1. Field of the Invention
This invention is related to semiconductor materials, methods, and devices, and more particularly, to the manufacturing and fabrication of III-nitride photovoltaic devices, such as solar cells.
2. Description of the Related Art
(Note: This application references a number of different publications as indicated throughout the specification by one or more reference numbers within brackets, e.g., [x]. A list of these different publications ordered according to these reference numbers can be found below in the section entitled “References.” Each of these publications is incorporated by reference herein.)
The usefulness of III-nitride material system has been well established for the fabrication of visible and ultraviolet light-emitting devices and high-frequency and high-power electronic devices. More recently, though, the III-nitride material system has begun to gain attention for use in photovoltaic (PV) applications. [1-5]
The III-nitride material system has several properties which give it key advantages over existing materials currently used in high-efficiency solar cells. To increase device efficiency beyond current levels, it will be necessary to move toward devices with increasing numbers of cells with bandgaps that span the entire solar spectrum. Unlike other III-V based alloys, which have bandgaps limited to less than ˜2.5 eV, the bandgap of InGaN-based alloys ranges from 0.7 eV for InN to 3.4 eV for GaN, which spans nearly the entire solar spectrum. [8] Moreover, InGaN alloys have a direct bandgap for the entire range of In compositions and therefore have very high absorption coefficients on the order of 1×105 cm−1. [9] These large absorption coefficients allow for the absorption of large amounts of light in very thin layers, enabling the growth of high-quality pseudo-morphic device structures and potentially leading to significant cost savings.
Unlike III-nitride-based light-emitting devices and high-frequency and high-power electronic devices, which are now commercially available, III-nitride solar cells are still in the research and development stage. Among the limited reports of III-nitride solar cells in the scientific literature, all of the devices have functioned by collecting light that was incident on the top-side of the III-nitride device layers. [1-5] In the case of III-nitride LEDs, significant improvements in light extraction efficiency were demonstrated for devices with back-side light-emitting geometries compared to devices with traditional top-side light-emitting geometries. [6,10] Likewise, in the case of III-nitride solar cells, similar improvements in light collection efficiency should be possible for devices with back-side light collection geometries compared to devices with top-side light collection geometries.
Nonetheless, there is a need in the art for improved techniques for providing III-nitride solar cells. The present invention satisfies this need.
To overcome the limitations in the prior art described above, and to overcome other limitations that will become apparent upon reading and understanding the present specification, the present invention discloses a III-nitride photovoltaic device structure and method for fabricating the III-nitride photovoltaic device that increases the light collection efficiency of the III-nitride photovoltaic device. Specifically, the III-nitride photovoltaic device is comprised of one or more III-nitride device layers, and the III-nitride photovoltaic device functions by collecting light that is incident on the back-side of the III-nitride device layers.
The III-nitride device layers are grown on a substrate, wherein a planar or patterned wafer may be used as the substrate for growth of the III-nitride device layers. The substrate may be removed from the III-nitride device layers, wherein the III-nitride device layers are exposed when the substrate is removed and the exposed III-nitride device layers are then intentionally roughened to enhance their light collection efficiency.
The III-nitride device layers may contain one or more junctions of varying bandgaps, wherein a plurality of junctions with varying bandgaps improve overall device efficiency by spanning a broader spectrum associated with the incident light. The collection of the incident light via the back-side of the device simplifies the fabrication of the multiple junctions.
Variations in the structure of contacts is possible as well. The III-nitride photovoltaic device may include grid-like contacts, transparent or semi-transparent contacts, or reflective contacts.
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration a specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Overview
The present invention comprises a structure and method to increase the light collection efficiency of III-nitride photovoltaic devices, such as solar cells.
The term “III-nitrides” refers to any alloy composition of the (Ga,Al,In,B)N semiconductors having the formula GawAlxInyBzN where 0≦w≦1, 0≦x≦1, 0≦y≦1, 0≦z≦1, and w+x+y+z=1. Accordingly, it will be appreciated that the discussion of the invention hereinafter in reference to GaN and InGaN materials is applicable to the formation of various other (Ga,Al,In,B)N material species. Further, (Ga,Al,In,B)N materials within the scope of the invention may further include minor quantities of dopants and/or other impurity or inclusional materials.
Previously reported III-nitride solar cells functioned by collecting light that was incident on the top-side of the III-nitride device layers. [1-5] In the context of this invention, the term “back-side” refers to the side of the III-nitride device layers that are closest to the substrate on which they are grown or deposited, whereas the word “top-side” refers to the side of the III-nitride device layers that are furthest from the substrate on which they are grown or deposited. It is implied in this definition that the III-nitride device layers are grown during a process that is distinct from the substrate manufacturing process and that the III-nitride device layers are grown or deposited on only one side of the substrate, as is typically the case for semiconductor devices.
These definitions are illustrated in
In contrast to previously reported III-nitride solar cells, this invention describes a structure and method for collecting light that is incident on the back-side of the III-nitride device layers of a III-nitride photovoltaic device. This type of device structure is referred to herein as a “flip-chip” device.
In the context of this invention, the term “flip-chip” refers to any device which functions by collecting light that is incident on the back-side of the III-nitride device layers and would typically involve mounting the top-side of the III-nitride device layers to a carrier wafer. In the context of this invention, the term “carrier wafer” refers to a wafer or other piece of mechanically stable material onto which the top-side of the III-nitride device layers is mounted or bonded. The purpose of the carrier wafer is to provide mechanical stability for the device, to remove heat from the device, and/or to enable further processing of the back-side of the device. This is analogous to the case of a flip-chip light-emitting diode (LED), [6] wherein the top-side of the III-nitride device layers is typically mounted to a carrier wafer and light is emitted from the back-side of the III-nitride device layers. Use of a flip-chip device geometry in conjunction with other variations in device design should improve device efficiency by increasing the path length for light absorption [7] in the active layers of the device and by reducing the light absorption in the other layers of the device.
In this context of this invention, the term “flip-chip solar cell” refers to a photovoltaic device which is grown on a planar substrate, has the substrate intact in the final device structure, and is designed for collecting light incident on the back-side of the III-nitride device layers and producing a flow of electrons in response thereto. The advantage of a flip-chip III-nitride solar cell over a conventional III-nitride solar cell is that, in the case of a flip-chip solar cell, the incident light encounters the active region prior to reaching the absorbing metal contacts. Although such a device could be fabricated in many different ways, one such method is described below.
First, the III-nitride device layers are grown on the top-side of a substrate by a growth technique such as metalorganic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE). In the device shown in
The structure of this device is nearly identical to the device described in
In the case of III-nitride LEDs, similar device geometries have been used to significantly improve the light extraction efficiency compared to devices with traditional top-side light-emitting geometries. [6,10] Although such a device could be fabricated in many different ways, one such method is described below.
First, the III-nitride device layers are grown on the top-side of a substrate by a growth technique, such as metalorganic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE). In the device shown in
The devices shown in
In this design, the junction (InGaN active region #1506) with the largest bandgap (Eg1) is grown first, the junction (InGaN active region #2512) with the second largest bandgap (Eg2) is grown next, the junction (InGaN active region #3518) with the third largest bandgap (Eg3) is grown next, and so on. As is typically the case for GaAs-based tandem solar cells, each forward-biased junction is connected to the next forward-biased junction by a reverse-biased tunnel junction 528a, 528b. [14] For such a configuration, the active regions with high indium mole fractions would be less likely to be thermally damaged, because the active regions for each successive junction are grown at progressively lower temperatures. For the purposes of illustration, the tandem solar cell shown in
The devices shown in
This type of p-contact 606 would be used in a situation similar to the grid-like p-contact, where the majority of low-energy photons that are not absorbed by the III-nitride solar cell are transmitted through the structure to one or more smaller bandgap solar cells. This type of p-contact 606 could be made with transparent conducting oxide such as indium tin oxide [16] or with one or more semi-transparent thin metal layers. [17]
The devices shown in
The advantage of this configuration is that it doubles the effective path length of the light in the active region(s) 702 by creating a second pass for the light through the III-nitride device layers. Although this configuration increases the effective path length of the light in the active region(s) 702, it precludes integration with smaller bandgap solar cells and would probably work best in a monolithic tandem solar cell made entirely of III-nitrides, such as the device shown in
Possible Modifications
The III-nitride solar cells described above were grown on c-plane sapphire substrates. However, the scope of this invention includes the growth of III-nitride solar cells on all possible crystallographic orientations of all possible foreign substrates. These foreign substrates include, but are not limited to, silicon carbide, silicon dioxide, silicon, zinc oxide, boron nitride, lithium aluminate, lithium niobate, germanium, aluminum nitride, lithium gallate, partially substituted spinels, and quaternary tetragonal oxides sharing the γ-LiAlO2 structure.
The scope of this invention also covers III-nitride solar cells grown on crystallographic orientations other than the c-plane orientation cited in the technical description. This idea is also pertinent to all polar, nonpolar, and semipolar planes that can be used for growing III-nitride semiconductor devices. The term “nonpolar plane” includes the {11-20} planes, known collectively as a-planes, and the {10-10} planes, known collectively as m-planes. The term “semipolar plane” can be used to refer to any plane that cannot be classified as c-plane, a-plane, or m-plane. In crystallographic terms, a semipolar plane would be any plane that has at least two nonzero h, i, or k Miller indices and a nonzero l Miller index.
This invention also covers the selection of particular crystal polarities. The use of curly brackets, { }, throughout this document denotes a family of symmetry-equivalent planes. Thus, the {10-12} family includes the (10-12), (−1012), (1-102), (−1102), (01-12), and (0-112) planes. All of these planes are Ga-polarity, meaning that the crystal's c-axis points away from the substrate. Likewise, the {10-1-2} family includes the (10-1-2), (−101-2), (1-10-2), (−110-2), (01-1-2), and (0-11-2) planes. All of these planes are N-polarity, meaning that the crystal's c-axis will point towards the substrate. All planes within a single crystallographic family are equivalent for the purposes of this invention, though the choice of polarity can affect the behavior of the growth process. In some applications it would be desirable to grow on N-polarity planes, while in other cases growth on Ga-polarity planes would be preferred. Both polarities are acceptable for the practice of this invention.
Furthermore, variations in III-nitride nucleation (or buffer) layers and nucleation layer growth methods are acceptable for the practice of this invention. The growth temperature, growth pressure, orientation, and composition of the nucleation layers need not match the growth temperature, growth pressure, orientation, and composition of the subsequent thin films and heterostructures. The scope of this invention includes the growth of III-nitride solar cells on all possible substrates using all possible nucleation layers and nucleation layer growth methods.
The preferred embodiment presented above discussed the growth of c-plane III-nitride solar cells on foreign substrates. However, the scope of this invention includes the growth of polar, nonpolar, or semipolar III-nitride solar cells on all possible free-standing polar, nonpolar, or semipolar III-nitride wafers created by all possible crystal growth methods and wafer manufacturing techniques.
Variations in solar cell active region and heterostructure design are possible without departing from the scope of the present invention. The specific thickness and composition of the layers are variables inherent to particular device designs and may be used in alternative embodiments of the present invention. For instance, the c-plane solar cells in the preferred embodiment of the invention utilize InxGa1-xN-based layers for the active region. However, the scope of this invention also includes solar cells which utilize layers of any alloy composition of GawAlxInyBzN (where 0≦w≦1, 0≦x≦1, 0≦y≦1, 0≦z≦1, and w+x+y+z=1) for the active region. Likewise, the c-plane solar cells in the preferred embodiment of the invention utilize p-type GaN and n-type GaN layers for carrier transport between the active region and the contacts. However, the scope of this invention also includes solar cells which utilize layers of any alloy composition of GawAlxInyBzN (where 0≦w≦1,0≦x≦1,0≦y≦1,0≦z≦1, and w+x+y+z=1) for carrier transport between the active region and the contacts.
The preferred embodiment of this invention discussed growing the III-nitride device layers by MOCVD or MBE. However, different growth methods could be used in alternative embodiments of the present invention. Other potential growth methods include HVPE, LPE, CBE, PECVD, sublimation, and sputtering.
The III-nitride solar cells described above were comprised of multiple homogenous layers. However, the scope of this invention also includes III-nitride solar cells comprised of multiple layers having varying or graded compositions.
Additional impurities or dopants can also be incorporated into the III-nitride thin films described in this invention. For example, Fe, Mg, Si, and Zn are frequently added to various layers in III-nitride heterostructures to alter the conduction properties of those and adjacent layers. The use of such dopants and others not listed here are within the scope of the invention.
Some of the III-nitride solar cells described above were grown on patterned sapphire substrates. However, the scope of this invention includes the growth of III-nitride solar cells on all possible crystallographic orientations of all possible patterned substrates. These substrates include, but are not limited to, silicon carbide, silicon dioxide, silicon, zinc oxide, boron nitride, lithium aluminate, lithium niobate, germanium, aluminum nitride, lithium gallate, partially substituted spinels, and quaternary tetragonal oxides sharing the γ-LiAlO2 structure. Moreover, in the preferred embodiment, the substrate was patterned on the surface on which the III-nitride device layers were grown. However, the substrate may have also been patterned on the back surface or at an interface inside the substrate itself. The scope of this invention involves the growth of III-nitride solar cells on any patterned substrate, regardless of the physical location of the substrate patterning.
Some of the III-nitride solar cell structures described above involved removing the sapphire substrate by laser lift-off (LLO). However, the substrate may have been removed by any other possible substrate removal method, such as wet etching, dry etching, grinding, lapping, polishing, or other wafer thinning or removal technique. All possible substrate removal methods are within the scope of this invention.
Some of the III-nitride solar cells described above involved roughening an exposed nitrogen-face c-plane GaN surface by PEC etching. However, the exposed III-nitride device layers could have been roughened by any other surface roughening technique. All surface roughening techniques are within the scope of this invention. Moreover, in the preferred embodiment, the exposed surface that was roughened was a nitrogen-face c-plane GaN surface. However, the exposed surface could have been of any crystallographic orientation or of any polarity. The roughening of all possible exposed surfaces of all possible crystallographic orientations and polarities is within the scope of this invention.
Some of the III-nitride solar cells described above contained a transparent p-contact made of a transparent conducting film such as indium tin oxide. However, the scope of this invention also includes flip-chip solar cells containing transparent p-contacts made of any possible material. These possible materials include, but are not limited to, conductive polymers and transparent conductive oxides such as ZnO, In2O3, SnO2, and CdO, as well as multicomponent oxides consisting of combinations of ZnO, In2O3, SnO2, and CdO. Additional impurities or dopants could also be incorporated into the transparent conducting films. For example, Al, Ga, In, and Sn are frequently added to transparent conducting oxides to alter their conduction properties. The use of all possible materials to form transparent p-contacts on III-nitride flip-chip solar cells is within the scope of this invention.
The tandem III-nitride solar cells described above contained several active regions connected in series by tunnel junctions. However, one or more of the active regions could have also been connected in parallel. This alternative configuration would alleviate the need for tunnel junctions, but would necessitate the use of more than two contacts to the device. The use of multiple active regions connected in series, in parallel, or in a combination of the two is within the scope of this invention.
Advantages and Improvements
The present invention describes an improved III-nitride photovoltaic device structure and method for fabricating the improved III-nitride photovoltaic device that provides both improved manufacturability and higher performance due to increased light collection efficiency.
Previously reported III-nitride solar cells function by collecting light that was incident on the top-side of the III-nitride device layers. [1-5] In contrast, this invention describes a structure and method for collecting light that is incident on the back-side of III-nitride device layers of a flip-chip III-nitride photovoltaic device.
Use of a flip-chip device geometry in conjunction with other variations in device design should improve device efficiency by increasing the path length for light absorption [7] in the active layers of the device and by reducing the light absorption in the other layers of the device.
The proposed device can be used for converting sunlight into electricity for various commercial, industrial, or scientific applications. The proposed device can be expected to find utility in the same applications as current commercially-available solar cells.
The following references are incorporated by reference herein.
1. Jani, I. Ferguson, C. Honsberg, and S. Kurtz, Appl. Phys. Lett. 91 (2007).
2. J. Neufeld, N. G. Toledo, S. C. Cruz, M. Iza, S. P. DenBaars, and U. K. Mishra, Appl. Phys. Lett. 93 (2008).
3. A. Berkman, N. A. El-Masry, A. Emara, and S. M. Bedair, Appl. Phys. Lett. 92 (2008).
4. Chen, K. D. Matthews, D. Hao, W. J. Schaff, and L. F. Eastman, Phys. Status Solidi A 205, 1103 (2008).
5. M. Cai, S. W. Zeng, and B. P. Zhang, Appl. Phys. Lett. 95 (2009).
6. R. Krames, O. B. Shchekin, R. Mueller-Mach, G. O. Mueller, L. Zhou, G. Harbers, and M. G. Craford, J. Disp. Technol. 3, 160 (2007).
7. Nelson, The Physics of Solar Cells, 1st ed. (Imperial College Press, London, 2003).
8. Wu, W. Walukiewicz, K. M. Yu, W. Shan, J. W. Ager, E. E. Haller, H. Lu, W. J. Schaff, W. K. Metzger, and S. Kurtz, J. Appl. Phys. 94, 6477 (2003).
9. F. Muth, J. H. Lee, I. K. Shmagin, R. M. Kolbas, H. C. Casey, B. P. Keller, U. K. Mishra, and S. P. DenBaars, Appl. Phys. Lett. 71, 2572 (1997).
10. Fujii, Y. Gao, R. Sharma, E. L. Hu, S. P. DenBaars, and S. Nakamura, Appl. Phys. Lett. 84, 855 (2004).
11. Yamada, T. Mitani, Y. Narukawa, S. Shioji, I. Niki, S. Sonobe, K. Deguchi, M. Sano, and T. Mukai, Jpn. J. Appl. Phys. 41, L1431 (2002).
12. Gao, T. Fujii, R. Sharma, K. Fujito, S. P. Denbaars, S. Nakamura, and E. L. Hu, Jpn. J. Appl. Phys. 43, L637 (2004).
13. Gao, M. D. Craven, J. S. Speck, S. P. DenBaars, and E. L. Hu, Appl. Phys. Lett. 84, 3322 (2004).
14. Tanabe, Energies 2, 504 (2009).
15. Queren, M. Schillgalies, A. Avramescu, G. Bruderl, A. Laubsch, S. Lutgen, and U. Strauss, J. Cryst. Growth 311, 2933 (2009).
16. Margalith, O. Buchinsky, D. A. Cohen, A. C. Abare, M. Hansen, S. P. DenBaars, and L. A. Coldren, Appl. Phys. Lett. 74, 3930 (1999).
17. K. Ho, C. S. Jong, C. C. Chiu, C. N. Huang, C. Y. Chen, and K. K. Shih, Appl. Phys. Lett. 74, 1275 (1999).
This concludes the description of the preferred embodiment of the present invention. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
This application claims the benefit under 35 U.S.C. Section 119(e) of the following co-pending and commonly-assigned application: U.S. Provisional Patent Application Ser. No. 61/405,492, filed on Oct. 21, 2010, by Robert M. Farrell, Carl J. Neufeld, Nikholas G. Toledo, Steven P. DenBaars, Umesh K. Mishra, James S. Speck, and Shuji Nakamura, entitled “III-NITRIDE FLIP-CHIP SOLAR CELLS,” attorneys' docket number 30794.388-US-P1 (Jan. 24, 2011); which application is incorporated by reference herein.
This invention was made with U.S. Government support under Grant No. HR0011-10-1-0049 awarded by DARPA. The U.S. Government has certain rights in this invention.
Number | Date | Country | |
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61405492 | Oct 2010 | US |