1. Field of the Invention
This invention relates to a method to reduce thermal conductivity of nitrides, while at the same time keeping electrical conductivity high.
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.)
III-V nitride is a wide band gap semiconductor, and therefore remains a good unipolar semiconductor even at high temperatures above, e.g., around 1000 degrees Kelvin (K). Furthermore, even at higher temperatures above 1000 K, the nitride semiconductor remains unipolar. This property makes the III-V semiconductor a promising material for use in thermoelectric devices. Generally, electrodes based on metal materials degrade at temperatures above about 1000 K, but some electrodes for nitrides still operate adequately at the high temperatures.
However, the nitride semiconductor's thermal conductivity is too large to use in a thermoelectric device (220 Watts per millikelvin (W/mK) measured by [1]). The application of III-V nitride films to thermoelectricity has been quite limited so far, and there is little documented research available in this area [2-4]. Because of the high thermal conductivity of nitride, nitride has not attracted attention. The thermoelectric performance can be described by the figure of merit, ZT=α2σT/κ, where α, σ, κ, and T, are Seebeck coefficient, electrical conductivity, thermal conductivity, and absolute temperature, respectively.
For example, the long arrow 100 in
This contrasts with
a) and
The present invention provides a method to reduce thermal conductivities by introducing randomly-located dislocation(s), in particular, high-density stacking faults, and/or by using microscopic alloy-fluctuation in an In-containing layer. These nano-scale structures in nitrides can disturb phonon propagation. Nano-scale composition fluctuations can also create electron barriers which can enhance the Seebeck coefficient through the process of thermionic emission. In addition, to increase stacking faults, the present invention uses state-of-the-art nonpolar/semipolar GaN technology. In such situations, the electrical conductivity can be kept at the same level as in usual nitride films. This is a novel approach for nitrides.
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
a) and
a) and 5(b) are schematics illustrating relevant planes in III-nitride wurtzite crystals.
a)-(c) are schematics of a thermoelectric device of the present invention.
a) is a top view schematic, and
a) is a schematic of a monolithic thermoelectric device of the present invention, and
a) is a schematic of a non-monolithic thermoelectric device of the present invention, and
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
Thermoelectric devices are promising candidates for next generation energy sources, after solar cells. Thermoelectric devices generate an energy source from a temperature gradient. However, the thermal conductivity of nitride semiconductors is typically too large to use nitride semiconductors in a thermoelectric device. The technology described in the present invention provides a method to reduce the thermal conductivity by utilizing enhanced phonon scattering by randomly-located dislocation(s), in particular, high-density stacking faults. Nonpolar or semipolar nitride films are used. At the same time, the nitride semiconductor's electrical conductivity can be kept at the same level as usual/typical nitride films along the direction parallel to stacking faults. In addition, potential barriers associated with composition fluctuations can enhance the Seebeck coefficient through the process of thermionic emission.
Technical Description
The present invention uses nonpolar (11-20) nitride (a-plane nitride). Planar nonpolar a-plane GaN templates were grown by Metal Organic Chemical Vapor Deposition (MOCVD). The details of the template growth are disclosed in U.S. Utility patent application Ser. No. 10/413,691 entitled “NON-POLAR A-PLANE GALLIUM NITRIDE THIN FILMS GROWN BY METALORGANIC CHEMICAL VAPOR DEPOSITION,” attorneys docket number 30794.100-US-U1, and U.S. Utility patent application Ser. No. 12/207,407, entitled “GROWTH OF PLANAR, NON-POLAR A-PLANE GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys docket number 30794.94-US-C1, which applications are incorporated by reference herein. These a-plane GaN templates provide a nearly lattice-matched layer on which the nonpolar InGaN films could be re-grown.
The MOCVD growths were carried out in a high-temperature vertical reactor with high-speed rotation. A rotation speed of 300 revolutions per minute (rpm) was employed. The precursors used for Ga, In, Al, Mg and Si sources were trimethylgalium (TMG), trimethylindium (TMI), trimethylaluminium (TMA), bis-cyclopentadienyl magnesium (Cp2Mg), and disilane, respectively. High-purity ammonia was used as the nitrogen source. The a-plane GaN template on r-plane sapphire substrate is grown by a two-step process which includes a low temperature (620-650° C.) GaN nucleation layer step and a high temperature (1130-1180° C.) GaN growth step. A V/III ratio between 650 and 670 is used. The GaN growth rate, measured by an in-situ thickness measurement using reflectance spectroscopy, is in the range 4-6 Angstroms/second. A total flow of 10 standard liters per minute (slpm) is employed during the unintentionally doped (UID) GaN growth. The total thickness of undoped GaN is about 0.1-5 microns (μm). Less than 0.1 micron is preferable to prevent undesired heat conduction through this layer.
a) and
After growth of the a-plane nitride (e.g. UID GaN) template, an InGaN/GaN heterostructure region for the device is grown on the UID a-plane GaN template at a reduced temperature, at atmospheric pressure (near or at approximately 600-850 Torr), using N2 carrier gas. The crystalline growth of the InGaN/GaN heterostructure comprises the following steps:
(1) The nonpolar InGaN layers are grown on the a-plane GaN substrate or template at a reduced temperature (near or at approximately 900° C.) using an N2 carrier gas to enhance In incorporation and decrease In desorption; in addition, the InGaN layers are grown near or at atmospheric pressure (near or at approximately 760 Torr) to enhance InGaN film quality and decrease carbon incorporation.
(2) A GaN layer is grown on the nonpolar InGaN layers (at the same temperature as, or a higher temperature than, the InGaN growth temperature in step (1)). Preferably, this growth is repeated, and the heterostructure is comprised of a 10-100 period multi quantum well (MQW) stack with 10 nm Si-doped GaN barriers and 5 nm Si—In0.2Gan0.8N quantum wells. It is also preferable to have a higher In-composition. The total InGaN/GaN thickness is 0.15-1.5 microns. Thicker is more preferable to reduce resistivity in thermoelectric devices.
After the crystalline growth of the InGaN/GaN heterostructure, the In-containing film may be subjected to, or suffer heat stress at a higher temperature than the growth temperature of the InGaN/GaN heterostructure [6] (
After the growth and/or heat stress of the MQW/heterostructure, the present invention can deposit Si-doped GaN (typically 50 nm thick) at 1065° C. to get good ohmic contact. Ti/Al/Ni/Au (typically 10/100/10/100 nm) is then deposited on this as-grown wafer, using the usual photolithography using photoresist, and an e-beam evaporator.
After deposition of the Ti/Al/Ni/Au, a mesa is formed, by dry etching, or etching to a UID or insulating substrate.
The end result of the above-described method is a thermoelectric device according to the present invention, as illustrated in
a)-(c) illustrate a thermoelectric device 900 using a group III-V nitride semiconductor 908 including stacking faults or dislocations 920. The nitride semiconductor 908 may be a film, for example. Heat conduction of the semiconductor 908 is mainly determined by phonon propagation. Basically, dislocation and disorder act as a phonon scattering center. The heat conductivity is reduced by increasing phonon scattering using the stacking faults 920.
The nitride film 908 is typically grown on a foreign substrate 902 having a lattice misfit with nitride 908, thereby causing a large lattice mismatch between the substrate 902 and the nitride 908. The large lattice mismatch causes high density stacking faults 920 and threading dislocations. The nitride semiconductor film 908 is typically also grown toward a direction which is not along the c-axis. If the growth direction is not along c-axis, stacking faults 920 parallel to c-plane are generated effectively. For example, the nitride semiconductor film 908 may be grown along nonpolar (e.g. (10-10) and (11-20)) axes, because in the nonpolar nitrides 908 on a foreign substrate 902, there exist many stacking faults 920 parallel to the c-plane [7]. Alternatively, the nitride semiconductor film 908 may be grown toward a semipolar direction, e.g. (11-22), (10-1-1), or (10-1-3) axes, for example, because semipolar nitrides also include many stacking faults 920. The effect of growing the film 908 in a direction that is not along the c-axis is to generate stacking faults effectively.
The foreign substrate 902 could be an r-sapphire, m-SiC, LiAlO2, or m-sapphire substrate, for example, because nonpolar and semipolar nitride 908 can be grown on these substrates 902. Moreover, sapphire is a good insulator and has relatively low heat conductivity. It is also able to isolate electrically and thermally.
After device fabrication, thinning the substrate 902 is preferable to reduce undesirable heat conduction through the substrate 902.
The density of stacking faults 920 is typically more than 106 cm−1 (in nonpolar and semipolar GaN, this value is typical). The typical separation S between each fault 920 is about 10 nm. A previous study on nanowire GaN showed that a phonon mean free path of 10 nm was effective at reducing thermal conductivity [8,9].
In the thermoelectric device 900, the temperature gradient is imposed along the plane of stacking fault 920, in order to cause high electrical conductivity [10, 11, 12].
The device 900 of
The present invention has described lateral thermoelectric devices on thermally and electrically insulating substrates.
Thus,
When considering the internal resistance (parasitic resistance) of the device 1100 (or 1102a-d), a shorter distance 1108 is preferable. However, a metal electrode 1110a-d, 1112a-d, that has a contact resistance, must also be fabricated. Therefore, the length 1108 (or size) of the device 1100 (or 1102a-d) is limited by the contact resistance of the metal electrodes 1110a-d, 1112a-d; when this contact resistance is considered, the preferable length 1108 of the device 1100 (or 1102a-d) is more than 1 micron.
Preferably, mesas 1102a, 1102b, 1102c, and 1102d should be connected in series to get larger thermopower, as shown in
a) is a schematic top view of a monolithic device 1200, comprising a contact or interconnection 1202, and a heat conductor (good heat conducting materials such as thick metal or remaining nitride mesa) 1204 on/under the contact or interconnection 1202 to obtain a good thermal conduction in the regions except for the region of the device comprising the III-nitride mesas 1206.
a) is a schematic top view of a non-monolithic device 1300, comprising contact or interconnection 1302, high thermal conductivity materials 1304, and thermopower between electrodes A and B.
Possible Modifications
If the present invention uses a GaN bulk substrate, some kind of buffer layer can be used at the beginning of growth. A low-temperature (less than 800° C.) or AlN buffer is typically used. In order to introduce this buffer, it is possible to increase stacking faults and dislocations.
If the present invention uses a substrate with a thermal conductivity which is quite high, such as a GaN bulk substrate, SiC or Si, this high thermal conductivity substrate should be removed, or thinned, for example, by chemical mechanical polishing (CMP), mechanical polishing (MP) polishing, detachment by laser-irradiation, heating, or mechanical stress.
The present invention can grow various nitrides according to established technology. Combinations of substrate and grown nitride may be as follows:
1. {0001} GaN on {0001}/{11-20}-sapphire or {0001}GaN bulk substrate, {0001}SiC, {111}Si;
2. {10-10} GaN on {10-10} SiC, or LiAlO2;
3. {10-1-1} GaN on {100} spinel;
4. {10-1-3} GaN on {110} spinel;
5. {11-22} GaN on {1-100} sapphire; and
6. {10-1-3} GaN on {1-100} sapphire.
Alternatively, for all cases, a GaN bulk substrate is applicable and may be used.
In order to obtain a p-type layer, the present invention uses Mg dopants instead of Si, thereby obtaining a p-type thermoelectric device. For p-type thermoelectric devices, possible electrodes (for contact metal) include, but are not limited to, Pd/Au, metal alloys including the platinum group, Ni/Au, ZnO, ZnO: Ga and ITO, etc Annealing at high temperature (more than 400° C.), in N2 ambient to activate the acceptors (Mg) by removing H, is also required. A typical condition is annealing at more than 700° C., for less than 1 minute in N2.
For n-type thermoelectric devices, possible electrodes include metal alloys such as Ti/Al/Ni/Au, Ti/Al, other Al-containing metal alloys, or silicides.
The present invention is effective in any III-V nitride, including simple c-plane GaN.
Instead of stacking faults, other kinds of dislocations, such as threading dislocations, are effective. Instead of MOCVD, other kinds of growth can be used, for example, Hydride Vapor Phase Epitaxy and Molecular Beam Epitaxy.
Further Information
Further information on the present invention can be found in the Appendix of to the parent U.S. Provisional Application Ser. No. 61/325,177, filed on Apr. 16, 2010, by Hiroaki Ohta, Hiroaki Ohta, Alexander Sztein, Steven P. DenBaars, and Shuji Nakamura, entitled “III-V NITRIDE-BASED THERMOELECTRIC DEVICE,” attorney's docket number 30794.304-US-P2 (2009-389-1), which application is incorporated by reference herein. The Appendix comprises a publication by Alexander Sztein, Hiroaki Ohta, Junichi Sonoda, Ashok Ramu, John E. Bowers, Steven P. DenBaars, and Shuji Nakamura, entitled “GaN-Based Integrated Lateral Thermoelectric Device for Micro-Power Generation,” Applied Physics Express 2 (2009) 111003, which publication is incorporated by reference herein.
The following references are incorporated by reference herein.
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 Application Ser. No. 61/325,177, filed on Apr. 16, 2010, by Hiroaki Ohta, Hiroaki Ohta, Alexander Sztein, Steven P. DenBaars, and Shuji Nakamura, entitled “III-V NITRIDE-BASED THERMOELECTRIC DEVICE,” attorney's docket number 30794.304-US-P2 (2009-389-1); which application is incorporated by reference herein. This application is related to the following co-pending and commonly-assigned U.S. patent applications: U.S. Utility patent application Ser. No. 10/413,691, filed Apr. 15, 2003, by Michael D. Craven and James S. Speck, entitled “NON-POLAR A-PLANE GALLIUM NITRIDE THIN FILMS GROWN BY METALORGANIC CHEMICAL VAPOR DEPOSITION,” attorneys docket number 30794.100-US-U1 (2002-294-2), which application claims priority to U.S. Provisional Patent Application Ser. No. 60/372,909, filed Apr. 15, 2002, by Michael D. Craven, Stacia Keller, Steven P. DenBaars, Tal Margalith, James S. Speck, Shuji Nakamura, and Umesh K. Mishra, entitled “NON-POLAR GALLIUM NITRIDE BASED THIN FILMS AND HETERO STRUCTURE MATERIALS,” attorneys docket number 30794.95-US-P1 (2002-294/301/303); U.S. Utility patent application Ser. No. 12/207,407, filed Sep. 9, 2008, by Benjamin A. Haskell, Paul T. Fini, Shigemasa Matsuda, Michael D. Craven, Steven P. DenBaars, James S. Speck, and Shuji Nakamura, entitled “GROWTH OF PLANAR, NON-POLAR A-PLANE GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys docket number 30794.94-US-C1 (2003-225-2), which application is a continuation under 35 U.S.C. §120 of U.S. Utility patent application Ser. No. 10/537,385, filed on Jun. 3, 2005, by Benjamin A. Haskell, Paul T. Fini, Shigemasa Matsuda, Michael D. Craven, Steven P. DenBaars, James S. Speck, and Shuji Nakamura, entitled “GROWTH OF PLANAR, NON-POLAR GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys' docket number 30794.94-US-WO (2003-225-2), now U.S. Pat. No. 7,427,555, issued on Sep. 23, 2008, which application claims the benefit under 35 U.S.C. §365(c) of PCT International Application No. PCT/US03/21916, filed on Jul. 15, 2003, by Benjamin A. Haskell, Michael D. Craven, Paul T. Fini, Steven P. DenBaars, James S. Speck, and Shuji Nakamura, entitled “GROWTH OF PLANAR, NON-POLAR A-PLANE GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys' docket number 30794.94-WO-U1 (2003-225-2), which application claims priority to and the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Ser. No. 60/433,843, filed on Dec. 16, 2002, by Benjamin A. Haskell, Michael D. Craven, Paul T. Fini, Steven P. DenBaars, James S. Speck, and Shuji Nakamura, entitled “GROWTH OF REDUCED DISLOCATION DENSITY NON-POLAR GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys' docket number 30794.93-US-P1 (2003-224-1), and U.S. Provisional Application Ser. No. 60/433,844, filed on Dec. 16, 2002, by Benjamin A. Haskell, Paul T. Fini, Shigemasa Matsuda, Michael D. Craven, Steven P. DenBaars, James S. Speck, and Shuji Nakamura, entitled “TECHNIQUE FOR THE GROWTH OF PLANAR, NON-POLAR A-PLANE GALLIUM NITRIDE BY HYDRIDE VAPOR PHASE EPITAXY,” attorneys' docket number 30794.94-US-P1 (2003-225-1); and U.S. Provisional Patent Application Ser. No. 61/169,984, filed on Apr. 16, 2009, by Hiroaki Ohta, Steven P. DenBaars, and Shuji Nakamura, entitled “III-V NITRIDE-BASED THERMOELECTRIC DEVICE,” attorney's docket number 30794.304-US-P1 (2009-389-1); all of which applications are incorporated by reference herein.
Number | Date | Country | |
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61325177 | Apr 2010 | US |