective layer 8500. Figure Ic shows solar cell 102 comprising (in overlying sequence) glass substrate 8000, transparent conductive layer 7000, electron conducting material layer 1000, semiconductor and oxide layer 2100, hole conducting material layer 3000, metal contact layer 9000, and non-transparent protective layer 8500. In Figure Id, solar cell 103 comprises (in overlying sequence) glass substrate 8000, transparent conductive layer 7000, electron conducting material layer 1000, semiconductor and oxide layer 2100, hole conducting material layer 3000, second transparent conductive layer 7000, and a transparent protective layer 8700. As Figure Ie provides, solar cell 104 may include, in overlying sequence, non-transparent substrate 8600, a transparent conductive layer 7000, electron conducting material layer 1000, semiconductor and oxide layer 2100, hole conducting material layer 3000, second transparent conductive layer 7000 and glass layer 8000. In Figure If, solar cell 105 comprises (in overlying sequence) non- transparent substrate 8600, metal contact layer 9000, electron conducting material layer 1000, semiconductor and oxide layer 2100, hole conducting material layer 3000, transparent conductive layer 7000 and glass layer 8000. [0038] Electron conducting material layer 1000, semiconductor and oxide layer 2100, and hole conducting material layer 3000 are, relative to the solar cells shown in Figures Ia to If, a composite photoactive conversion layer that can be configured to produce a photovoltaic effect in response to solar energy. Semiconductor and oxide layer 2100, in some implementations, is a sensitizing or absorber layer disposed between hole conducting material layer 3000 and«an electron conducting material layer 1000. In some implementations, upon photo excitation, electrons are efficiently injected from the conducting band of the semiconductor grains of semiconductor and oxide layer 2100 into the conducting band of electron conducting material layer 1000, creating a charge separation and producing photovoltaic effect. Regeneration of the absorber semiconductor grains can occur by capture of electrons from the hole conducting material layer 3000. [0039] The material composition, layer configuration and layer arrangement of the photovoltaic cells can be configured to achieve a variety of objectives. For example, depending on material choice, the nanometer-sized grains of the intrinsic semiconductor and oxide layer 2100 can operate as absorbers in a p-n heterojunction between an oxide material (such as TiO2) and a hole conducting material (such as OMeTAD). To achieve efficient electron injection into the electron conducting layer, the bottom edge of the conductive band of the absorber, Ec(absorber), should be higher than the bottom edge of the conductive band of the electron conducting layer, Ec(electron conducting layer). On the other hand, the top edge of the valence band of the absorber, Ey(absorber), should be lower than the top edge of the valence band of the hole conducting layer, Ey,or the Fermi level of organic hole conductor material, to promote efficient regeneration of the absorber semiconductor grains. In other implementations, the layers of the cell structure can be configured to create p-n junctions with an electric field across the depletion region between a p-type semiconductor layer and an n-type semiconductor layer. One or more intrinsic semiconductor layers can be disposed between these p-type and n-type semiconductor layers, as well.

[004O]As Figures 2a to 2d provide, the structure and composition of this composite photoactive conversion layer can be varied to achieve a vast array of different photovoltaic cell structures and configurations. Figure 2a illustrates a composite photoactive conversion layer comprising, deposited in overlying sequence, an electron conducting material layer 1000 (such as an oxide material or n-type semiconductor layer), semiconductor and oxide layer 2100, and hole conducting material layer 3000 (such as a p-type semiconductor layer). As Figure 2b illustrates, the composite photoactive conversion layer may be deposited in a reverse relation comprising, in overlying deposited sequence, hole conducting material layer 3000, semiconductor and oxide layer 2100, and electron conducting material layer 1000.

[0041] Other implementations are possible. For example, a metal and oxide layer 2200 may replace the semiconductor and oxide layer 2100 as a sensitizing layer. For example, as Figure 2c shows, the composite photoactive conversion layer may comprise, in overlying sequence, electron conducting material layer 1000, metal and oxide layer 2200 and hole conducting material layer 3000. Alternatively, as Figure 2d illustrates, the composite photoactive conversion layer may comprise, in overlying sequence, hole conducting material layer 3000, metal and oxide layer 2200, and electron conducting material layer 1000. As discussed below, the metal and oxide layer 2200 may also be used in combination with the semiconductor and oxide layer 2100.

[0042] Glass layer 8000 can be a glass substrate or deposited layer made of a variety of materials, such as silicon dioxide. Alternatively, a polymer can be used. Still further, one or more of the transparent conducting layers 7000 can be replaced by metal contacts arranged in a grid (e.g., fingers and busbars) on one side (or both sides) and a full area metal contact on the other side. Additional layers, such as anti-reflection coatings can also be added. The layer stack can be deposited on glass, polymer or metal substrates. If the layer stack is deposited on top of a non- transparent substrate, the top contact is transparent to allow light penetration into the photoactive conversion layer. Glass layer 8000 can be replaced by other suitable protective layers or coatings, or be added during construction of a solar module or panel. Still further, the layers described herein may be deposited on a flat substrate (such as a glass substrate intended for window installations), or directly on one or more surfaces of a non-imaging solar concentrator, such as a trough-like or Winston optical concentrator.

A.1. Semiconductor and Oxide Layer

[0043] Structurally, semiconductor and oxide layer 2100 is a granular layer comprising a plurality of nanometer-sized cylinder-like semiconductor grains 98 contained in, or surrounded by, a matrix of oxide material 99. In other words, the oxide material is dispersed at grain boundaries 97 of the semiconductor. Formation of the semiconductor and oxide layer 2100 is discussed below. In the semiconductor and oxide layer(s), upon photoexcitation of semiconductor grains 98, electrons are injected into the surrounding oxide matrix 99 or generated charge carriers (electrons and holes) are separated by an electric field created by p-type and n-type semiconductor materials in the adjacent layers. [0044] Figures Ig to Ii illustrate an example microstructure of the semiconductor and oxide layer 2100 according to one possible implementation of the invention. One skilled in the art will recognize that these Figures are idealized representations of the microstructure of the semiconductor grains 98 and that the boundaries between the semiconductor grains and the oxide matrix may, and often will, not be defined by perfect cylinders. For example, in the semiconductor and oxide layers, the semiconductor grains will generally not have a perfect cylindrical shape. In addition, in some instances, neighboring semiconductor grains may be in direct contact as opposed to being completely separated by oxide material. The size of cylinder-like semiconductor grains in the semiconductor and oxide layer is defined by the diameter and the height of these grains. The diameters of the semiconductor grains at a given layer may vary from a minimum to a maximum grain diameter. The average semiconductor grain diameter can be defined as the mean or average value of all semiconductor grain diameters in the semiconductor and oxide layer 2100. Figure Ij shows an example of a semiconductor grain 98 surrounded by an oxide material. Since grains generally do not have a perfect cylindrical shape, the diameter of the grain can be defined as 2*(S/π)⁰⁵ where S is the area of the top surface of the grain, i.e., S is the surface area that the semiconductor grain shares with the layer deposited on top of the semiconductor and oxide layer 2100. The average diameter of the semiconductor grains in the semiconductor and oxide layer can vary considerably up to about 100 nm. However, a preferred average diameter of the semiconductor grains in the semiconductor and oxide layer can be up to 10, 15, 20 or 40 nm. Some semiconductor and oxide layers may have smaller average diameters as well. The height of the semiconductor grain is substantially equal to the thickness of the semiconductor and oxide layer 2100. The thickness of the layers can vary considerably up to about 4000 nm. However, a preferred thickness of the semiconductor and oxide layer can be up to 400 nm. In some implementations, multiple semiconductor and oxide sub-layers (each with varying the average semiconductor grain diameters ranging from 3 to 12 nm and thicknesses ranging from 3 to 25 nm) can be deposited. In one example configuration, five semiconductor and oxide sub-layers with the average semiconductor grain diameter, in descending order, of 12/10/7/5/3 nanometers and thicknesses, in descending order, of 25/10/7/5/3 nanometers can be deposited. Still further, the oxide content of the semiconductor and oxide layers can range from 1 to 99 percent of a given layer by volume. However, a preferred oxide content of the semiconductor and oxide layers can range from 5 to 75 percent of a given layer by volume.

[0045] As discussed, multiple semiconductor and oxide layers may be deposited. Furthermore, the semiconductor material in semiconductor and oxide layers may be an intrinsic semiconductor material, a p-type semiconductor material, or an n- type semiconductor material. Various implementations discussed below utilize one or more of these semiconductor and oxide layers in varying configurations, combinations and arrangements to yield high efficiency solar cells. For purposes of description, this disclosure refers to an intrinsic semiconductor and oxide layers using a reference number convention of 2 IxO, where x equals a layer number from 1 to N (where N equals the number of layers). Similarly, this disclosure refers to n- type semiconductor and oxide layers using a reference number convention of 21x1, where x equals a layer number from 1 to N. Lastly, this disclosure refers to p-type semiconductor and oxide layers using a reference number convention of 21x2, where x equals a layer number from 1 to N.

[0046] In the photovoltaic cells illustrated in Figures Ia to Ic, for example, intrinsic semiconductor grains operate as absorbers. In other words, light excites electrons in the absorber semiconductor grains 98, which are injected into the conduction band of the oxide matrix 99 or into the conduction band of an electron conductor. The absorber semiconductor grains 98 are regenerated by capture of electrons from the valence band of a hole conducting material layer 3000 (such as a p-type semiconductor). For intrinsic semiconductor and oxide layer 2100, the semiconductor material may be an intrinsic semiconductor comprising one or more of silicon (Si), germanium (Ge), tin (Sn), beta iron suicide (β-FeSi2), indium antimony (InSb), indium arsenic (InAs), indium phosphate (InP), gallium phosphate (GaP), gallium arsenic (GaAs), gallium antimony (GaSb), aluminum antimony (AlSb), silicon carbide (SiC), tellurium (Te), zinc antimony (ZnSb), mercury telluride (HgTe), led sulfide (PbS), led selenide (PbSe), led telluride (PbTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), tin telluride (SnTe), copper sulfide (CuuS (x varies from 1 to 2)), copper selenide (Cui-xSe (x varies from 1 to 2)), copper indium disulfide (CuInS₂), copper gallium disulfide (CuGaS₂), copper indium gallium disulfide, (Cu(In^Ga_x)S₂ (x varies form 0 to I)), copper indium diselenide (CuInSe₂), copper gallium diselenide (CuGaSe₂), copper indium gallium diselenide (Cu(In₁^GaJSe₂ (x varies form 0 to I)), copper silver indium gallium disulfide

(x varies form 0 to 1, y varies form 0 to I)), copper silver indium gallium diselenide (Cu^Ag J(In^Ga_J1)Se₂ (x varies form 0 to 1, y varies form 0 to I)), indium sulfide (IB12S3), indium selenide (In₂Se₃), aluminum nitride (AlN), indium nitride (InN), gallium nitride (GaN), bismuth sulfide (Bi₂Sa), antimony sulfide (Sb₂Sa), silver sulfide (Ag₂S), tungsten sulfide (WS2), tungsten selenide (WSea), molybdenum sulfide (M0S2), molybdenum selenide (MoSe2), tin sulfide (SnS_x (x varies from 1 to 2)), tin selenide (SnSe_x (x varies from 1 to 2)), and copper tin sulfide (Cu-jSnSO. [0047] The oxide material, for intrinsic semiconductor and oxide layers, may include one or more of magnesium (Mg) oxide, aluminum (Al) oxide, silicon (Si) oxide, titanium (Ti) oxide, vanadium (V) oxide, chromium (Cr) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide, copper (Cu) oxide, zinc (Zn) oxide, gallium (Ga) oxide, germanium (Ge) oxide, selenium (Se) oxide, yttrium (Y) oxide, zirconium (Zr) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, indium (In) oxide, tin (Sn) oxide, antimony (Sb) oxide, tellurium (Tl) oxide, hafnium (Hf) oxide, tantalum (Ta) oxide, tungsten (W) oxide, mercury (Hg) oxide, lead (Pb) oxide, and bismuth (Bi) oxide.

[0048]For n-type semiconductor and oxide layers 2101, 2111, and 2121, for example, the semiconductor material may be an n-type semiconductor comprising one or more of silicon (Si), germanium (Ge), tin (Sn), beta iron suicide (β-FeSia), indium antimony (InSb), indium arsenic (InAs), indium phosphate (InP), gallium phosphate (GaP), gallium arsenic (GaAs), gallium antimony (GaSb), aluminum antimony (AlSb), silicon carbide (SiC), tellurium (Te), zinc antimony (ZnSb), mercury telluride (HgTe), led sulfide (PbS), led selenide (PbSe), led telluride (PbTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), tin telluride (SnTe), copper sulfide (Cui-_vS (x varies from 1 to 2)), copper selenide (Cui._λSe (x varies from 1 to 2)), copper indium disulfide (CuInS₂), copper gallium disulfide (CuGaS₂), copper indium gallium disulfide, (Cu(In_LxGa_x)S₂ (x varies form 0 to I)). copper indium diselenide (CuInSe₂), copper gallium diselenide (CuGaSe₂), copper indium gallium diselenide (Cu(In₁^Ga_x)Se₂ (x varies form 0 to I)). copper silver indium gallium disulfide-<Cu₁._xAg_x)(In₁._>Gay)S2 (x varies form 0 to 1, y varies form 0 to I)), copper silver indium gallium diselenide

(x varies form 0 to 1, y varies form 0 to I)), indium sulfide (In₂Sa), indium selenide (In^Ses), aluminum nitride (AlN), indium nitride (InN), gallium nitride (GaN), bismuth sulfide (R-2S3), antimony sulfide (Sb2Ss), silver sulfide (Ag2S), tungsten sulfide (WS2), tungsten selenide (WSe₂), molybdenum sulfide (M0S2), molybdenum selenide (MoSβ2), tin sulfide (SnSx (x varies from 1 to 2)), tin selenide (SnSe_x (x varies from 1 to 2)), copper tin sulfide (CmSnS.)). Such semiconductors may be doped by adding an impurity of valence-five elements such as nitrogen (N), phosphorus (P), arsenic (As), or antimony (Sb)), in order to increase the number of free (in this case negative (electron)) charge carriers.

[0049] The oxide material, for n-type semiconductor and oxide layers, may include one or more of magnesium (Mg) oxide, aluminum (Al) oxide, silicon (Si) oxide, titanium (Ti) oxide, vanadium (V) oxide, chromium (Cr) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide, copper (Cu) oxide, zinc (Zn) oxide, gallium (Ga) oxide, germanium (Ge) oxide, selenium (Se) oxide, yttrium (Y) oxide, zirconium (Zr) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, indium (In) oxide, tin (Sn) oxide, antimony (Sb) oxide, tellurium (Tl) oxide, hafnium (Hf) oxide, tantalum (Ta) oxide, tungsten (W) oxide, mercury (Hg) oxide, lead (Pb) oxide, and bismuth (Bi) oxide.

[0050]For p-type semiconductor and oxide layers 2102, 2112, and 2122, for example, the semiconductor material may be an n-type semiconductor comprising one or more of silicon (Si), germanium (Ge), tin (Sn), beta iron suicide (β-FeSi2), indium antimony (InSb), indium arsenic (InAs), indium phosphate (InP), gallium phosphate (GaP), gallium arsenic (GaAs), gallium antimony (GaSb), aluminum antimony (AlSb), silicon carbide (SiC), tellurium (Te), zinc antimony (ZnSb), mercury telluiϊde (HgTe), led sulfide (PbS), led selenide (PbSe), led telluride (PbTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), tin telluride (SnTe), copper sulfide (Cui-vS (x varies from 1 to 2)), copper selenide (Cui_-λSe (x varies from 1 to 2)), copper indium disulfide (CuInS₂), copper gallium disulfide

(CuGaS₂), copper indium gallium disulfide, (Cu(In_LxGa_x)S₂ (x varies form 0 to I)), copper indium diselenide (CuInSe₂), copper gallium diselenide (CuGaSe₂), copper indium gallium diselenide (Cu(In_1-1JGa_x)Se₂ (x varies form 0 to I)). copper silver indium gallium disulfide (Cu,

(x varies form 0 to 1, y varies form 0 to I)), copper silver indium gallium diselenide (CuL_xAg_x)(InI-_XGa_J1)Se₂ (x varies form 0 to 1, y varies form 0 to I)), indium sulfide (In₂S^), indium selenide (I^Sea), aluminum nitride (AlN), indium nitride (InN), gallium nitride (GaN), bismuth sulfide (BiaSe), antimony sulfide (Sb2Sa), silver sulfide (Ag2S), tungsten sulfide (WS₂), tungsten selenide (WSe₂), molybdenum sulfide (M0S2), molybdenum selenide (MoSβ2), tin sulfide (SnS_x (x varies from 1 to 2)), tin selenide (SnSe_x (x varies from 1 to 2)), copper tin sulfide (Cu₄SnS-O. Such semiconductors may be doped by adding an impurity of valence-three elements such as boron (B), gallium (Ga), indium (In), or aluminum (Al), in order to increase the number of free (in this case positive (hole)) charge carriers. [0051] The oxide material, for p-type semiconductor and oxide layers, may include one or more of magnesium (Mg) oxide, aluminum (Al) oxide, silicon (Si) oxide, titanium (Ti) oxide, vanadium (V) oxide, chromium (Cr) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide, copper (Cu) oxide, zinc (Zn) oxide, gallium (Ga) oxide, germanium (Ge) oxide, selenium (Se) oxide, yttrium (Y) oxide, zirconium (Zr) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, indium (In) oxide, tin (Sn) oxide, antimony (Sb) oxide, tellurium (Tl) oxide, hafnium (Hf) oxide, tantalum (Ta) oxide, tungsten (W) oxide, mercury (Hg) oxide, lead (Pb) oxide, and bismuth (Bi) oxide.

[0052] Metal and oxide layer 2200 includes a metal and an oxide. In a particular implementation, the metal may be at least one metal material selected from group consisting of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru₁ Rh, Pd, Pt, Ag, Hf, Ta, W, Re, Ir, Au. The oxide material may be at least one oxide material selected from group consisting of: magnesium (Mg) oxide, aluminum (Al) oxide, silicon (Si) oxide, titanium (Ti) oxide, vanadium (V) oxide, chromium (Cr) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide, copper (Cu) oxide, zinc (Zn) oxide, gallium (Ga) oxide, germanium (Ge) oxide, selenium (Se) oxide, yttrium (Y) oxide, zirconium (Zr) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, indium (In) oxide, tin (Sn) oxide, antimony (Sb) oxide, tellurium CTl) oxide, hafnium (Hf) oxide, tantalum (Ta) oxide, tungsten (W) oxide, mercury (Hg) oxide, lead (Pb) oxide, and bismuth (Bi) oxide.

A.2. Electron Conducting Material Layer

[0053] Electron conducting material layer 1000 may be an oxide material, an n-type semiconductor material, or an organic electron conducting material. Inorganic electron conducting materials, such as oxides and n-type semiconductors, may have a crystalline structure. The melting temperature of an inorganic electron conducting material (oxide or n-type semiconductor) and glass temperature of organic electron conducting material should be above 80 C. [0054] Electron conducting material layer 1000 may be an oxide material including one or more of titanium CTi) oxide (such as TiOa), aluminum (Al) oxide, cobalt (Co) oxide, silicon (Si) oxide, tin (Sn) oxide, zinc (Zn) oxide, molybdenum (Mo) oxide, tantalum (Ta) oxide, tungsten (W) oxide, indium (In) oxide, magnesium (Mg) oxide, bismuth (Bi) oxide, copper (Cu) oxide, vanadium (V) oxide, chromium (Cr) oxide. Electron conducting material layer 1000 may be an n-type semiconductor material including one or more of silicon (Si), germanium (Ge), tin (Sn), beta iron suicide (β- FeSi2), indium antimony (InSb), indium arsenic (InAs), indium phosphate (InP), gallium phosphate (GaP), gallium arsenic (GaAs), gallium antimony (GaSb), aluminum antimony (AlSb), silicon carbide (SiC), tellurium (Te), zinc antimony (ZnSb), mercury telluride (HgTe), led sulfide (PbS), led selenide (PbSe), led telluride (PbTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), tin telluride (SnTe), copper sulfide (Cui._xS (x varies from 1 to 2)), copper selenide (Cui- _xSe (x varies from 1 to 2)), copper indium disulfide (CuInS₂), copper gallium disulfide (CuGaS₂), copper indium gallium disulfide, (Cu(In₁^Ga_x)S₂ (x varies form 0 to I)), copper indium diselenide (CuInSe₂), copper gallium diselenide (CuGaSe₂), copper indium gallium diselenide (Cu(In_LxGa_x)Se₂ (x varies form 0 to I)), copper silver indium gallium disulfide (Cu₁._λAg_x)(Ini._yGa_y)S₂ (x varies form 0 to 1, y varies form 0 to I)), copper silver indium gallium diselenide (Cu₁._xAg_x)(Ini._yGa_y)Se₂ (x varies form 0 to 1, y varies form 0 to I)), indium sulfide (In₂S₃), indium selenide (In₂Se₃), aluminum nitride (AlN), indium nitride (InN), gallium nitride (GaN), bismuth sulfide (Bi₂Ss), antimony sulfide (Sb2S.s), silver sulfide (Ag2S), tungsten sulfide (WS2), tungsten selenide

molybdenum sulfide (M0S2), molybdenum selenide (MoSe2), tin sulfide (SnS_x (x varies from 1 to 2)), tin selenide (SnSe_x (x varies from 1 to 2)), copper tin sulfide (Cu4SnS,i). Such semiconductors may be doped by adding an impurity of valence-five elements such as nitrogen (N), phosphorus (P), arsenic (As), or antimony (Sb)), in order to increase the number of free (in this case negative (electron)) charge carriers. [0055] Alternatively, electron conducting material layer 1000 may be an organic electron conducting material such as perylene benzimidazole (PBI), perylene bis(piridylethylimide) (PPyEI), perylene-bis(phenethylimide) OPPEI) and [6,6]- phenyl-C?! -butyric acid methyl ester (PCBM).

A.3. Hole Conducting Material Layer

[0056] Hole conducting material layer 3000 may be ap-type semiconductor or other inorganic or organic hole conducting material. In a particular implementation, the melting temperature of an inorganic hole conducting material and the glass temperature of organic hole conducting material should be above 80 C. [0057] In one implementation, hole conducting material layer 3000 may comprise a semiconductor material that may be doped by adding an impurity of valence-three elements such as boron (B), gallium (Ga), indium (In) or aluminum (Al), in order to increase the number of free (in this case positive (hole)) charge carriers, including at least one of the following materials: silicon (Si), germanium (Ge), tin (Sn), beta iron suicide φ-FeSi2), indium antimony (InSb), indium arsenic (InAs), indium phosphate (InP), gallium phosphate (GaP), gallium arsenic (GaAs), gaUium antimony (GaSb), aluminum antimony (AlSb), silicon carbide (SiC), tellurium CTe), zinc antimony (ZnSb), mercury telluride (HgTe), led sulfide (PbS), led selenide (PbSe), led telluride (PbTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), tin telluride (SnTe), copper sulfide (Cui._xS (x varies from 1 to 2)), copper selenide (Cui.jSe (x varies from 1 to 2)), copper indium disulfide (CuInS₂), copper gallium disulfide (CuGaSa), copper indium gallium disulfide, (Cu(In_LxGa_x)S₂ (x varies form 0 to I)), copper indium diselenide (CuInSe₂), copper gallium diselenide (CuGaSe₂), copper indium gallium diselenide (Cu(In₁^Ga_x)Se₂ (x varies form 0 to I)), copper silver indium gallium disulfide (Cu_LxAg_x)(In_1-J1Ga_J1)S₂ (x varies form 0 to 1, y varies form 0 to l))rcopper silver indium gallium diselenide (Cu_11xAg_x)(In_I. _J1Ga₁₁)Se₂ (x varies form 0 to 1, y varies form 0 to I)), indium sulfide (In≤Sg), indium selenide (!112Se₃), aluminum nitride (AlN), indium nitride (InN), gallium nitride (GaN), bismuth sulfide (BiaSβ), antimony sulfide (Sb2Sa), silver sulfide (Ag2S), tungsten sulfide (WS2), tungsten selenide (\VSe2), molybdenum sulfide (M0S2), molybdenum selenide (MoSea), tin sulfide (SnS_λ (x varies from 1 to 2)), tin selenide (SnSe_x (x varies from 1 to 2)), copper tin sulfide (CuiSnS-i). Such semiconductors may be doped by adding an impurity of valence-three elements such as boron (B) or aluminum (Al), in order to increase the number of free (in this case positive (hole)) charge carriers. Other suitable p-type semiconductor materials include copper thiocyanate (CuSCN), cuprous iodide (CuI), copper aluminum oxide (CuAlOa) and organic hole-conductors, such as spiro-OMeTAD (2,2',7,7'-tretakis(N,N-di-_Jp- methoxyphenyl- amine)-9-9'-spirofifluorene) (partial oxidation of spiro-OMeTAD by N(PhBr)aSbClβ can be used to control the dopant level), MEH-PPV tpoly[2- methoxy-[5-(2'-ethyl)hexyl]oxy-p-phenylenevinylene]] and PEDOTiPSS £poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate)] (to increase its conductivity PEDOTrPSS can be mixed with glycerin, N-methylpyrrolidone, and isopropanol).

B. Fabrication of Photovoltaic Cell Layers

[0058] The semiconductor and oxide layers can be fabricated using a sputter deposition process (such as magnetron sputtering) in order to produce a layer structure that comprises semiconductor grains surrounded by an oxide matrix. Sputtering conditions and other process settings result in dispersal of oxide at grain boundaries of the semiconductor, as well as control the size of semiconductor grains and the ratio between the volume fraction of semiconductor and oxide materials. In a particular implementation, a semiconductor and oxide layer including semiconductor grains isolated in a matrix of oxide can be prepared by sputtering a metal interlayer (such as an Ru interlayer) and then cosputtering a semiconductor with an oxide material with low adatom mobility. The oxide material moves into the, semiconductor grain boundaries and isolates the semiconductor grains. To reduce decomposition of oxide during the sputtering, an oxide material with large diatomic bond strength between metal and oxygen can be used.

[0059] As discussed above, the semiconductor grains 98 have a generally cylindrical or columnar shape where the dimension of the cylinder depends on the semiconductor grain diameter and the thickness of the semiconductor and oxide layer. The ratio between the volume fraction of oxide and semiconductor material can be controlled by varying the composition of sputtering target (source). Additionally, the diameter of absorber semiconductor grains can be controlled by sputtering an interlayer prior to sputtering the semiconductor and oxide layer. Semiconductor grains in the semiconductor and oxide layer grow on top of the interlayer grains while oxide is dispersed around the semiconductor grains. Thus, in most instances, the diameter of interlayer grains can control or strongly influence the diameter of semiconductor grains in the semiconductor and oxide layer deposited on the interlayer. Sometimes, if the interlayer grains are large (over 15 nm), it is also possible that two or more semiconductor grains grow on a single interlayer grain. The interface area between semiconductor grains 98 and oxide (both the oxide matrix and oxide in an adjacent layer) depends on the semiconductor grain diameter and the thickness of the semiconductor and oxide layer. However, the interface area can be over 100 times larger than that for a flat junction between an oxide layer and a semiconductor layer or films. As illustrated above, the semiconductor and oxide layer can be located between an oxide material (or other n-type semiconductor) and a p-type semiconductor (or other hole conducting material) that can also be sputtered with magnetron sputtering. This layer structure is used in solar cells where the semiconductor grains absorb the solar radiation. This process also allows fabrication of multilayer structures with semiconductor grains surrounded with oxide materials, where an oxide material preferentially grows on top of an oxide material and a semiconductor material preferentially grows on top of a semiconductor material. In multilayer structures the composition of oxide and semiconductor in each layer can be varied separately to increase the efficiency of photon conversion.

[006O]In an example sputtering process, argon (Ar) ions strike a source generating atoms that are deposited on a substrate as shown in Figure 8. Positive argon ions may be accelerated toward the source by applying negative potential on the source. The distance from the target to the substrate is D and Ar pressure in the sputter chamber is p. Mobility of atoms deposited on the substrate is affected by the kinetic energy of the deposited atoms as well as the kinetic energy of Ar neutrals that strike the substrate surface. Ar ions that strike the target source receive an electron and bounce off the source as Ar neutrals. If these Ar neutrals strike the substrate surface they increase the mobility of the deposited atoms. High pressure in the sputtering chamber, p, will also increase the probability of collision between Ar neutrals and the rest of the Ar atoms in the chamber reducing Ek of the Ar neutrals and reducing the effect of Ar neutrals on mobility of deposited atoms. In addition, a low negative voltage bias may be applied to the substrate to influence or further control surface mobility.

[0061] Similarly, the kinetic energy, Eu, and angle, α, (see Fig. 9) at which deposited atoms land on a substrate surface depend on Ar pressure in the sputtering chamber. If the pressure is high, the probability of collisions between deposited atoms and Ar atoms is larger resulting in a reduction of Ek(atoms) and an increase of α of the deposited atoms (see Fig. 9). In other words, these collisions alter the direction or angle at which atoms are deposited on the substrate surface. As Figure 9 illustrates, α is an angle between the direction that is normal to the film plane and the direction of deposited atom. Without collisions with Ar atoms, the majority of atoms will be deposited at low α angles (i.e., closer to perpendicular to the substrate surface). Collisions increase the average deposition angle α resulting in reduced deposition rate in the valleys in comparison to the tops of the substrate surface.

[0062] As an example, a ruthenium (Ru) interlayer can be sputtered at high pressure 6 Pa (45 mTorr) of Ar on a seed layer. Sputtering at higher pressure reduces the mean free path of sputtered Ru atoms (and Ar neutrals reflected from a Ru target) due to collisions with Ar atoms on their path from target to substrate. The collisions reduce the kinetic energy of deposited Ru atoms reducing surface diffusion of Ru atoms, and randomize the angle at which Ru atoms are deposited onto the substrate away from the direction that is normal to film surface. This causes roughness to increase with increasing film thickness because the "tops" of neighboring column structures block the adatoms incident line-of-sight path to the "valleys". Thus, the sputtering rate in the "valleys" is lower than that on the "tops" of the rough area due to the shadowing effect. Continued growth under controlled sputtering conditions (such as low temperature and high pressure) therefore results in increasingly voided (physically separated) columnar structures. [0063] Applying a similar sputtering process to a composite target of (or otherwise co-sputtering) a semiconductor and an oxide results in a similar structure. That is, the semiconductor atoms deposited on the substrate surface form columnar structures during the sputtering process, while the oxide material is dispersed by the semiconductor grain boundaries forming a matrix that surrounds or isolates the semiconductor grains.

[0064] While the semiconductor and oxide layer can be formed directly on an oxide or other layer, it can also be grown or sputter deposited on an interlayer, such as an Ru interlayer (as formed above), which induces or promotes vertical columnar growth in the semiconductor and oxide layer. That is, the interlayer can control the crystallographic growth orientation, grain diameter of semiconductor and most importantly surface roughness required for segregating oxide in grain boundaries. For example, cosputtering of semiconductor and oxide, under high pressure, causes semiconductor grains to grow on top of the Ru grains with oxide segregating to semiconductor grain boundaries. In addition, a metal material may be added to the semiconductor and oxide layer to promote growth of the desired composition and rαicrostructure of the semiconductor and oxide layer. The metal material may be at least one of the following materials: Al, Ti, V, Cr, Mn, Pe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Pt, Ag, Hf, Ta, W, Re, Ir, and Au. The metal; material may be embodied in a separate target and co-sputtered with semiconductor and oxide target(s) or be mixed into the same target.

[0065] Still further, after deposition of one or more semiconductor and oxide layers, the structure may be annealed in the presence of inert or reactive gasses to obtain desired composition, compound and crystal structures and/or to reduce defects. Annealing temperatures may vary up to 1000 degrees C; however, annealing temperatures in the range of 150 to 600 degrees C are preferred. After a given annealing step, the structure is preferably cooled if the next layer to be sputtered is also semiconductor and oxide layer.

[0066] In a particular implementation, the semiconductor and oxide layer can be formed using a magnetron sputtering in the presence of a gas, under one or more of the following sputtering conditions: 1) a total atmospheric pressure during sputtering of at least 0.8 Pa (6 mTorr); 2) an applied bias on a substrate during the sputtering of less than 400 V, and 3) a temperature of a substrate during the sputtering below 200 degrees C. Total atmospheric pressure in the chamber, ptot, required to achieve the segregation of oxide to grain boundaries in the semiconductor and oxide layer depends on the distance from source to the substrate, D, and the deposition rate, DR, (the number of atoms that land on a substrate per second and can be also defined as a thickness of the deposited layer per second). As D increases, oxide segregation at semiconductor grain boundaries can be achieved with lower ptot pressure. IfD increases the probability of collisions between deposited atoms and Ar atoms increases. On the other hand, as DR increases, ptot pressure has to be higher to lower the surface mobility of deposited atoms required for the oxide segregation. For example, if D = 2 cm, and DR is larger than 1 nm/s, ptot pressure should be larger than 1.3 Pa (10 mTorr). If D = 2 cm, and DR is larger than 5 nm/s, ptot pressure should be larger than 2 Pa (15 mTorr). If D = 5 cm, and DR is larger than 1 nm/s, ptot pressure should be larger than 1 Pa (8 mTorr). If D = 10 cm, and DR is larger than 1 nm/s, ptot pressure should be larger than 0.8 Pa (6 mTorr). If D = 10 cm, and DR is larger than 5 nm/s, ptot pressure should be larger than 1 Pa (δ mTorr).

[0067] In some cases a negative bias can be applied to the substrate. The bias increases mobility of deposited atoms on the substrate surface. The semiconductor and oxide layer is sputtered with the bias that is less than 400 Volts (V). In many instances, the bias can be below 200 V. In addition, the semiconductor and oxide layer can be sputtered in the presence of at least one of the gasses argon (Ar), krypton (Kr) and xenon (Xe). The semiconductor and oxide layer can be sputtered in a reactive environment that, in addition to one or more of Ar, Kr and Xe, can also contain oxygen (O2), nitrogen (N2), hydrogen (H), hydrogen sulfide (H2S), and hydrogen selenide (BbSe). The semiconductor and oxide layer can be sputtered from a single target including both semiconductor and oxide materials, or co- sputtered at the same time from two or more different targets. The semiconductor and oxide layer can be also annealed in CdCIa vapors.

[0068] As mentioned above, in order to obtain surface roughness that can improve oxide segregation, an interlayer can be sputtered prior to sputtering the semiconductor and oxide layer. The presence of the interlayer can improve crystallographic growth of the semiconductor and oxide layer and narrow the diameter distribution of semiconductor grains. Figures 10a and 10b illustrate different possible interlayer structures that can be formed. Figure 10a shows the semiconductor and oxide layer 2100 and an interlayer 5000. Interlayer 5000 may include 1) one or more metallic layers, 2) one or more semiconductor layers, or 3) one or more oxide layers. Alternatively, Figure 10b shows semiconductor and oxide layer 2100 and an interlayer 5001 that comprises one or more layers of a metal and an oxide material, where the oxide is dispersed at grain boundaries of the metal. [0069] Suitable metals for the interlayer 5000 or 5001 include Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Ir, and Au. Suitable semiconductors for the interlayer 5000 or 5001 include Si, Ge, Sn, β-FeSia, InSb, InAs, InP, GaP, GaAs, GaSb, AlSb, SiC, Te, ZnSb, HgTe, PbS, PbSe, PbTe, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, SnTe, CULXS (x = 1 to 2),

(x = 1 to 2), CuInS₂, CuGaS₂, Cu(In_LxGa_x)S₂ (x = 0 to 1), CuInSe₂, CuGaSe₂, Cu(In_LxGa_x)Se₂ (x = 0 to I)),

(x = 0 to 1, y = 0 to 1), (Cu_LxAg_x)(In_LyGa_V)Se₂ (_x = o to 1, y = 0 to 1), In₂S₃, In₂Se₃, AlN, InN, GaN, Bi₂S₃, Sb₂S₃, Ag₂S, WS₂, WSe₂, MoS₂, MoSe2, SnS_x (x = 1 to 2), SnSe_x (x = 1 to 2), Cu4SnS.t. Suitable oxide materials for the interlayer 5000 or 5001 include magnesium (Mg) oxide, aluminum (Al) oxide, silicon (Si) oxide, titanium (Ti) oxide, vanadium (V) oxide, chromium (Cr) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide, copper (Cu) oxide, zinc (Zn) oxide, gallium (Ga) oxide, germanium (Ge) oxide, selenium (Se) oxide, yttrium (Y) oxide, zirconium (Zr) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, indium (In) oxide, tin (Sn) oxide, antimony (Sb) oxide, tellurium (Tl) oxide, hafnium (Hf) oxide, tantalum (Ta) oxide, tungsten (W) oxide, mercury (Hg) oxide, lead (Pb) oxide, and bismuth (Bi) oxide. The interlayer can sputtered with a magnetron sputtering technique, where the sputtering conditions comprise one or more of 1) a total atmospheric pressure of at least 0.8 Pa (6 mTorr), 2) an applied bias to the substrate of less than 400 V, and 3) a substrate temperature of below 200 C. The interlayer can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr), and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) to achieve columnar growth of interlayer grains and to promote growth of semiconductor grains on top of the interlayer grains with oxide segregating to semiconductor grain boundaries. Sputtering can be performed in at least one of the gasses, Ar, Kr and Xe. Sputtering can be also performed in a reactive environment that also contains oxygen (O2), nitrogen (N2), hydrogen (H), hydrogen sulfide (H₂S), and hydrogen selenide (HaSe). The interlayer can be subsequently annealed in an environment that contains argon (Ar), krypton (Kr), xenon (Xe), oxygen (O2), nitrogen (Na), hydrogen (H), hydrogen sulfide (H₂S), hydrogen selenide (H₂Se) and/or CdCIa vapors. [007O]In order to further improve growth of the interlayer and therefore the semiconductor and oxide layer 2100, a seed layer 6000 can be sputtered on the substrate before sputtering the interlayer 5000 (see Figs.10c and 1Od). A method of manufacturing the semiconductor and oxide layer can comprise sputter depositing the seed layer 6000 with a magnetron sputtering technique at a total atmospheric pressure less than 0.8 Pa (6 mTorr) and a substrate temperature below 200 C, and then sputter depositing the interlayer 5000 under conditions including a total atmospheric pressure of at least 1.3 Pa (10 mTorr), an applied substrate bias less than 400 V, and a substrate temperature less than 150 C. The method may further comprise sputter depositing a semiconductor and oxide layer 2100 under conditions including a total atmospheric pressure of at least 1.3 Pa (10 mTorr), an applied substrate bias less than 200 V, and a substrate temperature below 150 C. The foregoing is only intended to be illustrative. Other process conditions can also be used.

[0071] Sputtering of seed layer 6000 can be performed in at least one of the gasses, Ar, Kr and Xe. Sputtering can be also performed in the reactive environment that also contains oxygen (O2), nitrogen (N2), hydrogen (H), hydrogen sulfide (H2S), and hydrogen selenide OføSe) with a total sputtering pressure lower than 1.3 Pa (10 mTorr). During the sputtering of the seed layer 6000 a bias voltage may be applied to the substrate to increase mobility of deposited atoms while growing the seed layer to yield a smooth layer surface that promotes desired growth and structure of the interlayer 5000.

[0072] A benefit of the high pressure sputtering processes described herein is the formation of semiconductor grains separated by an oxide matrix. This microstructure is desired in solar cells where semiconductor grains inject electrons in the conductive band of an oxide and/or an n-type semiconductor material, and inject holes in the valence band of a hole conducting material. Relaxation rates of hot carriers are very fast in bulk semiconductors. However, the rate can be slowed if semiconductor grain diameter is reduced below about 10 to 20 nm. This allows the extraction of hot carriers before they can relax to the band edge (and/or generation of two or more electron-hole pairs from a single photon), increasing the efficiency of the photon conversion in nanometer-sized semiconductor absorbers. The high pressure sputtering process can be used to produce semiconductor grains with the average diameter below 10 nm. The average semiconductor grain diameter can be controlled by varying one or more of 1) sputtering pressure of the seed layer, interlayer and/or the semiconductor and oxide layer, 2) the thickness of the seed layer and the interlayer, and 3) the ratio between the semiconductor and oxide volume fraction in the semiconductor and oxide layer. Furthermore, the shape of the semiconductor grains can be controlled using a high pressure sputtering process. By changing the semiconductor and oxide layer thickness, for example, the shape of the semiconductor grains can be varied from that of a thin to that of thick cylindrical like shape.

[0073] As Figure 1Od illustrates, the high pressure sputtering method can also be used to create a composite semiconductor and oxide layer having multiple sublayers 2100, 2110, and 2120 ("SOL sub-layer"). One or more characteristics of each semiconductor and oxide layer may be varied to achieve desired results, such as varying semiconductor grain diameter and height (achieved by varying the semiconductor and oxide layer thickness) to vary the resulting band gap of the semiconductor grains. For example, each SOL sub-layer may contain the same or different semiconductor materials. Each SOL sub-layer may contain the same or different oxide materials. In addition the ration between the semiconductor and oxide volume fraction can be varied across the layers.

[0074] The described flexibility of the process is quite advantageous for solar cells because it allows varying the band gap, E₈, of semiconductor grains in each SOL sub-layer. For example, assume that semiconductor and oxide absorption layers 2100, 2110, 2120 in a solar cell are designed as shown in Figure 1Od and that solar illumination enters from the top of the layer structure. To increase efficiency of the solar cell, energy or band gap, E_g, of semiconductor grains can be varied from a larger value in the top sub-layer 2120 to a smaller value in the bottom sub-layer 2100. The band gap can be varied between about 0.5 to 3 eV to capture or take advantage of a broader spectrum of light energy. The band gap, E_g, of semiconductor grains can be varied by changing the diameter and the height of the semiconductor grains in the SOL sub-layers and/or by changing the composition of the semiconductor grains. The band gap of each layer can be step wise varied over a range of the solar spectrum to achieve a high-efficiency cell. [0075] Figure 11 illustrates a possible solar cell structure that may be constructed with the semiconductor and oxide layer (s), as well as seed layer 6000 and interlayer 5000, disposed between an electron conducting layer 1000 and a hole conducting layer 3000. Electric contacts (such as transparent conductive layers, metal grids and layers), non-reflective coatings, and/or protective layers can also be added to the layered structure of the solar cell as described above. Additional example solar cell structures are described below in Section C.

C. Alternative Cell Structures and Configurations

[0076] Figure 3a shows a solar cell structure according to which is deposited in overlying sequence, an oxide material or n-type semiconductor layer 1000, a metal and oxide layer 2200, a semiconductor and oxide layer 2100, a p-type semiconductor or other hole conducting material layer 3000. As mentioned above, layers 1000, 2200 and 2100 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Oxide material or n-type semiconductor layer 1000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr), and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) to form an interlayer to promote desired growth of metal grains of the metal and oxide layer 2200. Hole conducting material layer 3000 can sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr).

[0077] Figure 3b illustrates a cell structure according to which is deposited, in overlying sequence, a p-type semiconductor or other hole conducting material layer 3000, a metal and oxide layer 2200, a semiconductor and oxide layer 2100, and an oxide material or n-type semiconductor layer 1000. Layers 3000, 2200 and 2100 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 3000 can be also be first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr) and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) to form an interlayer having a desired surface roughness that promotes growth of metal grains of the metal and oxide layer 2200. Layer 1000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr).

[0078] Figure 3c illustrates a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, a semiconductor and oxide layer 2100, a metal and oxide layer 2200, and a p-type semiconductor or other hole conducting material layer 3000. Layers 1000, 2200 and 2100 can deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 1000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr), and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) to yield desired surface properties. Layer 3000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr).

[0079] Figure 3d shows a cell structure in which are deposited, in overlying sequence, a p-type semiconductor or other hole conducting material layer 3000, semiconductor and oxide layer 2100, metal and oxide layer 2200, an oxide material or n-type semiconductor layer 1000. Layers 3000, 2200 and 2100 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 3000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr) and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr). Layer 1000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). [0080] Figure 4a provides a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, two or more semiconductor and oxide layers (2100, 2110, ... 2InO), and p-type semiconductor or other hole conducting material layer 3000. As discussed above, the variable n refers to a layer number. The composition of semiconductor material in layers 2100, 2110, ..., 2InO can be varied to vary the band gap of semiconductor material and increase efficiency of the solar cell. For example, the semiconductor of layer 2100 can be different from the semiconductor of layer 2110. Layers 1000, 2100, 2110, ..., 2InO can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 1000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr) and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) as discussed above. Layer 3000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr).

[0081] Figure 4b shows a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, two or more semiconductor and oxide layers 2100, 2110, ..., 2 InO, a p-type semiconductor or other hole conducting material 3000. The size (diameter and/or height) of semiconductor grains in layers 2100, 2110, ..., 2InO can be varied to vary the band gap of semiconductor material and increase photovoltaic efficiency of this structure. In a particular implementation, the size of the semiconductor grains in the first layer 2100 is the largest (relative to all other semiconductor and oxide layers), with semiconductor grain size decreasing with each successive layer. Layers 1000, 2100, 2110, ..., 2InO can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 1000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr) and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr). Layer 3000 can sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). Similarly, Figure 4c illustrates a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, two or more semiconductor and oxide layers 2100, 2110, ..., 2 InO, ap-type semiconductor or other hole conducting material 3000. The size of the semiconductor grains and the composition of the semiconductor grains in layers 2100, 2110, ..., 2InO can be varied to vary the band gap of semiconductor material and increase photovoltaic efficiency. In any of the foregoing configurations, an intervening layer (3500, 3510, .... 35(n+l)0), such as a thin layer of oxide, may be deposited between each of the semiconductor and oxide layers 2100, 2110, ..., 2InO to isolate the semiconductor grains as shown in Figures 4f, 4g, and 4h. The thickness of layers 3500, 3510, ..., 35(n+l)0 can be below 10 nm. In one implementation, the thickness of layers 3500, 3510, ..., 35(n+ 1)0 is below 4 nm. _j

[0082] In some particular implementations, solar cell structures including semiconductor and oxide layers where the semiconductor material (or grain) is a p- type semiconductor or an n-type semiconductor can also be constructed. Figure 4d, for example, illustrates, a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, n-type semiconductor and oxide layer 2101, p-type semiconductor and oxide layer 2112, and semiconductor or other hole conducting material layer 3000. Seed layers and interlayers may also be disposed between layer 1000 and n-type semiconductor and oxide layer 2101. In addition, one or more intrinsic semiconductor and oxide layers 2110 (see Figure 4e) can be disposed between the n-type semiconductor and oxide layer 2101 and p-type semiconductor and oxide layer 2122. In any of the foregoing configurations, an intervening layer (3500, 3510, ..., 35(n+l)0), such as a thin layer of oxide, may be deposited between each of the semiconductor and oxide layers 2101, 2110, ..., 2112 to isolate the semiconductor grains as shown in Figures 4i, and 4j. The size (diameter and/or height) and/or composition of the semiconductor grains of one or more of these semiconductor and oxide layers 2101, 2110, 2112, etc. can be varied to vary band gap of semiconductor material and increase photovoltaic efficiency. As Figure 6a illustrates, one or more metal and oxide layers 2200 may be disposed between the n-type semiconductor and oxide layer 2101 and p-type semiconductor and oxide layer 2112.

[0083] Still further, as Figures 5a to 5c provide, the hole conducting material layer 3000 may be deposited before the electron conducting material layer 1000 and intervening layers. Figure 5a, for example, provides a cell structure in which are deposited, in overlying sequence, a p-type semiconductor or other hole conducting material layer 3000, two or more semiconductor and oxide layers 2100, 2110, ... 2InO, and an oxide material or n-type semiconductor 1000 layer. The diameter and height of semiconductor grains and the composition of semiconductor grains in layers 2100, 2110, ... 2InO can be varied to vary band gap of the semiconductor material and increase efficiency. As mentioned before, layers 3000, 2100, 2110, ... 2InO can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Layer 3000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr) and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr). Layer 1000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). [0084] Figure 5b shows a cell structure in which are deposited, in overlying sequence, a p-type semiconductor or other hole conducting material layer 3000, p- type semiconductor and oxide layer 2102, n-type semiconductor and oxide layer 2111, and an oxide material or n-type semiconductor 1000. In addition, one or more intrinsic semiconductor and oxide layers 2110 (see Figure 5c) can be disposed between the p-type semiconductor and oxide layer 2102 and n-type semiconductor and oxide layer 2121. The size (diameter and/or height) and/or composition of the semiconductor grains of one or more of these semiconductor and oxide layers 2102, 2121, etc. can be varied to vary band gap of semiconductor material and increase photovoltaic efficiency. In addition, as Figure 6b illustrates, one or more metal and oxide layers 2200 may be disposed between the p-type semiconductor and oxide layer 2102 and n-type semiconductor and oxide layer 2111. [0085] Still further, one or more metal and oxide layers 2200 may be disposed between intrinsic semiconductor and oxide layers. Figure 6c shows a cell structure in which are deposited, in overlying sequence, an oxide material or n-type semiconductor layer 1000, one or more sub-structures where each sub-structure consists of semiconductor and oxide layer 2100, metal and oxide layer 2200 and semiconductor and oxide layer 2110, and a p-type semiconductor or other hole conducting material layer 3000. The size (diameter and/or height) of semiconductor grains and the composition of semiconductor grains in layers can be varied to vary band gap of semiconductor material and increase efficiency. Similarly, Figure 6d illustrates a similar cell structure in which p-type semiconductor or other hole conducting material layer 3000 is deposited prior to electron conducting layer 1000. [0086] A variety of other configurations are possible. For example, Figures 7a and 7b illustrate cell structures in which a metallic layer 4000 can be disposed between semiconductor and oxide layers, such as between intrinsic semiconductor and oxide layers 2100 and 2110 (Figure 7a), or between p-type semiconductor and oxide layer 2102 and n-type semiconductor and oxide layer 2111. [0087] Still further, Figures 12 a to 12d illustrate additional photo cell configurations. Figure 12a shows a cell structure in which are deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, an electron conducting material layer 1000, a semiconductor and oxide layer 2100, and a p-type semiconductor or other hole conducting material layer 3000. As mentioned before, layers 1000 and 2100 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). A layer 3000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). Similarly, as Figure 12b shows, the hole conducting material layer can be deposited on interlayer 5000, while electron conducting material layer 1000 can be deposited on semiconductor and oxide layer 2100.

[0088] Figure 12c shows a cell structure in which are deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, an electron conducting layer 1000, a metal and oxide layer 2200, a p-type semiconductor and oxide layer 2102, p-type semiconductor or other hole conducting material layer 3000. As mentioned before, layers 1000, 2200 and 2102 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). Hole conducting material layer 3000 can be sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). Similarly, Figure 12d shows a cell structure in which are deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, a metal and oxide layer 2200, an electron conducting material layer 1000, an n-type semiconductor and oxide layer 2101, and a p-type semiconductor or other hole transporting material layer 3000. The illustrated layer structures of Figures 12a to 12d can be combined with additional conductive contacts or layers, protective layers and the like as illustrated above.

D. Additional Embodiments

[0089] Figures 13a to 13d illustrate example structures and configurations of solar cells according to several possible implementations of the invention. As Figure 13a illustrates, a solar cell 100a may comprise, in overlying sequence a glass or other transparent substrate 8000, a transparent conductive layer 7000, a photoactive conversion layer 80, a second transparent conductive layer 7000 and a second glass or other transparent material layer 8000. In a particular implementation, the transparent conductive layer 7000 may be indium oxide doped with tin oxide. [009O]In other implementations, solar cell 101a, as Figure 13b shows, may comprise (in overlying sequence) non-transparent substrate 8600, metal contact layer 9000, photoactive conversion layer 80, transparent conductive layer 7000, and glass or other transparent material substrate 8000. Figure 13c shows solar cell 102a comprising (in overlying sequence) glass substrate 8000, transparent conductive layer 7000, photoactive conversion layer 80, metal contact layer 9000, and non-transparent protective layer 8500.

[0091] As Figure 13d illustrates, photoactive conversion layer 80 may include a plurality of sub-layers including one or more of a seed layer 6000, one or more interlayers 5000, one or more n-type semiconductor and oxide layers 2101, and a hole conducting material layer 3000. Figures 13e to 13g show other alternative photoactive conversion layers. For example, as Figure 13e illustrates, photoactive conversion layer 80a may comprise seed layer 6000, interlayer 5000, p-type semiconductor and oxide layer 2102, and electron conducting material layer 1000. The photoactive conversion layer may include other layers as well. As Figures I3f and 13g show, photoactive conversion layers 8Oh, 80c may include a metal and oxide layer 2200 disposed on the interlayer 5000.

[0092J Photoactive conversion layer 80 includes multiple sub-layers having various conductive properties and other characteristics, which, in combination, can be configured to produce a photovoltaic effect in response to solar energy. The material composition, layer configuration and layer arrangement of the photovoltaic cells can be configured to achieve a variety of objectives. For example, the materials used in these layers may be configured to create p-n heterojunctions. N-type semiconductor and oxide layer 2101 and p-type semiconductor and oxide layer 2102, in some implementations, are sensitizing or absorber layers. With reference to Figure 13d (for example), upon photo excitation, electrons are efficiently injected from the conducting band of the semiconductor grains of n-type semiconductor and oxide layer 2101 into the conducting band of electron conducting material, creating a charge separation and producing photovoltaic effect. Regeneration of the absorber semiconductor grains can occur by capture of electrons from the hole conducting material layer 3000. [0093] One or more intrinsic semiconductor layers (see, e.g., Figure 14a) can be disposed between these p-type and n-type semiconductor layers, as well. The material composition, layer configuration and layer arrangement of the photovoltaic cells can be configured to achieve a variety of objectives. For example, depending on material choice, the nanometer-diameter grains of the intrinsic semiconductor and oxide layer 2100 can operate as absorbers in a p-n heterojunction between an oxide material (such as TiO2) and a hole conducting material (such as OMeTAD). To achieve efficient electron injection into the electron conducting layer, the bottom edge of the conductive band of the absorber, Ec(absorber), should be higher than the bottom edge of the conductive band of the electron conducting layer, Ec(electron conducting layer). On the other hand, the top edge of the valence band of the absorber, Ey(absorber), should be lower than the top edge of the valence band of the hole conducting layer, Ey.or the Fermi level of organic hole conductor material, to promote efficient regeneration of the absorber semiconductor grains. In other implementations, the layers of the cell structure can be configured to create p-n junctions with an electric field across the depletion region between a p-type semiconductor layer and an n-type semiconductor layer. One or more intrinsic semiconductor layers can be disposed between these p-type and n-type semiconductor layers, as well.

[0094] Glass layer 8000 can be a glass substrate or deposited layer made of a variety of materials, such as silicon dioxide. Alternatively, a transparent polymer can be used. Still further, one or more of the transparent conducting layers 7000 can be replaced by metal contacts arranged in a grid (e.g., fingers and busbars) on one side (or both sides) and a full area metal contact on the other side. Additional layers, such as anti-reflection coatings can also be added. The layer stack can be deposited on glass, polymer or metal substrates. If the layer stack is deposited on top of a non-transparent substrate, the top contact is transparent to allow light penetration into the photoactive conversion layer. Glass layer 8000 can be replaced by other suitable protective layers or coatings, or be added during construction of a solar module or panel. Still further, the layers described herein may be deposited on a flat substrate (such as a glass substrate intended for window installations), or directly on one or more surfaces of a non-imaging solar concentrator, such as a trough-like or Winston optical concentrator.

[0095] Structurally, semiconductor and oxide layers 2101 and 2102 are granular layers comprising a plurality of nanometer- diameter semiconductor grains 98 contained in, or surrounded by, a matrix of oxide material 99. In other words, the oxide material is dispersed at grain boundaries 97 of the semiconductor. For purposes of this disclosure, reference numbers for the semiconductor and oxide layers follow a convention of 21Xy, where X denotes the sub-layer position and y denotes the type of semiconductor (y = 1 corresponds to n-type, y = 2 corresponds to p-type and y = 0 corresponds to i-type or intrinsic semiconductor). Formation of the semiconductor and oxide layers 2 IXy is discussed below. In the semiconductor and oxide layer(s), upon photoexcitation of semiconductor grains 98, electrons are injected into the surrounding oxide matrix 99 or generated charge carriers (electrons and holes) are separated by an electric field created by p-type and n-type semiconductor materials in the adjacent layers.

[0096] As discussed above, multiple semiconductor and oxide layers may be deposited. Furthermore, the semiconductor material in semiconductor and oxide layers may be an intrinsic semiconductor material, a p-type semiconductor material, or an n-type semiconductor material. Various implementations discussed below utilize one or more of these semiconductor and oxide layers in varying configurations, combinations and arrangements to yield high efficiency solar cells. As discussed above, this disclosure refers to an intrinsic semiconductor and oxide layers using a reference number convention of 21X0, where X equals a layer number from 1 to N (where N equals the number of layers). Similarly, this disclosure refers to n-type semiconductor and oxide layers using a reference number convention of 21X1, where X equals a layer number from 1 to N. Lastly, this disclosure refers to p-type semiconductor and oxide layers using a reference number convention of 21X2, where X equals a layer number from 1 to N. In the photovoltaic cells illustrated in Figures 14a and 14b, for example, intrinsic semiconductor grains in the semiconductor and oxide layer 2110 operate as absorbers. In other words, light excites electrons in the absorber semiconductor grains 98, which are injected into the conduction band of the oxide matrix 99 or into the conduction band of an electron conductor. The absorber semiconductor grains 98 are regenerated by capture of electrons from the valence band of a hole conducting material layer (such as a p-type semiconductor). [0097] Figure 14a shows a solar cell structure according to which is deposited in overlying sequence, a seed layer 6000, an interlayer 5000, an n-type semiconductor and oxide layer 2101, an intrinsic semiconductor and oxide layer 2110, a p-type semiconductor or other hole conducting material layer 3000. As mentioned above, multiple intrinsic semiconductor and oxide layers 21X0 can be deposited. As mentioned above, layers 2101, 2110 can be deposited with a magnetron sputtering technique at a total atmospheric pressure of at least 1.2 Pa (10 mTorr). A seed layer 6000 can be also first sputtered at a total atmospheric pressure below 0.8 Pa (6 mTorr), and then sputtered at a total atmospheric pressure above 1.6 Pa (12 mTorr) to form an interlayer 5000 to promote desired growth of semiconductor grains of the n-type semiconductor and oxide layer 2101. Hole conducting material layer 3000 can sputtered at a total atmospheric pressure below 1.2 Pa (10 mTorr). Figure 14b illustrates an alternative embodiment including p-type semiconductor and oxide layer 2102 sputtered deposited on the interlayer 5000, and an electron conducting material layer 1000 deposited on the intrinsic semiconductor and oxide layer 2110.

[0098] Figure 15a illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, an n-type semiconductor and oxide layer 2101, an intrinsic semiconductor and oxide layer 2110, one or more p-type semiconductor and oxide layers 21n2, and a p-type semiconductor or other hole conducting material layer 3000. As mentioned above, multiple intrinsic semiconductor and oxide layers 21X0 can be deposited. In another implementation, the intrinsic semiconductor and oxide layer can be omitted. Additionally, multiple p-type semiconductor and oxide layers 21X2 can be deposited between the last intrinsic semiconductor and oxide layer 21 NO and the hole conducting material layer 3000. Similarly, multiple n-type semiconductor and oxide layers 21X1 can be deposited between the interlayer 5000 and the first intrinsic semiconductor and oxide layers 2110. In some implementations, a thin layer of oxide can be deposited between each, or select ones, of these multiple semiconductor and oxide layers 21Xy to segregate the semiconductor grains. The diameter and height of semiconductor grains and the composition of semiconductor grains in layers 21Xy can be varied to vary band gap of semiconductor material and increase efficiency of the cell structures. In a particular implementation, the size of the semiconductor grains in the first semiconductor and oxide layer 21X0 is the largest (relative to all other semiconductor and oxide layers), with semiconductor grain size decreasing with each successive layer. In addition, as Figure 15c illustrates, a metal and oxide layer 2200 can also be deposited on the interlayer 5000 to underlie the n-type semiconductor and oxide layer 2101.

[0099] Figure 15b illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, a p-type semiconductor and oxide layer 2102, an intrinsic semiconductor and oxide layer 2110, and one or more n-type semiconductor and oxide layers 2 InI, and electron conducting material layer 1000. As mentioned above, multiple intrinsic semiconductor and oxide layers 21X0 can be deposited. Additionally, multiple n-type semiconductor and oxide layers 21X1 can be deposited between the last intrinsic semiconductor and oxide layer 21N0 and the electron conducting material layer 1000. Similarly, multiple p-type semiconductor and oxide layers 21X2 can be deposited between the interlayer 5000 and the first intrinsic semiconductor and oxide layers 2110. In some implementations, a thin layer of oxide can be deposited between each, or select ones, of these multiple semiconductor and oxide layers 21Xy to segregate the semiconductor grains.

[00100] Still further, as Figures 15d and 15e show, in any of the foregoing configurations, an intervening layer (3500, 3510, ..., 35(n+l)0), such as a thin layer of oxide, may be deposited between each of the semiconductor and oxide layers 21Xy to isolate the semiconductor grains. The thickness of layers 3500, 3510, ..., 35(n+l)0 can be below 10 nm. Preferably, in one implementation, the thickness of layers 3500, 3510, ..., 35(n+l)0 is below 4 nm. [00101] The photoactive conversion layer 80 may also include one or more metal and oxide layers. Figure 16a illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, an n-type semiconductor and oxide layer 2101, a metal and oxide layer 2200, a p-type semiconductor and oxide layer 2122, and a p-type semiconductor or other hole conducting material layer 3000. Additionally, multiple n-type semiconductor and oxide layers 21X1 can be deposited between interlayer 5000 and the metal and oxide layer 2200. Similarly, multiple p-type semiconductor and oxide layers 21X2 can be deposited between the metal and oxide layers 2200 the hole conducting material layer 3000.In addition, one or more intrinsic semiconductor and oxide layers 21X0 can be deposited. Figure 16b illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, a p-type semiconductor and oxide layer 2102, a metal and oxide layer 2200, an n-type semiconductor and oxide layer 2121, and electron conducting material layer 1000. Additionally, multiple n-type semiconductor and oxide layers 21X1 can be deposited between the metal and oxide layer 2200 and the electron conducting material layer 1000. Similarly, multiple p-type semiconductor and oxide layers 21X2 can be deposited between the interlayer 5000 and the metal and oxide layers 2200. As mentioned above, one or more intrinsic semiconductor and oxide layers 21X0 can also be deposited.

[00102] As Figures 17a to 17e illustrate, some of the layers discussed above can be omitted from photoactive conversion layer 80. Electron and hole conducting layers 1000 or 3000, as well as seed layer 6000 and interlayer 5000, may be omitted. For example, as Figure 17a shows, photoactive conversion layer may comprise one or more p-type semiconductor and oxide layers 2102, one or more intrinsic semiconductor and oxide layers 2110, and one or more n-type semiconductor and oxide layers 2101. Figure 17b illustrates the addition of seed layer 6000 and interlayer 5000. Figure 17c illustrates the addition of a metal and oxide layer 2200. Lastly, Figures 17d and 17e show the addition of thin intervening layers 3500, 3510, .... 35(n+l)0 deposited between the semiconductor and oxide layers 21Xy.

[00103] In other implementations, tandem solar cells can be constructed utilizing one or more semiconductor and oxide layers. Figure 18a illustrates a cell structure according to which is deposited, in overlying sequence, an electron conducting material layer 1000, and one or more composite layer structures including an n-type semiconductor and oxide layer 2101, a p-type semiconductor and oxide layer 2112, and an electron conducting material layer 1000. The illustrated cell structure also includes an n-type semiconductor and oxide layer 2 InI, a p-type semiconductor and oxide layer 21(n+l)2, and a hole conducting material layer 3000. Figure 18b illustrates a cell structure according to which is deposited, in overlying sequence, an electron conducting material layer 1000, a p- type semiconductor and oxide layer 2102, an interconnecting layer 3600, a n-type semiconductor and oxide layer 2111, and a hole conducting material layer 3000. [00104] Figure 19a illustrates a cell structure according to which is deposited, in overlying sequence, an electron conducting material layer 1000, and one or more composite layer structures including an n-type semiconductor and oxide layer 2101, a p-type semiconductor and oxide layer 2112, and an interconnecting layer 3600. The illustrated cell structure also comprises an n-type semiconductor and oxide layer 2 InI, a p-type semiconductor and oxide layer 21(n+l)2, and a hole conducting material layer 3000. A cell structure illustrated in Figure 19b also includes intrinsic semiconductor and oxide layers 21X0 deposited between n-type and p-type semiconductor and oxide layers of the composite layer structures. [00105] Figure 20a illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, and one or more composite layer structures including an n-type semiconductor and oxide layer 2101, a p-type semiconductor and oxide layer 2112, and an interconnecting layer 3600. The cell structure further includes an n-type semiconductor and oxide layer 2 InI, a p-type semiconductor and oxide layer 2l(n+l)2, and a hole conducting material layer 3000. A cell structure illustrated in Figure 20b also includes intrinsic semiconductor and oxide layers 21X0 deposited between n-type and p-type semiconductor and oxide layers of the composite layer structures. [00106] Figure 21a illustrates a cell structure according to which is deposited, in overlying sequence, a seed layer 6000, an interlayer 5000, and one or more composite layer structures including an n-type semiconductor and oxide layer 2101, a p-type semiconductor and oxide layer 2112, and an interconnecting layer 3600. The illustrated cell structure also includes an n-type semiconductor and oxide layer 2 InI, and a p-type semiconductor and oxide layer 21 (n+ 1)2. A cell structure illustrated in Figure 21b also includes intrinsic semiconductor and oxide layers 21X0 deposited between n-type and p-type semiconductor and oxide layers of the composite layer structures.

[00107] An interconnecting layer 3600 may include one or more oxide (of particular interest are conductive oxides such as indium-tin-oxide and doped zinc oxide) or semiconductor layers. The interconnecting layer 3600 can be up to 200 nm in thickness. In one implementation, the interconnecting layer is about 20 nm or less in thickness. The role of the interconnecting layer 3600 is to connect sub- cells (p-n junctions). Preferably, the inter-cell ohmic contacts should cause very low loss of electrical power between cells. Therefore, the interconnecting layer 3600 should have minimal electrical resistance. For this reason interconnecting layer can be metal, conductive oxide layer, and a tunnel junction (or tunnel diodes). The metal interconnects can provide low electrical resistance, but they are difficult to fabricate and they strongly absorb light that can cause substantial loss in the device efficiency. Therefore, conductive oxide layers, tunnel junctions (or tunnel diodes) are preferred. The material used for interconnecting layer 3600 should have low resistivity, low optical energy losses, and often crystallographic compatibility through lattice-matching between top and bottom cell.

[00108] In the previous description, numerous specific details are set forth, such as specific materials, structures, processes, etc., in order to provide a better understanding of the present invention. However, the present invention can be practiced without resorting to the details specifically set forth. In other instances, well-known processing materials and techniques have not been described in detail in order not to unnecessarily obscure the present invention. Only the preferred embodiments of the present invention and but a few examples of its versatility are shown and described in the present disclosure. It is to be understood that the present invention is capable of use in various other combinations and is susceptible of changes and/or modifications within the scope of the inventive concept as' expressed herein.

Claims

CLAIMSWhat is claimed is:

1. A photovoltaic cell, comprising a first layer comprising an electron conducting material; a second layer comprising a hole conducting material; and a third layer, disposed between the first layer and the second layer, comprising an oxide and a semiconductor, wherein the oxide is dispersed at grain boundaries of the semiconductor.

2. The photovoltaic cell of claim 1 wherein the electron conducting material comprises an n-type semiconductor or an oxide.

3. The photovoltaic cell of claim 1 wherein the hole conducting material comprises a p-type semiconductor.

4. The photovoltaic cell of claim 1 wherein the hole conducting material comprises an organic hole conducting material.

5. The photovoltaic cell of claim 1 further comprising a first conductive layer operatively connected to the first layer; and a second conductive layer operatively connected to the second layer.

6. The photovoltaic cell of claim 5 wherein at least one of the first and second conductive layers are transparent.

7. The photovoltaic cell of claim 5 wherein at least one of the first and second conductive layers comprises a metal.

8. The photovoltaic cell of claim 5 further comprising at least one glass layer overlying a select one of the first or second conductive layer.

9. The photovoltaic cell of claim 1 wherein the first layer comprises two or more sub-layers wherein at least one sub-layer of the two or more sub-layers has a different composition from at least one other sub-layer of the two ore more sublayers.

10. The photovoltaic cell of claim 1 wherein the third layer comprises two or more sub-layers, each comprising an oxide and a semiconductor, wherein the oxide is dispersed at grain boundaries of the semiconductor.

11. The photovoltaic cell of claim 10 wherein at least one sub-layer of the two or more sub-layers includes a semiconductor and oxide composition different from at least one other sub-layer of the two or more sub-layers.

12. The photovoltaic cell of claim 10 wherein at least one sub-layer of the two or more sub-layers includes an average semiconductor grain diameter different from at least one other sub-layer of the two or more sub-layers.

13. The photovoltaic cell of claim 10 wherein at least one sub-layer of the two or more sub-layers includes semiconductor grains having a band gap different from at least one other sub-layer of the two or more sub-layers.

14. The photovoltaic cell of claim 10 wherein each sub-layer is separated from an adjacent sub-layer with an oxide layer having a thickness less than 4 urn.

15. The photovoltaic cell of claim 1 wherein the third layer comprises two or more sub-layers wherein at least one sub-layer of the two or more sub-layers has a different composition from at least one other sub-layer of the two ore more sublayers.

16. The photovoltaic cell of claim 1 further comprising one or more metal and oxide layers disposed between the first layer and the second layer, each comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

17. The photovoltaic cell of claim 1 wherein the semiconductor and oxide layer comprises a plurality of semiconductor grains surrounded by the oxide, and wherein the semiconductor grains have an average diameter of less than 15 nanometers.

18. The photovoltaic cell of claim 1 further comprising one or more metal layers disposed between the first layer and the second layer.

19. The photovoltaic cell of claim 1 further comprising an interlayer disposed between the first and second layer, and wherein the third layer is deposited on the interlayer.

20. The photovoltaic cell of claim 1 further comprising a seed layer disposed between the first and second layer, and an interlayer deposited on the seed layer, and wherein the third layer is deposited on the interlayer.

21. The photovoltaic cell of claim 1 wherein the semiconductor is an intrinsic semiconductor.

22. The photovoltaic cell of claim 1 further comprising an interlayer, wherein either the first layer or the second layer is deposited on the interlayer, and wherein the semiconductor of the semiconductor and oxide layer is an intrinsic semiconductor.

23. The photovoltaic cell of claim 1 further comprising a seed layer and an interlayer, wherein either the first layer or the second layer is deposited on the interlayer, and wherein the semiconductor of the semiconductor and oxide layer is an intrinsic semiconductor.

24. A photovoltaic cell, comprising a first layer comprising an electron conducting material; a second layer comprising a hole conducting material; a third layer, disposed between the first layer and the second layer, comprising an oxide and a p-type semiconductor, wherein the oxide is dispersed at grain boundaries of the p-type semiconductor; and a fourth layer, disposed between the first layer and the second layer, comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor.

25. A photovoltaic cell, comprising a metallic interlayer; an electron conducting material layer formed on the metallic interlayer; a hole conducting material layer; a semiconductor and oxide layer, disposed between the electron conducting material layer and the hole conducting material layer, comprising an oxide and a p- type semiconductor, wherein the oxide is dispersed at grain boundaries of the p- type semiconductor; and a metal and oxide layer, disposed between the electron conducting material layer and the semiconductor and oxide layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

26. A photovoltaic cell, comprising a metallic interlayer; a metal and oxide layer, deposited on the metallic interlayer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal; an electron conducting material layer deposited over the metal and oxide layer; a hole conducting material layer; and a semiconductor and oxide layer, disposed between electron conducting material layer and the hole conducting material layer, comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n- type semiconductor.

27. A method of fabricating a photovoltaic cell, comprising forming a first layer comprising an electron conducting material; sputter depositing a semiconductor and oxide layer, wherein the oxide is dispersed at grain boundaries of the semiconductor; and forming a third layer comprising a hole conducting material.

28. The method of claim 27 wherein sputter depositing a semiconductor and oxide layer comprises sputter depositing the semiconductor and oxide layer sputter depositing the layer using process conditions that create low surface mobility of deposited semiconductor adatoms.

29. The method of claim 27 wherein sputter depositing a semiconductor and oxide layer comprises sputter depositing the semiconductor and oxide layer in an atmosphere containing a gas at an atmospheric pressure of at least 0.8 Pa (6 mTorr).

30. The method of claim 27 further comprising sputter depositing an interlayer in an atmosphere containing a gas at an atmospheric pressure of at least 0.8 Pa (6 mTorr) prior to sputter depositing the semiconductor and oxide layer.

31. A photovoltaic cell, comprising a first layer comprising an electron conducting material; a second layer comprising a hole conducting material; and wherein at least one of the first and second layers comprises a plurality of absorher semiconductor grains and an oxide material dispersed at boundaries of the absorber semiconductor grains.

32. The photovoltaic cell of claim 31 further comprising a one or more additional semiconductor and oxide layers, disposed between the first layer and the second layer, each comprising semiconductor material and an oxide material, wherein the oxide material is dispersed at grain boundaries of the semiconductor material.

33. The photovoltaic cell of claim 32 wherein at least one of the semiconductor and oxide layers is separated from an adjacent semiconductor and oxide layer with an oxide layer having a thickness less than 4 nm.

34. A photovoltaic cell, comprising an interlayer; a semiconductor and oxide layer comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor; and a hole conducting material layer.

35. The photovoltaic cell of claim 34 wherein the interlayer comprises a metal.

36. The photovoltaic cell of claim 34 wherein the hole conducting material layer comprises a p-type semiconductor.

37. The photovoltaic cell of claim 34 further comprising a seed layer, wherein the interlayer is deposited on the seed layer.

38. The photovoltaic cell of claim 34 further comprising a transparent conductive layer formed on the hole conducting material layer.

39. The photovoltaic cell of claim 38 further comprising a transparent protective layer formed over the transparent conductive layer.

40. The photovoltaic cell of claim 34 further comprising a metal and oxide layer, disposed between the interlayer and the semiconductor and oxide layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

41. The photovoltaic cell of claim 34 further comprising a second semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the hole conducting material layer, comprising an intrinsic semiconductor and an oxide, wherein the oxide is dispersed at grain boundaries of the intrinsic semiconductor.

42. The photovoltaic cell of claim 41 wherein at least one of the semiconductor and oxide layers is separated from an adjacent semiconductor and oxide layer with an oxide layer having a thickness less than 4 nm.

43. The photovoltaic cell of claim 41 further comprising a third semiconductor and oxide layer, disposed between the second semiconductor and oxide layer and the hole conducting material layer, comprising an oxide and a p-type semiconductor, wherein the oxide is dispersed at grain boundaries of the p-type semiconductor.

44. The photovoltaic cell of claim 34 further comprising a semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the hole conducting material layer, comprising an oxide and a p-type semiconductor, wherein the oxide is dispersed at grain boundaries of the p-type semiconductor.

45. The photovoltaic cell of claim 34 further comprising a metal and oxide layer, disposed between the semiconductor and oxide layer and the hole conducting material layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

46. The photovoltaic cell of claim 34 further comprising a second semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the hole conducting material layer, comprising an oxide and an p-type semiconductor, wherein the oxide is dispersed at grain boundaries of the p- type semiconductor; and a metal and oxide layer, disposed between the semiconductor and oxide layer and the second semiconductor and oxide layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

47. A photovoltaic cell, comprising a interlayer; a semiconductor and oxide layer comprising an oxide and an p-type semiconductor, wherein the oxide is dispersed at grain boundaries of the p-type semiconductor; and an electron conducting material layer.

48. The photovoltaic cell of claim 47 wherein the electron conducting material layer comprises an n-type semiconductor.

49. The photovoltaic cell of claim 47 further comprising a seed layer, wherein the interlayer is deposited on the seed layer.

50. The photovoltaic cell of claim 47 further comprising a transparent conductive layer formed on the electron conducting material layer.

51. The photovoltaic cell of claim 50 further comprising a transparent protective layer formed over the transparent conductive layer.

52. The photovoltaic cell of claim 47 further comprising a metal and oxide layer disposed between the interlayer and the semiconductor and oxide layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

53. The photovoltaic cell of claim 47 further comprising a second semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the electron conducting material layer, comprising an intrinsic semiconductor and an oxide, wherein the oxide xs dispersed at grain boundaries of the intrinsic semiconductor.

54. The photovoltaic cell of claim 53 further comprising a third semiconductor and oxide layer, disposed between the second semiconductor and oxide layer and the electron conducting material layer, comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor.

55. The photovoltaic cell of claim 47 further comprising a semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the electron conducting material layer, comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor.

56. The photovoltaic cell of claim 47 further comprising a metal and oxide layer, disposed between the semiconductor and oxide layer and the electron conducting material layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

57. The photovoltaic cell of claim 47 further comprising a second semiconductor and oxide layer, disposed between the semiconductor and oxide layer and the electron conducting material layer, comprising an oxide and an n-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor; and a metal and oxide layer, disposed between the semiconductor and oxide layer and the second semiconductor and oxide layer, comprising an oxide and a metal, wherein the oxide is dispersed at grain boundaries of the metal.

58. A method comprising sputter depositing an interlayer under sputter process conditions promoting low surface mobility of deposited atoms to create the interlayer having a desired surface roughness; sputter depositing on the interlayer, under low surface mobility process conditions, a semiconductor and oxide layer comprising an oxide and an ή-type semiconductor, wherein the oxide is dispersed at grain boundaries of the n-type semiconductor; and sputter depositing a hole conducting material layer on the semiconductor and oxide layer.

59. The method of claim 58 wherein the sputter depositing a semiconductor and oxide layer comprises sputter depositing a semiconductor and an oxide in an atmosphere containing a gas at a first atmospheric pressure, and wherein forming the first layer comprises sputter depositing the electron conducting material in an atmosphere containing a gas at a second atmospheric pressure lower than the first atmospheric pressure.

60. The method of claim 58 wherein sputter depositing a semiconductor and oxide layer comprises sputter depositing the semiconductor and oxide layer in an atmosphere containing a gas at an atmospheric pressure of at least 0.8 Pa (6 mTorr).

61. The method of claim 58 wherein sputter depositing an interlayer comprises sputter depositing an interlayer in an atmosphere containing a gas at an atmospheric pressure of at least 0.8 Pa (6 mTorr).