# Patent

## Title
Nanowire array based solar energy harvesting device

## Abstract

A photovoltaic device operable to convert light to electricity, comprising a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a planar mirror on a bottom wall thereof and each recess filled with a transparent material. The structures have p-n or p-i-n junctions for converting light into electricity. The planar mirrors function as an electrode and can reflect light incident thereon back to the structures to be converted into electricity.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to U.S. patent application Ser. No. 12/204,686 (granted as U.S. Pat. No. 7,646,943), Ser. Nos. 12/648,942, 12/270,233, 12/472,264, 12/472,271, 12/478,598, 12/573,582, 12/575,221, 12/633,323, 12/633,318, 12/633,313, 12/633,305, 12/621,497, 12/633,297, 61/266,064, 61/357,429, 61/360,421, 12/945,492, 12/910,664, 12/966,514, 12/966,535, 12/966,573, 12/967,880 and 12/974,499, the disclosures of which are hereby incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
A photovoltaic device, also called a solar cell is a solid state device that converts the energy of sunlight directly into electricity by the photovoltaic effect. Assemblies of cells are used to make solar modules, also known as solar panels. The energy generated from these solar modules, referred to as solar power, is an example of solar energy.
The photovoltaic effect is the creation of a voltage (or a corresponding electric current) in a material upon exposure to light. Though the photovoltaic effect is directly related to the photoelectric effect, the two processes are different and should be distinguished. In the photoelectric effect, electrons are ejected from a material's surface upon exposure to radiation of sufficient energy. The photovoltaic effect is different in that the generated electrons are transferred between different bands (i.e. from the valence to conduction bands) within the material, resulting in the buildup of a voltage between two electrodes.
Photovoltaics is a method for generating electric power by using solar cells to convert energy from the sun into electricity. The photovoltaic effect refers to photons of light-packets of solar energy-knocking electrons into a higher state of energy to create electricity. At higher state of energy, the electron is able to escape from its normal position associated with a single atom in the semiconductor to become part of the current in an electrical circuit. These photons contain different amounts of energy that correspond to the different wavelengths of the solar spectrum. When photons strike a PV cell, they may be reflected or absorbed, or they may pass right through. The absorbed photons can generate electricity. The term photovoltaic denotes the unbiased operating mode of a photodiode in which current through the device is entirely due to the light energy. Virtually all photovoltaic devices are some type of photodiode.
A conventional solar cell often has opaque electrodes on a surface that receives light. Any light incident on such opaque electrodes is either reflected away from the solar cell or absorbed by the opaque electrodes, and thus does not contribute to generation of electricity. Therefore, a photovoltaic device that does not have this drawback is desired.
BRIEF SUMMARY OF THE INVENTION
Described herein is a photovoltaic device operable to convert light to electricity, comprising a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a sidewall and a bottom wall, and a planar reflective layer disposed on the bottom wall of each recess, wherein the structures comprise a single crystalline semiconductor material; the sidewall of each recess is free of the planar reflective layer; and each recess is filled with a transparent material. Unlike a conventional solar cell, light incident on the planar reflective layer is not wasted but reflected to the structures to be absorbed and converted to electricity. This photovoltaic device can also be used as a photo detector.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic cross sectional view of a photovoltaic device according to an embodiment.
FIG. 1B is a process of manufacturing the photovoltaic device of FIG. 1A, according to an embodiment.
FIG. 2A is a schematic cross sectional view of a photovoltaic device according to an embodiment.
FIG. 2B is a process of manufacturing the photovoltaic device of FIG. 2A, according to an embodiment.
FIG. 3A is a schematic cross sectional view of a photovoltaic device according to an embodiment.
FIG. 3B is a process of manufacturing the photovoltaic device of FIG. 3A, according to an embodiment.
FIG. 4A shows a method of print coating a resist layer, according to an embodiment.
FIG. 4B shows a method of print coating a resist layer, according to another embodiment.
FIG. 5 shows a schematic of light concentration in the structures of the photovoltaic device.
FIG. 6 shows an exemplary top cross sectional view of the photovoltaic device.
FIG. 7 shows an exemplary perspective view of the photovoltaic device.
FIGS. 8A-8C shows schematics of drawing electrical current from the photovoltaic devices of FIG. 1A, FIG. 2A and FIG. 3A, respectively.
FIG. 9 shows a top view of an alternative stripe-shaped structures of the photovoltaic device.
FIG. 10 shows a top view of an alternative mesh-shaped structures of the photovoltaic device.
FIG. 11A and FIG. 11B show a process of making vias.
FIG. 12A and FIG. 12B show top views of exemplary vias.



DETAILED DESCRIPTION OF THE INVENTION
Described herein is a photovoltaic device operable to convert light to electricity, comprising a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a sidewall and a bottom wall, and a planar reflective layer disposed on the bottom wall of each recess, wherein the structures comprise a single crystalline semiconductor material; the sidewall of each recess is free of the planar reflective layer; and each recess is filled with a transparent material. The term “photovoltaic device” as used herein means a device that can generate electrical power by converting light such as solar radiation into electricity. That the structures are single crystalline as used herein means that the crystal lattice of the entire structures is continuous and unbroken throughout the entire structures, with no grain boundaries therein. An electrically conductive material can be a material with essentially zero band gap. The electrical conductivity of an electrically conductive material is generally above 103 S/cm. A semiconductor can be a material with a finite band gap upto about 3 eV and general has an electrical conductivity in the range of 103 to 108 S/cm. An electrically insulating material can be a material with a band gap greater than about 3 eV and generally has an electrical conductivity below 108 S/cm. The term “structures essentially perpendicular to the substrate” as used herein means that angles between the structures and the substrate are from 85° to 90°. The term “recess” as used herein means a hollow space in the substrate and is open to a space outside the substrate.
According to an embodiment, the single crystalline semiconductor material is selected from a group consisting of silicon, germanium, group III-V compound materials, group II-VI compound materials, and quaternary materials. A group III-V compound material as used herein means a compound consisting of a group III element and a group V element. A group III element can be B, Al, Ga, In, Tl, Sc, Y, the lanthanide series of elements and the actinide series of elements. A group V element can be V, Nb, Ta, Db, N, P, As, Sb and Bi. A group II-VI compound material as used herein means a compound consisting of a group II element and a group VI element. A group II element can be Be, Mg, Ca, Sr, Ba and Ra. A group VI element can be Cr, Mo, W, Sg, O, S, Se, Te, and Po. A quaternary material is a compound consisting of four elements.
According to an embodiment, the structures are cylinders or prisms with a cross-section selected from a group consisting of elliptical, circular, rectangular, and polygonal cross-sections, strips, or a mesh. The term “mesh” as used herein means a web-like pattern or construction.
According to an embodiment, the structures are pillars with diameters from 50 nm to 5000 nm, heights from 1000 nm to 20000 nm, a center-to-center distance between two closest pillars of 300 nm to 15000 nm.
According to an embodiment, the structures have an overhanging portion along an entire contour of a top surface of the structures. The term “overhanging portion” as used herein means a portion of the structures that project over the sidewall of the recesses. The term “contour of a top surface of the structures” as used herein means the edge of the top surface of the structures. The top surface of the structures can be broken by the recesses. An edge of the top surface is the boundary on the top surface between the structures and the recesses.
According to an embodiment, each recess has a rounded or beveled inner edge between the sidewall and the bottom wall thereof.
According to an embodiment, the planar reflective layer is a material selected from a group consisting of ZnO, Al, Au, Ag, Pd, Cr, Cu, Ti, Ni and a combination thereof; the planar reflective layer is an electrically conductive material; the planar reflective layer is a metal; the planar reflective layer has a reflectance (i.e., the fraction of incident electromagnetic power that is reflected) of at least 50% for visible light (i.e., light have a wavelength from 390 to 750 nm) of any wavelength; the planar reflective layer has a thickness of at least 5 nm; the planar reflective layers in all the recesses are connected; the planar reflective layer is functional to reflect light incident thereon to the structures so that the light is absorbed by the structures; and/or the planar reflective layer is functional as an electrode of the photovoltaic device. The term “electrode” as used herein means a conductor used to establish electrical contact with the photovoltaic device.
According to an embodiment, the substrate has a flat surface opposite the structures.
According to an embodiment, the flat surface has a doped layer and optionally a metal layer metal layer disposed on and forming an Ohmic contact with the doped layer. An Ohmic contact is a region a current-voltage (I-V) curve across which is linear and symmetric.
According to an embodiment, total area of the planar reflective layer is at least 40% of a surface area of the flat surface.
According to an embodiment, the substrate has a thickness of at least 50 microns.
According to an embodiment, the structures are pillars arranged in an array; each structure is about 5 microns in height; a pitch of the structures is from 300 nm to 15 microns.
According to an embodiment, the transparent material has a surface coextensive with a top surface of the structures; the transparent material is substantially transparent to visible light with a transmittance of at least 50%; the transparent material is an electrically conductive material; the transparent material is a transparent conductive oxide; the transparent material forms an Ohmic contact with the planar reflective layer; and/or the transparent material is functional as an electrode of the photovoltaic device.
According to an embodiment, the photovoltaic device further comprises an electrode layer and optionally a coupling layer, wherein: the electrode layer is disposed on the transparent material and the structures; the electrode layer is the same material as the transparent material or different material from the transparent material; the electrode layer is substantially transparent to visible light with a transmittance of at least 50%; the electrode layer is an electrically conductive material; the electrode layer is a transparent conductive oxide; the electrode layer is functional as an electrode of the photovoltaic device; and/or the coupling layer is disposed on the electrode layer and only above a top surface of the structures. The term “coupling layer” as used herein means a layer effective to guide light into the structures.
According to an embodiment, the photovoltaic device further comprises a passivation layer and optionally a coupling layer, wherein: the passivation layer is disposed on the sidewall, and on the bottom wall under the planar reflective layer; a top surface of the structures is free of the passivation layer; and the passivation layer is effective to passivate the sidewall and the bottom wall; and/or each of the structures has a top portion and a bottom portion having dissimilar conduction types. The terms “passivation” and “passivate” as used herein means a process of eliminating dangling bonds (i.e., unsatisfied valence on immobilized atoms).
According to an embodiment further of the embodiment, the structures have one of the following doping profiles: (i) the bottom portion is intrinsic and the top portion is p type; (ii) the bottom portion is n type and the top portion is p type; (iii) the bottom portion is intrinsic and the top portion is n type; (iv) the bottom portion is p type and the top portion is n type.
According to an embodiment further of the embodiment, the top portion has a height of 1 micron to 20 micron; the passivation layer has a thickness from 1 nm to 100 nm; the passivation layer is an electrically insulating material selected from a group consisting of HfO2, SiO2, Si3N4, Al2O3, an organic molecule monolayer; the doped layer has an opposite conduction type from the top portion; the doped layer is electrically connected to the bottom portion; the doped layer, the bottom portion and the top portion form a p-n or p-i-n junction; the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or a refractive index of the structures n1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.
According to an embodiment, the photovoltaic device further comprises a junction layer wherein: the junction layer is a doped semiconductor; the junction layer is disposed on the sidewall, on the bottom wall under the planar reflective layer, and on a top surface of the structures; and the junction layer is effective to passivate the sidewall and the bottom wall.
According to an embodiment further of the embodiment, the structures are a doped semiconductor and the structures and the junction layer have opposite conduction types; or the structures are an intrinsic semiconductor. An intrinsic semiconductor, also called an undoped semiconductor or i-type semiconductor, is a substantially pure semiconductor without any significant dopant species present. The number of charge carriers is therefore determined by the properties of the material itself instead of the amount of impurities. External electric field is not substantially screened in an intrinsic semiconductor because the intrinsic semiconductor does not have mobile electrons or holes supplied by dopants. It is thus more efficient to remove and/or collect electrons and/or holes generated in an intrinsic semiconductor by photons, using an external electric field.
According to an embodiment further of the embodiment, the junction layer has a thickness from 5 nm to 100 nm; the doped layer has an opposite conduction type from the junction layer; the doped layer is electrically connected to each of the structures; the doped layer, the structures and the junction layer form a p-n or p-i-n junction; the cladding layer has a thickness of about 175 nm; the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or a refractive index of the structures n1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.
According to an embodiment, each of the structures has a top portion and a bottom portion having dissimilar conduction types.
According to an embodiment further of the embodiment, the top portion and the junction layer have the same conduction type; and the structures have one of the following doping profiles: (i) the bottom portion is intrinsic and the top portion is p type; (ii) the bottom portion is n type and the top portion is p type; (iii) the bottom portion is intrinsic and the top portion is n type; (iv) the bottom portion is p type and the top portion is n type.
According to an embodiment further of the embodiment, the junction layer has a thickness from 5 nm to 100 nm; the doped layer has an opposite conduction type from the junction layer; the doped layer is electrically connected to the bottom portion of each of the structures; the doped layer, the bottom portion, the top portion and the junction layer form a p-n or p-i-n junction; the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or a refractive index of the structures n1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.
According to an embodiment, a method of making the photovoltaic device comprises: generating a pattern of openings in a resist layer using a lithography technique; forming the structures and recesses by etching the substrate; depositing the planar reflective layer such that the sidewall of each recess is free of the planar reflective layer; depositing the transparent material such that each recess is completely filled by the transparent material. A resist layer as used herein means a thin layer used to transfer a pattern to the substrate which the resist layer is deposited upon. A resist layer can be patterned via lithography to form a (sub)micrometer-scale, temporary mask that protects selected areas of the underlying substrate during subsequent processing steps. The resist is generally proprietary mixtures of a polymer or its precursor and other small molecules (e.g. photoacid generators) that have been specially formulated for a given lithography technology. Resists used during photolithography are called photoresists. Resists used during e-beam lithography are called e-beam resists. A lithography technique can be photolithography, e-beam lithography, holographic lithography. Photolithography is a process used in microfabrication to selectively remove parts of a thin film or the bulk of a substrate. It uses light to transfer a geometric pattern from a photo mask to a light-sensitive chemical photo resist, or simply “resist,” on the substrate. A series of chemical treatments then engraves the exposure pattern into the material underneath the photo resist. In complex integrated circuits, for example a modern CMOS, a wafer will go through the photolithographic cycle up to 50 times. E-beam lithography is the practice of scanning a beam of electrons in a patterned fashion across a surface covered with a film (called the resist), (“exposing” the resist) and of selectively removing either exposed or non-exposed regions of the resist (“developing”). The purpose, as with photolithography, is to create very small structures in the resist that can subsequently be transferred to the substrate material, often by etching. It was developed for manufacturing integrated circuits, and is also used for creating nanotechnology artifacts.
According to an embodiment, the method of making the photovoltaic device further comprises: planarizing the transparent material; coating the substrate with the resist layer; developing (i.e., selectively removing either exposed or non-exposed regions of the resist) the pattern in the resist layer; depositing a mask layer; and lifting off the resist layer. A mask layer as used herein means a layer that protects an underlying portion of the substrate from being etched.
According to an embodiment, the method of making the photovoltaic device further comprises ion implantation or depositing a dopant layer. A dopant, also called a doping agent, is a trace impurity element that is inserted into a substance (in very low concentrations) in order to alter the electrical properties or the optical properties of the substance. Ion implantation is process by which ions of a material can be implanted into another solid, thereby changing the physical properties of the solid. Ion implantation is used in semiconductor device fabrication and in metal finishing, as well as various applications in materials science research. The ions introduce both a chemical change in the target, in that they can be a different element than the target or induce a nuclear transmutation, and a structural change, in that the crystal structure of the target can be damaged or even destroyed by the energetic collision cascades.
According to an embodiment, the structures and recesses are formed by deep etch followed by isotropic etch. A deep etch is a highly anisotropic etch process used to create deep, steep-sided holes and trenches in wafers, with aspect ratios of often 20:1 or more. An exemplary deep etch is the Bosch process. The Bosch process, also known as pulsed or time-multiplexed etching, alternates repeatedly between two modes to achieve nearly vertical structures: 1. a standard, nearly isotropic plasma etch, wherein the plasma contains some ions, which attack the wafer from a nearly vertical direction (For silicon, this often uses sulfur hexafluoride (SF6)); 2. deposition of a chemically inert passivation layer (for instance, C4F8 source gas yields a substance similar to Teflon). Each phase lasts for several seconds. The passivation layer protects the entire substrate from further chemical attack and prevents further etching. However, during the etching phase, the directional ions that bombard the substrate attack the passivation layer at the bottom of the trench (but not along the sides). They collide with it and sputter it off, exposing the substrate to the chemical etchant. These etch/deposit steps are repeated many times over resulting in a large number of very small isotropic etch steps taking place only at the bottom of the etched pits. To etch through a 0.5 mm silicon wafer, for example, 100-1000 etch/deposit steps are needed. The two-phase process causes the sidewalls to undulate with an amplitude of about 100-500 nm. The cycle time can be adjusted: short cycles yield smoother walls, and long cycles yield a higher etch rate. Isotropic etch is non-directional removal of material from a substrate via a chemical process using an etchant substance. The etchant may be a corrosive liquid or a chemically active ionized gas, known as a plasma.
According to an embodiment, the method of making the photovoltaic device further comprises applying a resist layer by a print coating method, the print coating method comprising: coating a roller of a flexible material with a resist layer; transferring the resist layer to a surface of a substrate by rolling the roller on the surface, wherein the surface is flat or textured. According to an embodiment, the roller is polydimethylsiloxane.
According to an embodiment, the method of making the photovoltaic device further comprises applying a resist layer by a print coating method, the print coating method comprising: coating a stamp of a flexible material with a resist layer; transferring the resist layer to a surface of a substrate by pressing the stamp on the surface, wherein the surface is flat or textured. According to an embodiment, the stamp is polydimethylsiloxane.
According to an embodiment, a method of converting light to electricity comprises: exposing the photovoltaic device to light; drawing an electrical current from the photovoltaic device. The electrical current can be drawn from the planar reflective layer.
According to an embodiment, a photo detector comprises the photovoltaic device, wherein the photo detector is functional to output an electrical signal when exposed to light.
According to an embodiment, a method of detecting light comprises exposing the photovoltaic device to light; measuring an electrical signal from the photovoltaic device. The electrical signal can be an electrical current, an electrical voltage, an electrical conductance and/or an electrical resistance.
According to an embodiment, photovoltaic devices produce direct current electricity from sun light, which can be used to power equipment or to recharge a battery. A practical application of photovoltaics was to power orbiting satellites and other spacecraft, but today the majority of photovoltaic modules are used for grid connected power generation. In this case an inverter is required to convert the DC to AC. There is a smaller market for off-grid power for remote dwellings, boats, recreational vehicles, electric cars, roadside emergency telephones, remote sensing, and cathodic protection of pipelines. In most photovoltaic applications the radiation is sunlight and for this reason the devices are known as solar cells. In the case of a p-n junction solar cell, illumination of the material results in the creation of an electric current as excited electrons and the remaining holes are swept in different directions by the built-in electric field of the depletion region. Solar cells are often electrically connected and encapsulated as a module. Photovoltaic modules often have a sheet of glass on the front (sun up) side, allowing light to pass while protecting the semiconductor wafers from the elements (rain, hail, etc.). Solar cells are also usually connected in series in modules, creating an additive voltage. Connecting cells in parallel will yield a higher current. Modules are then interconnected, in series or parallel, or both, to create an array with the desired peak DC voltage and current.
According to an embodiment, the photovoltaic device can also be associated with buildings: either integrated into them, mounted on them or mounted nearby on the ground. The photovoltaic device can be retrofitted into existing buildings, usually mounted on top of the existing roof structure or on the existing walls. Alternatively, the photovoltaic device can be located separately from the building but connected by cable to supply power for the building. The photovoltaic device can be used as as a principal or ancillary source of electrical power. The photovoltaic device can be incorporated into the roof or walls of a building.
According to an embodiment, the photovoltaic device can also be used for space applications such as in satellites, spacecrafts, space stations, etc. The photovoltaic device can be used as main or auxiliary power sources for land vehicles, marine vehicles (boats) and trains. Other applications include road signs, surveillance cameras, parking meters, personal mobile electronics (e.g., cell phones, smart phones, laptop computers, personal media players).
EXAMPLES
FIG. 1A shows a schematic cross-section of a photovoltaic device 100, according to an embodiment. The photovoltaic device 100 comprises a substrate 105, a plurality of structures 120 essentially perpendicular to the substrate 105, one or more recesses 130 between the structures 120, and an electrode layer 180. Each recess 130 is filled with a transparent material 140. Each recess 130 has a sidewall 130a and a bottom wall 130b. The sidewall 130a and the bottom wall 130b both have a passivation layer 131. A top surface 120a of the structures 120 is free of the passivation layer 131. The bottom wall 130b has a planar reflective layer 132 disposed on the passivation layer 131. The sidewall 130a does not have any planar reflective layer. Each structure 120 has a top portion 121 and a bottom portion 122, the top portion 121 and the bottom portion 122 having dissimilar conduction types. The transparent material 140 preferably has a surface coextensive with the top surface 120a of the structures 120. The photovoltaic device 100 further comprises an electrode layer 180 disposed on the transparent material 140 and the structures 120. The term “dissimilar conduction types” as used herein means that the top portion 121 and the bottom portion 122 cannot be both p type, or both n type. The structures 120 can have one of the following four doping profiles (i.e., doping level distribution): (i) the bottom portion 122 is intrinsic and the top portion 121 is p type; (ii) the bottom portion 122 is n type and the top portion 121 is p type; (iii) the bottom portion 122 is intrinsic and the top portion 121 is n type; (iv) the bottom portion 122 is p type and the top portion 121 is n type. The top portion 121 can have a doping profile with decreasing doping levels in a direction from the top surface 120a to the bottom portion 122. The structures 120 are a single crystalline semiconductor material. The photovoltaic device 100 can further comprise a coupling layer 160 disposed on the electrode layer 180 and only directly above the top surface 120a. 
The structures 120 can comprise any suitable single crystalline semiconductor material, such as silicon, germanium, group III-V compound materials (e.g., gallium arsenide, gallium nitride, etc.), group II-VI compound materials (e.g., cadmium selenide, cadmium sulfide, cadmium telluride, zinc oxide, zinc selenide, etc.), quaternary materials (e.g., copper indium gallium selenide).
The structures 120 can have any cross-sectional shape. For example, the structures 120 can be cylinders or prisms with elliptical, circular, rectangular, polygonal cross-sections. The structures 120 can also be strips, or a mesh as shown in FIG. 10. According to one embodiment, the structures 120 are pillars with diameters from 50 nm to 5000 nm, heights from 1000 nm to 20000 nm, a center-to-center distance between two closest pillars of 300 nm to 15000 nm. The top portion 121 preferably has a height of 1 micron to 20 micron. The top portion 121 preferably has a gradient of doping levels, with a highest doping level at the top surface 120a. Preferably, the structures 120 have an overhanging portion 124 along an entire contour of the top surface 120a of the structures 120.
Each recess 130 preferably has a rounded or beveled inner edge between the sidewall 130a and the bottom wall 130b. 
The passivation layer 131 can be any suitable electrically insulating material, such as HfO2, SiO2, Si3N4, Al2O3, an organic molecule monolayer, etc. The passivation layer 131 can have any suitable thickness, such as from 1 nm to 100 nm. The passivation layer 131 is effective to passivate the sidewall 130a and the bottom wall 130b. 
The planar reflective layer 132 can be any suitable material, such as ZnO, Al, Au, Ag, Pd, Cr, Cu, Ti, Ni, a combination thereof, etc. The planar reflective layer 132 preferably is an electrically conductive material, more preferably a metal. The planar reflective layer 132 preferably has a reflectance of at least 50%, more preferably has a reflectance of at least 70%, most preferably has a reflectance of at least 90%, for visible light of any wavelength. The planar reflective layer 132 has a thickness of preferably at least 5 nm, more preferably at least 20 nm. The planar reflective layer 132 in all the recesses 130 is preferably connected. The planar reflective layer 132 is functional to reflect light incident thereon to the structures 120 so the light is absorbed by the structures 120. A photovoltaic device often has opaque electrodes on a surface that receives light. Any light incident on such opaque electrodes is either reflected away from the photovoltaic device or absorbed by the opaque electrodes, and thus does not contribute to generation of electricity. The planar reflective layer 132 preferably is functional as an electrode of the photovoltaic device 100.
The transparent material 140 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The transparent material 140 can be an electrically conductive material. The transparent material 140 preferably is a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The transparent material 140 preferably forms an Ohmic contact with the planar reflective layer 132. The transparent material 140 preferably is functional as an electrode of the photovoltaic device 100. The transparent material 140 can also be a suitable electrically insulating material such as SiO2 or a polymer.
The substrate 105 preferably has a flat surface 150 opposite the structures 120. The flat surface 150 can have a doped layer 151 of the opposite conduction type from the top portions 121, i.e. if the top portion 121 is n type, the doped layer 151 is p type; if the top portion 121 is p type, the doped layer 151 is n type. The doped layer 151 is electrically connected to the bottom portion 122 of each of the structures 120. If the bottom portion 122 is intrinsic, the top portion 121, the bottom portion 122 and the doped layer 151 form a p-i-n junction. If the bottom portion 122 is n type or p type, the top portion 121 and the bottom portion 122 form a p-n junction. The flat surface 150 can also have a metal layer 152 disposed on the doped layer 151. The metal layer 152 forms an Ohmic contact with the doped layer 151. The substrate 105 preferably has a thickness of at least 50 microns. Total area of the planar reflective layer 132 is preferable at least 40% of a surface area of the flat surface 150.
The electrode layer 180 can be the same material as the transparent material 140 or different material from the transparent material 140. The electrode layer 180 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The electrode layer 180 is an electrically conductive material. The electrode layer 180 preferably is a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The electrode layer 180 preferably forms an Ohmic contact with the top portions 121 of the structures 120. The electrode layer 180 preferably is functional as an electrode of the photovoltaic device 100.
The coupling layer 160 can be the same material as the transparent material 140 or different material from the transparent material 140. As shown in FIG. 5, refractive index of the structure 120 n1, refractive index of the transparent material 140 n2, refractive index of the coupling layer 160 n3, preferably satisfy relations of n1>n2 and n1>n3, which lead to enhanced light concentration in the structures 120.
In one embodiment, the structures 120 are pillars arranged in an array, such as a rectangular array, a hexagonal array, a square array, concentric ring. Each structure 120 is about 5 microns in height. A pitch of the structures 120 is from 300 nm to 15 microns. The term “pitch” is defined as a distance of a structure 120 to a nearest neighbor of the structure 120 along a direction parallel to the substrate 105. The term “array” as used herein means a spatial arrangement having a particular order.
A method of making the photovoltaic device 100 as shown in FIG. 1B, according to an embodiment, comprises the following steps:
In step 1000, providing the substrate 105 having the doped layer 151 and an epi layer 11 disposed on the doped layer 151. Epitaxy is a process of growing a crystal of a particular orientation on top of another crystal, where the orientation is determined by the underlying crystal. The term “epi layer” as used herein means a layer grown by epitaxy.
In step 1001, an upper layer 12 of the epi layer 11 is doped by ion implantation.
In step 1002, a resist layer 14 is applied on the doped upper layer 12. The resist layer 14 can be applied by spin coating. The resist layer 14 can be a photo resist or an e-beam resist.
In step 1003, lithography is performed. The resist layer 14 now has a pattern of openings in which the doped upper layer 12 is exposed. Shapes and locations of the openings correspond to the shapes and locations of the recesses 130. The resolution of the lithography is limited by the wavelength of the radiation used. Photolithography tools using deep ultraviolet (DUV) light with wavelengths of approximately 248 and 193 nm, allows minimum feature sizes down to about 50 nm. E-beam lithography tools using electron energy of 1 keV to 50 keV allows minimum feature sizes down to a few nanometers.
In step 1004, a mask layer 15 is deposited. The deposition can be done using a technique such as thermal evaporation, e-beam evaporation, sputtering. The mask layer 15 can be a metal such as Cr or Al, or a dielectric such as SiO2 or Si3N4. The thickness of the mask layer 15 can be determined by a depth of the recesses 130 and etching selectivity (i.e., ratio of etching rates of the mask layer 15 and the substrate 105).
In step 1005, remainder of the resist layer 14 is lift off by a suitable solvent or ashed in a resist asher to remove any mask layer 15 support thereon. A portion of the mask layer 15 in the openings of the resist layer 14 is retained. A portion of the doped upper layer 12 is now exposed through the retained mask layer 15.
In step 1006, the exposed portion of the doped upper layer 12 and the portion of the epi layer 11 directly therebelow are deep etched to a desired depth (e.g., 1 to 20 microns) followed by an isotropic etch, until the epi layer 11 is partially exposed, to form the structures 120 with the overhanging portion 124 and the recesses 130 with the beveled inner edge. Each of the structures 120 now has the top portion 121 which is part of the upper doped layer 12 and a bottom portion 122 which is part of the epi layer 11. Deep etching includes alternating deposition and etch steps and can lead to “scalloping” on the sidewall 130a of the recesses 130, i.e. the sidewall 130a is not smooth. The sidewall 130a can be smoothed by thermal annealing or dipping into an etchant such as potassium hydroxide (KOH) followed by rinsing. The deep etching can use gases such as C4F8 and SF6.
In step 1007, the passivation layer 131 is conformally (i.e., isotropically) deposited on surfaces of the recesses 130 and a top surface 15a of the retained mask layer 15. A conformal layer, such as the passivation 131, is a layer that covers a morphologically uneven surface and has an essentially uniform thickness. The passivation layer 131 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition.
In step 1008, a resist layer 16 is selectively applied such that the sidewall 130a and bottom wall 130b of the recesses are free of the resist layer 16 and a top surface 131a of the passivation layer 131 is completely covered by the resist layer 16. The resist layer 16 can be selectively applied by a suitable method such as a print coating method detailed hereinbelow according an embodiment.
In step 1009, a metal layer 17 is anisotropically deposited (i.e., non-conformally) such that the resist layer 16 and the bottom wall 130b are covered by the metal layer 17 while the sidewall 130a is free of the metal layer 17. The metal layer 17 can be deposited by a suitable technique such as thermal evaporation, e-beam evaporation. The metal 17 can be any suitable metal such as aluminum.
In step 1010, the resist layer 16 is lift off by a suitable solvent or ashed in a resist asher to remove any metal layer 17 support thereon. The top surface 131a of the passivation layer 131 is now exposed.
In step 1011, the top surface 131a of the passivation layer 131 is selected removed by a suitable technique such as ion milling, dry etching, sputtering, while leaving the passivation layer 131 on the sidewall 130a and bottom wall 130b of the recesses 130 intact. The top surface 15a of the retained mask layer 15 is now exposed. The metal layer 17 on the bottom wall 130b protects the passivation layer 131 underneath from being removed.
In step 1012, the retained mask layer 15 and the metal layer 17 are removed by a suitable technique such as wet etch in a suitable etchant. Now the top surface 120a of the structures 120 is exposed.
In step 1013, a resist layer 18 is selectively applied such that the sidewall 130a and bottom wall 130b of the recesses are free of the resist layer 18 and the top surface 120a of the structures 120 is completely covered by the resist layer 18. The resist layer 18 can be selectively applied by a suitable method such as the print coating method detailed hereinbelow according an embodiment.
In step 1014, the planar reflective layer 132 is anisotropically deposited (i.e., non-conformally) such that the resist layer 18 and the bottom wall 130b are covered by the planar reflective layer 132 while the sidewall 130a is free of the planar reflective layer 132. The planar reflective layer 132 can be deposited by a suitable technique such as thermal evaporation, e-beam evaporation. The planar reflective layer 132 can be any suitable material such as silver.
In step 1015, the resist layer 18 is lift off by a suitable solvent or ashed in a resist asher to remove any portion of the planar reflective layer 132 support thereon. The top surface 120a of the structures 120 is now exposed.
In step 1016, the transparent material 140 is deposited such that the planar reflective layer 132, the passivation layer 131 and the top surface 120a are completely covered and the recesses 130 are completely filled. The transparent material 140 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition.
In step 1017, the transparent material 140 is planarized using a suitable technique such as chemical mechanical polishing/planarization (CMP) such that the transparent material 140 has a surface coextensive with the top surface 120a of the structures 120 and the top surface 120a is exposed.
In step 1018, the electrode layer 180 is deposited using a suitable technique such as thermal evaporation, e-beam evaporation, sputtering, onto the transparent material 140 and the top surfaces 120a. The coupling layer 160 can be then deposited using a suitable technique such as sputtering, thermal evaporation or e-beam evaporation onto the electrode layer 180.
In step 1019, the metal layer 152 is deposited on the doped layer 151.
The method can further comprise one or more steps of thermal annealing.
FIG. 2A shows a schematic cross-section of a photovoltaic device 200, according to another embodiment. The photovoltaic device 200 comprises a substrate 205, a plurality of structures 220 essentially perpendicular to the substrate 205, one or more recesses 230 between the structures 220 and an electrode layer 280. Each recess 230 is filled with a transparent material 240. Each recess 230 has a sidewall 230a and a bottom wall 230b. The sidewall 230a, the bottom wall 230b of each recess 230 and a top surface 220a of the structures 220 have a junction layer 231 disposed thereon. The junction layer 231 is a doped semiconductor. The bottom wall 230b has a planar reflective layer 232 disposed on the junction layer 231. The sidewall 230a does not have any planar reflective layer. The structures 220 are a single crystalline semiconductor material. The structure 220 can be an intrinsic semiconductor or a doped semiconductor. If the structure 220 is a doped semiconductor, the structures 220 and the junction layer 231 have opposite conduction types, i.e., if the structures 220 are p type, the junction layer 231 is n type; if the structures 220 are n type, the junction layer 231 is p type. The transparent material 240 preferably has a surface coextensive with the top surface 220a of the structures 220. The photovoltaic device 200 further comprises an electrode layer 280 disposed on the transparent material 240 and the structures 220. The photovoltaic device 200 can further comprise a coupling layer 260 disposed on the electrode layer 280 and only directly above the top surface 220a. 
The structures 220 can comprise any suitable single crystalline semiconductor material, such as silicon, germanium, group III-V compound materials (e.g., gallium arsenide, gallium nitride, etc.), group II-VI compound materials (e.g., cadmium selenide, cadmium sulfide, cadmium telluride, zinc oxide, zinc selenide, etc.), quaternary materials (e.g., copper indium gallium selenide).
The structures 220 can have any cross-sectional shape. For example, the structures 220 can be cylinders or prisms with elliptical, circular, rectangular, polygonal cross-sections. The structures 220 can also be strips as shown in FIG. 9, or a mesh as shown in FIG. 10. According to one embodiment, the structures 220 are pillars with diameters from 50 nm to 5000 nm, heights from 1000 nm to 20000 nm, a center-to-center distance between two closest pillars of 300 nm to 15000 nm. Preferably, the structures 220 have an overhanging portion 224 along an entire contour of the top surface 220a of the structures 220.
Each recess 230 preferably has a rounded or beveled inner edge between the sidewall 230a and the bottom wall 230b. 
The junction layer 231 preferably has a thickness from 5 nm to 100 nm. The junction layer 231 is effective to passivate surfaces of the structures 220.
The planar reflective layer 232 can be any suitable material, such as ZnO, Al, Au, Ag, Pd, Cr, Cu, Ti, Ni, a combination thereof, etc. The planar reflective layer 232 preferably is an electrically conductive material, more preferably a metal. The planar reflective layer 232 preferably has a reflectance of at least 50%, more preferably has a reflectance of at least 70%, most preferably has a reflectance of at least 90%, for visible light of any wavelength. The planar reflective layer 232 has a thickness of preferably at least 5 nm, more preferably at least 20 nm. The planar reflective layer 232 in all the recesses 230 is preferably connected. The planar reflective layer 232 is functional to reflect light incident thereon to the structures 220 so the light is absorbed by the structures 220. The planar reflective layer 232 preferably is functional as an electrode of the photovoltaic device 200.
The transparent material 240 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The transparent material 240 can be an electrically conductive material. The transparent material 240 preferably is made of a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The transparent material 240 preferably forms an Ohmic contact with the junction layer 231. The transparent material 240 preferably forms an Ohmic contact with the planar reflective layer 232. The transparent material 240 preferably is functional as an electrode of the photovoltaic device 200. The transparent material 140 can also be a suitable electrically insulating material such as SiO2 or a polymer.
The substrate 205 preferably has a flat surface 250 opposite the structures 220. The flat surface 250 can have a doped layer 251 of the opposite conduction type from the junction layer 231, i.e. if the junction layer 231 is n type, the doped layer 251 is p type; if the junction layer 231 is p type, the doped layer 251 is n type. The doped layer 251 is electrically connected to each of the structures 220. If the structures 220 are intrinsic, the junction layer 231, the structures 220 and the doped layer 251 form a p-i-n junction. If the structures 220 are is n-type or p-type, the junction layer 231 and the structures 220 form a p-n junction. The flat surface 250 can also have a metal layer 252 disposed on the doped layer 251. The metal layer 252 forms an Ohmic contact with the doped layer 251. The substrate 205 preferably has a thickness of at least 50 microns. Total area of the planar reflective layer 232 is preferable at least 40% of a surface area of the flat surface 250.
The electrode layer 280 can be the same material as the transparent material 240 or different material from the transparent material 240. The electrode layer 280 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The electrode layer 280 is an electrically conductive material. The electrode layer 280 preferably is a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The electrode layer 280 preferably forms an Ohmic contact with the junction layer 231. The electrode layer 280 preferably is functional as an electrode of the photovoltaic device 200.
The coupling layer 260 can be the same material as the transparent material 240 or different material from the transparent material 240. As shown in FIG. 5, refractive index of the structure 220 n1, refractive index of the transparent material 240 n2, refractive index of the coupling layer 260 n3, preferably satisfy relations of n1>n2 and n1>n3, which lead to enhanced light concentration in the structures 220.
In one embodiment, the structures 220 are pillars arranged in an array, such as a rectangular array, a hexagonal array, a square array, concentric ring. Each pillar is about 5 microns in height. A pitch of the structures 220 is from 300 nm to 15 microns.
A method of making the photovoltaic device 200 as shown in FIG. 2B, according to an embodiment, comprises the following steps:
In step 2000, providing the substrate 205 having the doped layer 251 and an epi layer 21 disposed on the doped layer 251.
In step 2001, a resist layer 24 is applied on the epi layer 21. The resist layer 24 can be applied by spin coating. The resist layer 24 can be a photo resist or an e-beam resist.
In step 2002, lithography is performed. The resist layer 24 now has a pattern of openings in which the epi layer 21 is exposed. Shapes and locations of the openings correspond to the shapes and locations of the recesses 230. The resolution of the lithography is limited by the wavelength of the radiation used. Photolithography tools using deep ultraviolet (DUV) light with wavelengths of approximately 248 and 193 nm, allows minimum feature sizes down to about 50 nm. E-beam lithography tools using electron energy of 1 keV to 50 keV allows minimum feature sizes down to a few nanometers.
In step 2003, a mask layer 25 is deposited. The deposition can be done using a technique such as thermal evaporation, e-beam evaporation, sputtering. The mask layer 25 can be a metal such as Cr or Al, or a dielectric such as SiO2 or Si3N4. The thickness of the mask layer 25 can be determined by a depth of the recesses 230 and etching selectivity (i.e., ratio of etching rates of the mask layer 25 and the substrate 205).
In step 2004, remainder of the resist layer 24 is lift off by a suitable solvent or ashed in a resist asher to remove any mask layer 25 support thereon. A portion of the mask layer 25 in the openings of the resist layer 24 is retained. A portion of the epi layer 21 is now exposed through the retained mask layer 25.
In step 2005, the exposed portion of the epi layer 21 is deep etched to a desired depth (e.g., 1 to 20 microns) followed by an isotropic etch, to form the structures 220 with the overhanging portion 224 and the recesses 230 with the beveled inner edge. Deep etching includes alternating deposition and etch steps and can lead to “scalloping” on the sidewall 230b of the recesses 230, i.e. the sidewall 230b is not smooth. The sidewall 230b can be smoothed by thermal annealing or dipping into an etchant such as potassium hydroxide (KOH) followed by rinsing. The deep etching can use gases such as C4F8 and SF6.
In step 2006, the mask layer 25 is removed by a suitable such as wet etching with suitable etchant, ion milling, sputtering. The top surface 220a of the structures 220 is exposed.
In step 2007, a dopant layer 22 is conformally (i.e., isotropically) deposited on surfaces of the recesses 230 and a top surface 220a of the structures 220. The dopant layer 22 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition. The dopant layer 22 can comprise any suitable material such as trimethylboron, triisopropylborane ((C3H7)3B), triethoxyborane ((C2H5O)3B, and/or triisopropoxyborane ((C3H7O)3B. More details can be found in an abstract of a presentation titled “Atomic layer deposition of boron oxide as dopant source for shallow doping of silicon” by Bodo Kalkofen and Edmund P. Burte in the 218th Electrochemical Society Meeting, Oct. 10, 2010-Oct. 15, 2010, which is hereby incorporated by reference in its entirety.
In step 2008, a shield layer 23 is conformally (i.e., isotropically) deposited on surfaces of the dopant layer 22. The shield layer 23 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition. The shield layer 23 has a suitable material (such as silicon oxide, silicon nitride) and a suitable thickness (e.g., at least 10 nm, at least 100 nm or at least 1 micron) effective to prevent the dopant layer 22 from evaporation in step 2009.
In step 2009, the dopant layer 22 is diffused into the sidewall 230b, the bottom wall 230a and the top surface 220a by thermal annealing, which forms the junction layer 231 thereon. Thermal annealing can be conducted, for example, at about 850° C. for 10 to 30 minutes under a suitable atmosphere (e.g., argon).
In step 2010, the shield layer 23 is removed by a suitable technique such as wet etch using a suitable etchant such as HF. The junction layer 231 is now exposed.
In step 2011, a resist layer 26 is selectively applied such that the sidewall 230a and bottom wall 230b of the recesses 230 are free of the resist layer 26 and a top surface 231a of the junction layer 231 is completely covered by the resist layer 26. The resist layer 26 can be selectively applied by a suitable method such as the print coating method detailed hereinbelow according an embodiment.
In step 2012, the planar reflective layer 232 is anisotropically deposited (i.e., non-conformally) such that the resist layer 26 and the bottom wall 230b are covered by the planar reflective layer 232 while the sidewall 230a is free of the planar reflective layer 232. The planar reflective layer 232 can be deposited by a suitable technique such as thermal evaporation, e-beam evaporation. The planar reflective layer 232 can be any suitable material such as silver.
In step 2013, the resist layer 26 is lift off by a suitable solvent or ashed in a resist asher to remove any portion of the planar reflective layer 232 support thereon. The top surface 231a of the junction layer 220 is now exposed.
In step 2014, the transparent material 240 is deposited such that the planar reflective layer 232, the junction layer 231 and the top surface 231a are completely covered and the recesses 230 are completely filled. The transparent material 240 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition.
In step 2015, the transparent material 240 is planarized using a suitable technique such as CMP such that the transparent material 240 has a surface coextensive with the top surface 220a of the structures 220 and the top surface 231a of the junction layer 231 is exposed.
In step 2016, the electrode layer 280 is deposited using a suitable technique such as thermal evaporation, e-beam evaporation, sputtering, onto the transparent material 240 and the top surfaces 231a. The coupling layer 260 can be then deposited using a suitable technique such as sputtering, thermal evaporation or e-beam evaporation onto the electrode layer 280.
In step 2017, the metal layer 252 is deposited on the doped layer 251.
The method can further comprise one or more steps of thermal annealing.
FIG. 3A shows a schematic cross-section of a photovoltaic device 300, according to an embodiment. The photovoltaic device 300 comprises a substrate 305, a plurality of structures 320 essentially perpendicular to the substrate 305, one or more recesses 330 between the structures 320 and an electrode layer 380. Each recess 330 is filled with a transparent material 340. Each recess 330 has a sidewall 330a and a bottom wall 330b. The sidewall 330a, the bottom wall 330b of each recess 330 and a top surfaces 320a of the structures 320 have a junction layer 331 disposed thereon. The junction layer 331 is a doped semiconductor. The bottom wall 330b has a planar reflective layer 332 disposed on the junction layer 331. The sidewall 330a does not have any planar reflective layer. Each structure 320 has a top portion 321 and a bottom portion 322. The structures 320 can have one of the following four doping profiles (i.e., doping level distribution): (i) the bottom portion 322 is intrinsic and the top portion 321 is p type; (ii) the bottom portion 322 is n type and the top portion 321 is p type; (iii) the bottom portion 322 is intrinsic and the top portion 321 is n type; (iv) the bottom portion 322 is p type and the top portion 321 is n type. The top portion 321 can have a doping profile with decreasing doping levels in a direction from the top surface 320a to the bottom portion 322. The structures 320 are a single crystalline semiconductor material. The top portion 321 of the structures 320 and the junction layer 331 are semiconductor materials of the same conduction types, i.e., if the top portion 321 is p type, the junction layer 331 is p type; if the top portion 321 is n type, the junction layer 331 is n type. The transparent material 340 preferably has a surface coextensive with the top surface 320a of the structures 320. The photovoltaic device 300 further comprises an electrode layer 380 disposed on the transparent material 340 and the structures 320. The photovoltaic device 300 can further comprise a coupling layer 360 disposed on the electrode layer 280 and only directly above the top surface 320a. 
The structures 320 can comprise any suitable single crystalline semiconductor material, such as silicon, germanium, group III-V compound materials (e.g., gallium arsenide, gallium nitride, etc.), group II-VI compound materials (e.g., cadmium selenide, cadmium sulfide, cadmium telluride, zinc oxide, zinc selenide, etc.), quaternary materials (e.g., copper indium gallium selenide).
The structures 320 can have any cross-sectional shape. For example, the structures 320 can be cylinders or prisms with elliptical, circular, rectangular, polygonal cross-sections. The structures 320 can also be strips as shown in FIG. 9, or a mesh as shown in FIG. 10. According to one embodiment, the structures 320 are pillars with diameters from 50 nm to 5000 nm, heights from 1000 nm to 20000 nm, a center-to-center distance between two closest pillars of 300 nm to 15000 nm. The top portion 321 preferably has a height of 1 micron to 20 micron. The top portion 321 preferably has a gradient of doping levels, with a highest doping level at the top surface 320a. Preferably, the structures 320 have an overhanging portion 324 along an entire contour of the top surface 320a of the structures 320.
Each recess 330 preferably has a rounded or beveled inner edge between the sidewall 130a and the bottom wall 330b. 
The junction layer 331 preferably has a thickness from 5 nm to 100 nm. The junction layer 331 is effective to passivate surfaces of the structures 320.
The planar reflective layer 332 can be any suitable material, such as ZnO, Al, Au, Ag, Pd, Cr, Cu, Ti, Ni, a combination thereof, etc. The planar reflective layer 332 preferably is an electrically conductive material, more preferably a metal. The planar reflective layer 332 preferably has a reflectance of at least 50%, more preferably has a reflectance of at least 70%, most preferably has a reflectance of at least 90%, for visible light of any wavelength. The planar reflective layer 332 has a thickness of preferably at least 5 nm, more preferably at least 20 nm. The planar reflective layer 332 in all the recesses 330 is preferably connected. The planar reflective layer 332 is functional to reflect light incident thereon to the structures 320 so the light is absorbed by the structures 320. The planar reflective layer 332 preferably is functional as an electrode of the photovoltaic device 300.
The transparent material 340 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The transparent material 340 can be an electrically conductive material. The transparent material 340 preferably is made of a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The transparent material 340 preferably forms an Ohmic contact with the junction layer 331. The transparent material 340 preferably forms an Ohmic contact with the planar reflective layer 332. The transparent material 340 preferably is functional as an electrode of the photovoltaic device 300. The transparent material 340 can also be a suitable electrically insulating material such as SiO2 or a polymer.
The substrate 305 preferable has a flat surface 350 opposite the structures 320. The flat surface 350 can have a doped layer 351 of the opposite conduction type from the junction layer 331, i.e. if the junction layer 331 is n type, the doped layer 351 is also p type; if the junction layer 331 is p type, the doped layer 351 is also n type. The doped layer 351 is electrically connected to the bottom portion 322 of each of the structures 320. If the bottom portion 322 is intrinsic, the junction layer 331 and the top portion 321 form a p-i-n junction with the bottom portion 322 and the doped layer 351. If the bottom portion 322 is n type or p type, the junction layer 331 and the top portion 321 form a p-n junction with the bottom portion 322. The flat surface 350 can also have a metal layer 352 disposed on the doped layer 351. The metal layer 352 forms an Ohmic contact with the doped layer 351. The substrate 305 preferably has a thickness of at least 50 microns. Total area of the planar reflective layer 332 is preferable at least 40% of a surface area of the flat surface 350.
The electrode layer 380 can be the same material as the transparent material 340 or different material from the transparent material 340. The electrode layer 380 is substantially transparent to visible light, preferably with a transmittance of at least 50%, more preferably at least 70%, most preferably at least 90%. The electrode layer 380 is an electrically conductive material. The electrode layer 380 preferably is a transparent conductive oxide, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), ZIO (zinc indium oxide), ZTO (zinc tin oxide), etc. The electrode layer 380 preferably forms an Ohmic contact with the junction layer 331. The electrode layer 380 preferably is functional as an electrode of the photovoltaic device 300.
The coupling layer 360 can be the same material as the transparent material 340 or different material from the transparent material 340. As shown in FIG. 5, refractive index of the structure 320 n1, refractive index of the transparent material 340 n2, refractive index of the coupling layer 360 n3, preferably satisfy relations of n1>n2 and n1>n3, which lead to enhanced light concentration in the structures 320.
In one embodiment, the structures 320 are pillars arranged in an array, such as a rectangular array, a hexagonal array, a square array, concentric ring. Each pillar is about 5 microns in height. A pitch of the structures 320 is from 300 nm to 15 microns. The “pitch” is defined as a distance of a structure 320 to a nearest neighbor of the structure 320 along a direction parallel to the substrate 305.
A method of making the photovoltaic device 300 as shown in FIG. 3B, according to an embodiment, comprises the following steps:
In step 3000, providing the substrate 305 having the doped layer 351 and an epi layer 31 disposed on the doped layer 351.
In step 3001, an upper layer 32 of the epi layer 31 is doped by ion implantation.
In step 3002, a resist layer 34 is applied on the doped upper layer 32. The resist layer 34 can be applied by spin coating. The resist layer 34 can be a photo resist or an e-beam resist.
In step 3003, lithography is performed. The resist layer 34 now has a pattern of openings in which the doped upper layer 32 is exposed. Shapes and locations of the openings correspond to the shapes and locations of the recesses 330. The resolution of the lithography is limited by the wavelength of the radiation used. Photolithography tools using deep ultraviolet (DUV) light with wavelengths of approximately 248 and 193 nm, allows minimum feature sizes down to about 50 nm. E-beam lithography tools using electron energy of 1 keV to 50 keV allows minimum feature sizes down to a few nanometers.
In step 3004, a mask layer 35 is deposited. The deposition can be done using a technique such as thermal evaporation, e-beam evaporation, sputtering. The mask layer 35 can be a metal such as Cr or Al, or a dielectric such as SiO2 or Si3N4. The thickness of the mask layer 35 can be determined by a depth of the recesses 330 and etching selectivity (i.e., ratio of etching rates of the mask layer 35 and the substrate 305).
In step 3005, remainder of the resist layer 34 is lift off by a suitable solvent or ashed in a resist asher to remove any mask layer 35 support thereon. A portion of the mask layer 35 in the openings of the resist layer 34 is retained. A portion of the doped upper layer 32 is now exposed through the retained mask layer 35.
In step 3006, the exposed portion of the doped upper layer 32 and the portion of the epi layer 31 directly therebelow are deep etched to a desired depth (e.g., 1 to 20 microns) followed by an isotropic etch, until the epi layer 31 is partially exposed, to form the structures 320 with the overhanging portion 324 and the recesses 330 with the beveled inner edge. Each of the structures 320 now has the top portion 321 which is part of the upper doped layer 32 and a bottom portion 322 which is part of the epi layer 31. Deep etching includes alternating deposition and etch steps and can lead to “scalloping” on the sidewall 330b of the recesses 330, i.e. the sidewall 330b is not smooth. The sidewall 330b can be smoothed by thermal annealing or dipping into an etchant such as potassium hydroxide (KOH) followed by rinsing. The deep etching can use gases such as C4F8 and SF6.
In step 3007, the mask layer 35 is removed by a suitable such as wet etching with suitable etchant, ion milling, sputtering. The top surface 320a of the structures 320 is exposed.
In step 3008, a dopant layer 39 is conformally (i.e., isotropically) deposited on surfaces of the recesses 330 and a top surface 320a of the structures 320. The dopant layer 39 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition. The dopant layer 39 can comprise any suitable material such as trimethylboron, triisopropylborane ((C3H7)3B), triethoxyborane ((C2H5O)3B, and/or triisopropoxyborane ((C3H7O)3B. More details can be found in an abstract of a presentation titled “Atomic layer deposition of boron oxide as dopant source for shallow doping of silicon” by Bodo Kalkofen and Edmund P. Burte in the 218th Electrochemical Society Meeting, Oct. 10, 2010-Oct. 15, 2010, which is hereby incorporated by reference in its entirety.
In step 3009, a shield layer 33 is conformally (i.e., isotropically) deposited on surfaces of the dopant layer 39. The shield layer 33 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition. The shield layer 33 has a suitable material (such as silicon oxide, silicon nitride) and a suitable thickness (e.g., at least 10 nm, at least 100 nm or at least 1 micron) effective to prevent the dopant layer 39 from evaporation in step 3010.
In step 3010, the dopant layer 39 is diffused into the sidewall 330b, the bottom wall 330a and the top surface 320a by thermal annealing, which forms the junction layer 331 thereon. Thermal annealing can be conducted, for example, at about 850° C. for 10 to 30 minutes under a suitable atmosphere (e.g., argon).
In step 3011, the shield layer 33 is removed by a suitable technique such as wet etch using a suitable etchant such as HF. The junction layer 331 is now exposed.
In step 3012, a resist layer 36 is selectively applied such that the sidewall 330a and bottom wall 330b of the recesses 330 are free of the resist layer 36 and a top surface 331a of the junction layer 331 is completely covered by the resist layer 36. The resist layer 36 can be selectively applied by a suitable method such as the print coating method detailed hereinbelow according an embodiment.
In step 3013, the planar reflective layer 332 is anisotropically deposited (i.e., non-conformally) such that the resist layer 36 and the bottom wall 330b are covered by the planar reflective layer 332 while the sidewall 330a is free of the planar reflective layer 332. The planar reflective layer 332 can be deposited by a suitable technique such as thermal evaporation, e-beam evaporation. The planar reflective layer 332 can be any suitable material such as silver.
In step 3014, the resist layer 36 is lift off by a suitable solvent or ashed in a resist asher to remove any portion of the planar reflective layer 332 support thereon. The top surface 331a of the junction layer 320 is now exposed.
In step 3015, the transparent material 340 is deposited such that the planar reflective layer 332, the junction layer 331 and the top surface 331a are completely covered and the recesses 330 are completely filled. The transparent material 340 can be deposited by a suitable technique such as plating, chemical vapor deposition or atomic layer deposition.
In step 3016, the transparent material 340 is planarized using a suitable technique such as CMP such that the transparent material 340 has a surface coextensive with the top surface 320a of the structures 320 and the top surface 331a of the junction layer 331 is exposed.
In step 3017, the electrode layer 380 is deposited using a suitable technique such as thermal evaporation, e-beam evaporation, sputtering, onto the transparent material 340 and the top surfaces 331a. The coupling layer 360 can be then deposited using a suitable technique such as sputtering, thermal evaporation or e-beam evaporation onto the electrode layer 380.
In step 3018, the metal layer 352 is deposited on the doped layer 351.
The method can further comprise one or more steps of thermal annealing.
FIG. 6 shows an exemplary top cross sectional view of the photovoltaic device 100, 200 or 300, with the transparent material 140/240/340, the electrode layer 180/280/380 and the coupling layer 160/260/360 not shown for clarity. FIG. 7 shows an exemplary perspective view of the photovoltaic device 100, 200 or 300, with the transparent material 140/240/340, the electrode layer 180/280/380 and the coupling layer 160/260/360 not shown for clarity.
An embodiment of the print method used in steps 1008, 1013, 2011 and 3012 comprises: coating a roller 410 of a flexible material such as polydimethylsiloxane (PDMS) with a resist layer 420; transferring the resist layer 420 to a surface 405a of a substrate 405 by rolling the roller 410 on the surface 405a. The surface 405a can be flat or textured. During rolling the roller 410, the surface 405a can face upward or downward.
Another embodiment of the print method used in steps 1008, 1013, 2011 and 3012 comprises: coating a stamp 430 of a flexible material such as polydimethylsiloxane (PDMS) with a resist layer 420; transferring the resist layer 420 to a surface 405a of a substrate 405 by pressing the stamp 430 on the surface 405a. The surface 405a can be flat or textured. During rolling the roller 410, the surface 405a can face upward or downward.
As shown in FIG. 11B, the photovoltaic device 100, 200 or 300 can further comprise at least one via 599 in the transparent material 140, 240 or 340 and between the electrode layer 180, 280 or 380 and the planar reflective layer 132, 232 or 332, wherein the at least one via 599 is an electrically conductive material, preferably an electrically conductive transparent material (e.g. ITO, AZO, etc.) and the at least one via electrically connects the electrode layer 180, 280 or 380 and the planar reflective layer 132, 232 or 332. As shown in FIG. 11A, the via 599 can be made by etching a recess 598 through the electrode layer 180, 280 or 380 and the transparent material 140, 240 or 340 until the planar reflective layer 132, 232 or 332 is exposed and then filling the recess 598 to form the via 599. As shown in FIGS. 12A and 12B, the vias 599 can be any suitable shape such as rod-shaped or bar-shaped.
A method of converting light to electricity comprises: exposing the photovoltaic device 100, 200 or 300 to light; reflecting light to the structures 120, 220 or 320 using the planar reflective layer 132, 232 or 332; absorbing the light and converting the light to electricity using the structures 120, 220 or 320; drawing an electrical current from the photovoltaic device 100, 200 or 300. As shown in FIGS. 8A-8C, the electrical current can be drawn from the metal layer 152 and the planar reflective layer 132 or the metal layer 152 and the electrode layer 180, the metal layer 252 and the planar reflective layer 232, the metal layer 352 and the planar reflective layer 332, respectively, in the photovoltaic device 100, 200 or 300.
A photo detector according to an embodiment comprises the photovoltaic device 100, 200 or 300, wherein the photo detector is functional to output an electrical signal when exposed to light.
A method of detecting light comprises: exposing the photovoltaic device 100, 200 or 300 to light; measuring an electrical signal from the photovoltaic device 100, 200 or 300. The electrical signal can be an electrical current, an electrical voltage, an electrical conductance and/or an electrical resistance. A bias voltage can be applied to the structures 120, 220 and 320 respectively in the photovoltaic device 100, 200 or 300 when measuring the electrical signal.
While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

## Claims

1. A photovoltaic device operable to convert light to electricity, comprising a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a sidewall and a bottom wall, and a planar reflective layer disposed on the bottom wall of each recess, wherein the structures comprise a single crystalline semiconductor material; the sidewall of each recess is free of the planar reflective layer; and each recess is filled with a transparent material, wherein the structures have an overhanging portion along an entire contour of a top surface of the structures.

2. The photovoltaic device of claim 1, wherein the single crystalline semiconductor material is selected from a group consisting of silicon, germanium, group III-V compound materials, group II-VI compound materials, and quaternary materials.

3. The photovoltaic device of claim 1, wherein the structures are cylinders or prisms with a cross-section selected from a group consisting of elliptical, circular, rectangular, and polygonal cross-sections, strips, or a mesh.

4. The photovoltaic device of claim 1, wherein the structures are pillars with diameters from 50 nm to 5000 nm, heights from 1000 nm to 20000 nm, a center-to-center distance between two closest pillars of 300 nm to 15000 nm.

5. The photovoltaic device of claim 1, wherein each recess has a rounded or beveled inner edge between the sidewall and the bottom wall thereof.

6. The photovoltaic device of claim 1, wherein the planar reflective layer is a material selected from a group consisting of ZnO, Al, Au, Ag, Pd, Cr, Cu, Ti, Ni, and a combination thereof.

7. The photovoltaic device of claim 1, wherein the planar reflective layer is an electrically conductive material.

8. The photovoltaic device of claim 1, wherein the planar reflective layer is a metal.

9. The photovoltaic device of claim 1, whereinthe planar reflective layer has a reflectance of at least 50% for visible light of any wavelength.

10. The photovoltaic device of claim 1, wherein the planar reflective layer has a thickness of at least 5 nm.

11. The photovoltaic device of claim 1, wherein the planar reflective layer is functional to reflect light incident thereon to the structures so that the light is absorbed by the structures.

12. The photovoltaic device of claim 1, wherein the planar reflective layers in all the recesses are connected.

13. The photovoltaic device of claim 1, wherein the planar reflective layer is functional as an electrode of the photovoltaic device.

14. The photovoltaic device of claim 1, wherein the substrate has a flat surface opposite the structures.

15. The photovoltaic device of claim 14, wherein the flat surface has a doped layer and optionally a metal layer metal layer disposed on and forming an Ohmic contact with the doped layer.

16. The photovoltaic device of claim 15, wherein:
the transparent material has a surface coextensive with a top surface of the structures;
the transparent material is substantially transparent to visible light with a transmittance of at least 50%;
the transparent material is an electrically conductive material or an electrically insulating material;
the transparent material is a transparent conductive oxide;
the transparent material forms an Ohmic contact with the planar reflective layer; and/or
the transparent material is functional as an electrode of the photovoltaic device.

17. The photovoltaic device of claim 16, further comprising an electrode layer and optionally a coupling layer, wherein: the electrode layer is disposed on the transparent material and the structures; the electrode layer is the same material as the transparent material or different material from the transparent material; the electrode layer is substantially transparent to visible light with a transmittance of at least 50%; the electrode layer is an electrically conductive material; the electrode layer is a transparent conductive oxide; the electrode layer is functional as an electrode of the photovoltaic device; and/or the coupling layer is disposed on the electrode layer and only above a top surface of the structures.

18. The photovoltaic device of claim 17, further comprising a passivation layer, wherein: the passivation layer is disposed on the sidewall, and on the bottom wall under the planar reflective layer; a top surface of the structures is free of the passivation layer; and the passivation layer is effective to passivate the sidewall and the bottom wall; and/or each of the structures has a top portion and a bottom portion having dissimilar conduction types.

19. The photovoltaic device of claim 18, wherein the structures have one of the following doping profiles: (i) the bottom portion is intrinsic and the top portion is p type; (ii) the bottom portion is n type and the top portion is p type; (iii) the bottom portion is intrinsic and the top portion is n type; (iv) the bottom portion is p type and the top portion is n type.

20. The photovoltaic device of claim 18, further comprising a cladding layer, wherein:
the top portion has a height of 1 micron to 20 micron;
the passivation layer has a thickness from 1 nm to 100 nm;
the passivation layer is an electrically insulating material selected from a group consisting of HfO2, SiO2, Si3N4, Al2O3, an organic molecule monolayer;
the doped layer has an opposite conduction type from the top portion;
the doped layer is electrically connected to the bottom portion;
the doped layer, the bottom portion and the top portion form a p-n or p-i-n junction;
the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or a refractive index of the structures n1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.

21. The photovoltaic device of claim 17, further comprising a junction layer wherein: the junction layer is a doped semiconductor; the junction layer is disposed on the sidewall, on the bottom wall under the planar reflective layer, and on a top surface of the structures; and the junction layer is effective to passivate the sidewall and the bottom wall.

22. The photovoltaic device of claim 21, wherein the structures are a doped semiconductor and the structures and the junction layer have opposite conduction types; or the structures are an intrinsic semiconductor.

23. The photovoltaic device of claim 21, further comprising a cladding layer, wherein:
the junction layer has a thickness from 5 nm to 100 nm; the doped layer has an opposite conduction type from the junction layer;
the doped layer is electrically connected to each of the structures; the doped layer, the structures and the junction layer form a p-n or p-i-n junction;
the cladding layer has a thickness of about 175 nm;
the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or
a refractive index of the structures n.sub.1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.

24. The photovoltaic device of claim 21, wherein: each of the structures has a top portion and a bottom portion having dissimilar conduction types.

25. The photovoltaic device of claim 24, wherein the top portion and the junction layer have the same conduction type; and the structures have one of the following doping profiles: (i) the bottom portion is intrinsic and the top portion is p type; (ii) the bottom portion is n type and the top portion is p type; (iii) the bottom portion is intrinsic and the top portion is n type; (iv) the bottom portion is p type and the top portion is n type.

26. The photovoltaic device of claim 24, wherein: the junction layer has a thickness from 5 nm to 100 nm; the doped layer has an opposite conduction type from the junction layer; the doped layer is electrically connected to the bottom portion of each of the structures; the doped layer, the bottom portion, the top portion and the junction layer form a p-n or p-i-n junction; the coupling layer is the same material as the cladding layer or different material from the cladding layer; and/or a refractive index of the structures n1, a refractive index of the transparent material n2, a refractive index of the coupling layer n3, satisfy relations of n1>n2 and n1>n3.

27. The photovoltaic device of claim 17, further comprising at least one via in the transparent material and between the electrode layer and the planar reflective layer, wherein the at least one via is an electrically conductive material and the at least one via electrically connects the electrode layer and the planar reflective layer.

28. The photovoltaic device of claim 14, wherein total area of the planar reflective layer is at least 40% of a surface area of the flat surface.

29. The photovoltaic device of claim 1, wherein the substrate has a thickness of at least 50 microns.

30. The photovoltaic device of claim 1, wherein the structures are pillars arranged in an array; each structure is about 5 microns in height; a pitch of the structures is from 300 nm to 15 microns.

31. A photo detector comprising the photovoltaic device of claim 1, wherein the photo detector is functional to output an electrical signal when exposed to light.

32. The method of claim 31, wherein the electrical signal is an electrical current, an electrical voltage, an electrical conductance and/or an electrical resistance.

33. A method of detecting light comprises: exposing the photovoltaic device of claim 1 to light; measuring an electrical signal from the photovoltaic device.

34. The method of claim 33, wherein a bias voltage is applied to the structures in the photovoltaic device.

35. A method of making a photovoltaic device comprising a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a sidewall and a bottom wall, a planar reflective layer disposed on the bottom wall of each recess and each recess filled with a transparent material, the method comprising:
generating a pattern of openings in a resist layer using a lithography technique, wherein locations and shapes of the openings correspond to location and shapes of the structures;
forming the structures and recesses by etching the substrate;
depositing the planar reflective layer to the bottom wall, such that the sidewall of each recess is free of the planar reflective layer;
depositing the transparent material such that each recess is completely filled by the transparent material;
wherein the structures comprise a single crystalline semiconductor material, wherein the structures have an overhanging portion along an entire contour of a top surface of the structures.

36. The method of claim 35, further comprising:
planarizing the transparent material; coating the substrate with the resist layer;
developing the pattern in the resist layer;
depositing a mask layer; and
lifting off the resist layer.

37. The method of claim 35, further comprising ion implantation or depositing a dopant layer.

38. The method of claim 35, wherein the structures and recesses are formed by deep etch followed by isotropic etch.

39. The method of claim 35, further comprising applying a resist layer by a print coating method, the print coating method comprising:
coating a roller of a flexible material with a resist layer; transferring the resist layer to a surface of a substrate by rolling the roller on the surface, wherein the surface is flat or textured.

40. The method of claim 39, wherein the roller is polydimethylsiloxane.

41. The method of claim 35, further comprising applying a resist layer by a print coating method, the print coating method comprising:
coating a stamp of a flexible material with a resist layer; transferring the resist layer to a surface of a substrate by pressing the stamp on the surface, wherein the surface is flat or textured.

42. The method of claim 41, wherein the stamp is polydimethylsiloxane.

43. A method of converting light to electricity comprising:
exposing a photovoltaic device to light, wherein the photovoltaic device comprises a substrate, a plurality of structures essentially perpendicular to the substrate, one or more recesses between the structures, each recess having a sidewall and a bottom wall, a planar reflective layer disposed on the bottom wall of each recess, the sidewall of each recess being free of the planar reflective layer, and each recess filled with a transparent material;
reflecting light to the structures using the planar reflective layer;
absorbing the light and converting the light to electricity using the structures;
drawing an electrical current from the photovoltaic device;
wherein the structures comprise a single crystalline semiconductor material, wherein the structures have an overhanging portion along an entire contour of a top surface of the structures.

44. The method of claim 43, wherein the electrical current is drawn from the planar reflective layer.