WO2000030185A1 - Quantum well thermoelectric material on very thin substrate - Google Patents

Quantum well thermoelectric material on very thin substrate Download PDF

Info

Publication number
WO2000030185A1
WO2000030185A1 PCT/US1999/026996 US9926996W WO0030185A1 WO 2000030185 A1 WO2000030185 A1 WO 2000030185A1 US 9926996 W US9926996 W US 9926996W WO 0030185 A1 WO0030185 A1 WO 0030185A1
Authority
WO
WIPO (PCT)
Prior art keywords
semiconductor material
substrate
conducting
materials
thermoelectric
Prior art date
Application number
PCT/US1999/026996
Other languages
French (fr)
Other versions
WO2000030185A8 (en
Inventor
Saeid Ghamaty
Norbert B. Elsner
Original Assignee
Hi-Z Technology, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/192,098 external-priority patent/US6096965A/en
Priority claimed from US09/192,097 external-priority patent/US6096964A/en
Application filed by Hi-Z Technology, Inc. filed Critical Hi-Z Technology, Inc.
Priority to JP2000583095A priority Critical patent/JP4903307B2/en
Priority to AU17238/00A priority patent/AU1723800A/en
Priority to EP99960340A priority patent/EP1155460A4/en
Publication of WO2000030185A1 publication Critical patent/WO2000030185A1/en
Publication of WO2000030185A8 publication Critical patent/WO2000030185A8/en

Links

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/857Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/851Thermoelectric active materials comprising inorganic compositions
    • H10N10/855Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen

Definitions

  • thermoelectric devices and in particular to thermoelectric materials for such devices.
  • Thermoelectric devices for cooling and heating and the generation of electricity have been known for many years; however, their use has not been cost competitive except for limited applications.
  • thermoelectric material is measured by its "figure of merit" or Z, defined as where S is the Seebeck coefficient, p is the electrical resistivity, and K is the thermal conductivity.
  • the Seebeck coefficient is further defined as the ratio of the open- circuit voltage to the temperature difference between the hot and cold junctions of a circuit exhibiting the Seebeck effect, or
  • thermoelectric material V/(T h -T c ). Therefore, in searching for a good thermoelectric material, we look for materials with large values of S and low values of p and K.
  • Thermoelectric materials currently in use today include the materials listed below with their figures of merit shown:
  • thermoelectric element having a very large number of very thin alternating layers of semiconductor material having the same crystalline structure.
  • superlattice layers of SiGe with Si as barrier layers demonstrated figures of merit of more than six times better than bulk SiGe. These superlattice layers were grown on a Si substrate using a sputtering technique in an argon atmosphere.
  • Kapton® is a trademark of Dupont Corp. and is used to describe a well-known polyimide material. Films made of this material are also extensively used.
  • thermoelectric elements described in the above two patents represented a major advancement in thermoelectric technology
  • the prior art technology required the removal of the substrate on which the thin layers were laid down.
  • thermoelectric elements for use in a thermoelectric device.
  • the thermoelectric elements have a very large number of alternating layers of semiconductor material deposited on a very thin substrate.
  • the layers of semiconductor material alternate between barrier semiconductor material and conducting semiconductor material creating quantum wells within the thin layers of conducting semiconductor material.
  • the conducting semiconductor material is doped to create conducting properties.
  • the substrate preferably should be very thin, a very good thermal and electrical insulator with good thermal stability, strong and flexible.
  • the thin organic substrate is a thin polyimide film (specifically Kapton®) coated with an even thinner film of crystalline silicon.
  • the substrate is about .3 mills (127 microns) thick.
  • the crystalline silicon layer is about 0.1 micron thick.
  • This embodiment includes on each side of the thin Kapton® substrate about 3,000 alternating layers of silicon and silicon- germanium, each layer being about 100 A and the total thickness of the layers being about 30 microns.
  • the silicon layer is applied in an amorphous form and heated to about 350°C to 375°C to crystallize it.
  • the substrate material is thin films of other organic materials or thin films of inorganic materials such as silicon.
  • FIG. 1 is a simple drawing showing an apparatus for making superlattice materials.
  • FIG. 2A is a top view of a preferred deposition chamber for fabricating thermoelectric film.
  • FIG. 2B is a side view of a preferred deposition chamber for fabricating thermoelectric film.
  • FIG. 3 shows an enlarged view of a section of Kapton® tape with alternating layers attached.
  • FIGS. 4A and 4B show the top and bottom views of how copper connections are made to put the elements in series.
  • FIG. 5 A shows how 12 elements could be connected in series to provide 12mV/°C.
  • FIG. 5B shows how the 12 elements could be connected to provide 6 mV/°C from the same 12 elements.
  • FIG. 6 shows an expanded view of a tape with 250 couples connected in series to produce a thermoelectric module for generating 12.5 milliwatts at a 5 volt potential from a 10 °C temperature difference.
  • FIG. 7 shows another deposition technique that will permit the copper connections to be made more easily.
  • FIG. 8 shows the pattern from which thermoelectric elements are cut from the substrate on which grown and also shows a detailed enlarged view of the alternating layers.
  • thermoelectric material is deposited in layers on substrates.
  • heat loss through the substrate can greatly reduce the efficiency of a thermoelectric device made from the material. If the substrate is removed some of the thermoelectric layers could be damaged and even if not damaged the process of removal of the substrate could significantly increase the cost of fabrication of the devices.
  • the present invention provides a substrate that can be retained.
  • the substrate preferably should be very thin, a very good thermal and electrical insulator with good thermal stability and strong and flexible.
  • Kapton is a product of DuPont Corporation. According to DuPont bulletins:
  • Kapton® polyimide film possesses a unique combination of properties that make it ideal for a variety of applications in many different industries.
  • the ability of Kapton® to maintained its excellent physical, electrical, and mechanical properties over a wide temperature range has opened new design and application areas to plastic films.
  • Kapton® is synthesized by polymerizing an aromatic dianhydride and an aromatic diamine. It has excellent chemical resistance; there are no known organic solvents for the film. Kapton® does not melt or burn as it has the highest UL-94 flammability rating: V-0. The outstanding properties of Kapton® permit it to be used at both high and low temperature extremes where other organic polymeric materials would not be functional.
  • Adhesives are available for bonding Kapton® to itself and to metals, various paper types, and other films.
  • Kapton® polyimide film can be used in a variety of electrical and electronic insulation applications: wire and cable tapes, formed coil insulation, substrates for flexible printed circuits, motor slot liners, magnet wired insulation, transformer and capacitor insulation, magnetic and pressure-sensitive tapes, and tubing. Many of these applications are based on the excellent balance of electrical, thermal, mechanical, physical, and chemical properties of Kapton® over a wide range of temperatures. It is this combination of useful properties at temperature extremes that makes Kapton® a unique industrial material.
  • thermoelectric material on these thin flexible substrates provides some important advantages for the design of thermoelectric elements and devices.
  • Ge 0.2 layers were alternatively deposited on the initial crystalline Si layer to make Sio. 8 Ge 0.2 /Si superlattices with each layer being about 100 A thick.
  • the actual deposition configuration is illustrated schematically in FIG. 1.
  • Two Kapton® substrates 2 are mounted on the bottom of platen 4 that rotates at a rate of 1 revolution per minute. The platen is 20 cm in diameter and the substrates are each 5 cm in diameter.
  • Two deposition sources 6 and 8 are mounted on a source flange 7 such that their deposition charges are about 10 cm from the axis 5.
  • Deposition source 6 is pure silicon and deposition source 8 is silicon germanium doped to ⁇ 10 19 carriers per cc.
  • boron for the dopant
  • antimony for the dopant.
  • the rotating platen is positioned 20 cm above the sources. We alternate the plasma so layers of silicon only and silicon and germanium are deposited.
  • the apparatus could be computer controlled to evaporate the sources alternatively at intervals appropriate to achieve the desired thickness while the platen rotates above.
  • Two electroluminescent deposition meters 9 at the side of platen 4 could monitor layer thickness. Layers will continue to build on the substrates until we have a wafer with about 300,000 layers and a thickness of about 0.3 cm, which is the thickness needed for a preferred thermoelectric device.
  • the Kapton® substrate is 0.5 mills or 0.0127 cm thick. The wafer is then diced into chips as indicated in FIG. 8.
  • Test Results The inventors have tested materials produced in accordance with the teachings of this invention.
  • the tested thermoelectric properties of both n-type and p- type samples of Sio. Ge 0 . 2 /Si are compared in Table 1 with the properties of bulk material with the same ratios of Si and Ge.
  • Table 1 The data reported in Table 1 was obtained with thin samples of about 500 alternating layers, each about lOOA thick (for a total layer thickness of about 0.0005cm) deposited on a 1 mill (0.00254cm) Kapton substrate coated with a lOOOA (0.00001cm) silicon layer. All measured values didn't need any correction for the insulating Kapton®.
  • Typical samples comprised about 500 layers (250 each of Si and SiGe) for a total thickness of about 50,000A deposited on a Kapton® film.
  • the samples were about 1 cm 2 so that the element dimensions were about 1cm x 1cm x (0.00254cm + 0.0005cm + 0.00001cm) or about 1cm x 1cm x 0.003cm.
  • Both p-type and n-type thermoelectric elements were prepared and the thermoelectric properties were measured.
  • the test results provided about 1 millivolt per °C per 1cm x 1cm x 0.003cm element.
  • the test results indicated Z values in the range of about 3 x 10 "3 /K to 5 x 10 "3 /K, which are about 10 times larger than Z values for bulk Si 0 8 Ge 02 .
  • Intermediate Crystalline Layer Applicants have shown that a crystal layer laid down between the Kapton substrate and the series of very thin conducting and barrier layers greatly improve thermoelectric performance especially for n-type layers.
  • the preferred technique is to lay it on about 1000 A thick in an amorphous form then to crystallize it by heating the substrate and the silicon layer to about 350° C to 375° C.
  • the crystalline layer could also be germanium or Group 3 - 5 compounds such as GaAs and GaP since these compounds have the same structures as silicon and germanium.
  • Substrates Other than Kapton® Kapton® is an excellent film for the practice of this invention since it has extremely low thermal conductivity and is a very good insulator. It is also strong so the film thickness can be very thin.
  • Suppliers other than DuPont make thin films of polyimide, and substrates of these other polymides could be used. Many other organic materials such as Mylar, polyethylene, and polyamide, polyamide-imides and polyimide compounds could be used as substrates.
  • Other potential substrate materials are Si, Ge and oxide films such as SiO 2 , Al 2 O 3 and TiO 2 . Mica could also be used for substrate.
  • the substrate preferably should be very thin a very good thermal and electrical insulator with good thermal stability, strong and flexible.
  • n-Type and p-Type Material Sputtering equipment for making the n-type and p-type layered material is commercially available from several suppliers such as Kurt J. Lesker Co. with offices in Clairton, Pa.
  • Molecular beam epitaxy is done in a manner similar to the techniques used for the fabrication of X-ray optics. Vacuum is established and maintained by a two-stage mechanical roughing pump and a high-capacity cryogenic pump. The system usually achieves base pressures of approximately 10 "10 torr after bake-out and before deposition. Substrates are mounted on a rotating carousel driven by a precision stepper motor.
  • Well known chemical vapor deposition can also be utilized for laying down the layers of Si, SiGe, Ge and B-C alloys.
  • Substrates can be heated or cooled by the carousel during sputtering. Heating of the substrate during deposition and subsequent annealing is used as a means of controlling the structure and orientation of individual crystalline layers, as well as means of reducing the number of defects in the films. (We can also control the temperature in order to enhance strain within the layers as a function of temperature as discussed later).
  • One of the essential conditions for epitaxial film growth is a high mobility of condensed atoms and molecules on the surface of the substrate. Two lkW magnetrons, each having a 2-5 inch diameter target and a 1 kW power supply, are used to deposit films.
  • the sputter sources are operated at an argon pressure between 0.001 and 0.1 torr. Argon is admitted to the system by a precision flow controller. All functions of the system, including movement of the carousel, rates of heating and cooling, magnetron power, and argon pressure, could be computer controlled.
  • FIG. 2 A is a top view of a preferred deposition chamber for fabricating thermoelectric film.
  • FIG. 2B is a side view sketch.
  • Alternate layers (100 A thick) of Si and SiGe (P doped) are deposited on one side of the tape from sources 44 and 46 and alternate layers of Si and SiGe (n- type) are deposited on the other side from sources 48 and 50.
  • Stepper table 52 steps the tape back and forth so that 1500 layers of Si and 1500 layers of SiGe are deposited to form each thermoelectric element. After the 3000 layers are deposited on each side the tape is advanced toward take up roll 42 to permit a copper connection to be provided at the top and bottom of the top from copper targets 54 and 56. Masks 60 are provided to limit the deposition areas.
  • the completed thermoelectric material includes the 0.5 mil substrate that results in bypass losses of about 5 to 10 percent. This shows the importance of choosing a substrate film as thin as feasible with good thermal and electrical insulating properties.
  • FIG. 3 shows an enlarged view of a section of tape. Elements 62A and 62B are completed and elements 64A, 64B, 66A and 66B are in the deposition process.
  • FIG. 4A is the top view of the tape showing how the top copper connections are made and FIG. 4B is a bottom view showing how the bottom copper connections are made to put the elements in series.
  • FIG. 5 A shows how 12 elements could be connected in series to provide 12mV/°C.
  • FIG. 5B shows how the 12 elements could be connected to provide 6 mV/°C from the same 12 elements.
  • FIG. 6 shows an expanded view of a tape with 250 couples connected in series to produce a thermoelectric module for generating 12.5 milliwatts at a 5 volt potential from a 10 °C temperature difference.
  • FIG. 7 shows another deposition technique that will permit the copper connections to be made more easily.
  • the SiGe ratio could be any composition between about 5 percent Ge to 100 percent Ge; however, the preferred composition is between about 10 percent Ge and about 40 percent Ge.
  • the barrier layer need not be pure silicon. It could be a SiGe solid solution. The overall rational is that the band gap of the barrier layer should be higher than the conducting layer and these band gaps may be adjusted by altering the Si-Ge ratios in the respective layers. Those skilled in the art will envision many other possible variations within its scope. Persons skilled in thermoelectric art are aware of many different dopants other than the ones discussed above which would produce similar effects.
  • n- type dopants include antimony, nitrogen, phosphorus and arsenic.
  • p-type dopants in addition to boron are aluminum, gallium and indium.
  • Persons skilled in the are will recognize that it is possible to produce quantum layers having the same crystalline structures from materials having different crystal structures. For example, epitaxial layers of GeTe and PbTe could be fabricated even though PbTe and GeTe differ slightly in crystalline structure. Many film materials other than the ones identified could be used.
  • the principals of this invention could be used with an array of very small diameter threads, preferable of substrate materials identified such as Kapton®. Accordingly the reader is requested to determine the scope of the invention by the appended claims and their legal equivalents, and not by the examples which have been given.

Abstract

Thermoelectric elements (62A, 64A, 66A, 62B, 64B, and 66B) for use in a thermoelectric device. The thermoelectric elements have a very large number of alternating layers of semiconductor material deposited on a very thin substrate. The layers of semiconductor material aternate between barrier semiconductor material and conducting semiconductor material creating quantum wells within the thin layers of conducting semiconductor material. The conducting semiconductor material is doped to create conducting properties. The substrate preferably should be very thin, a very good thermal and electrical insulator with good thermal stability and strong and flexible. In a preferred embodiment, the thin organic substrate is a thin polyimide film (specifically Kapton®) coated with an even thinner film of crystalline silicon. The substrate is about .3 mills (127 micons) thick. The crystalline silicon layer is about 0.1 micron thick. This embodiment includes on each side of the thin Kapton substrate about 3,000 alternating layers of silicon and silicon-germanium, each layer being about 100 Å and the total thickness of the layers being about 30 microns.

Description

QUANTUM WELL THERMOELECTRIC MATERIAL ON VERY THIN SUBSTRATE
This invention relates to thermoelectric devices and in particular to thermoelectric materials for such devices.
BACKGROUND OF THE INVENTION
Thermoelectric devices for cooling and heating and the generation of electricity have been known for many years; however, their use has not been cost competitive except for limited applications.
A good thermoelectric material is measured by its "figure of merit" or Z, defined as
Figure imgf000003_0001
where S is the Seebeck coefficient, p is the electrical resistivity, and K is the thermal conductivity. The Seebeck coefficient is further defined as the ratio of the open- circuit voltage to the temperature difference between the hot and cold junctions of a circuit exhibiting the Seebeck effect, or
S = V/(Th-Tc). Therefore, in searching for a good thermoelectric material, we look for materials with large values of S and low values of p and K.
Thermoelectric materials currently in use today include the materials listed below with their figures of merit shown:
Thermoelectric Material Peak Zeta, Z (at temperature shown) ZT
Lead Telluride 1.8 x 10"3/°K at 500 °K 0.9
Bismuth Telluride 3.2 x 10"3/°K at 300 °K 1 -0
Silicon germanium 0.8 x 10'3/°K at 1100 °K 0-9
Workers in the thermoelectric field have been attempting to improve the figure of merit for the past 20 - 30 years with not much success. Most of the effort has been directed to reducing the lattice thermal conductivity (K) without adversely affecting the electric conductivity.
Applicants have been issued two United States Patents (U.S. Pat. No.'s 5,436,467 and 5,550,387), which are incorporated by reference herein. In those patents, Applicants disclosed a thermoelectric element having a very large number of very thin alternating layers of semiconductor material having the same crystalline structure. In a preferred embodiment, superlattice layers of SiGe with Si as barrier layers demonstrated figures of merit of more than six times better than bulk SiGe. These superlattice layers were grown on a Si substrate using a sputtering technique in an argon atmosphere.
Kapton® is a trademark of Dupont Corp. and is used to describe a well-known polyimide material. Films made of this material are also extensively used.
While the thermoelectric elements described in the above two patents represented a major advancement in thermoelectric technology, the prior art technology required the removal of the substrate on which the thin layers were laid down.
What are needed are better methods of preparing superlattice thermoelectric materials, elements and devices which does not require substrate removal.
SUMMARY OF THE INVENTION The present invention provides thermoelectric elements for use in a thermoelectric device. The thermoelectric elements have a very large number of alternating layers of semiconductor material deposited on a very thin substrate. The layers of semiconductor material alternate between barrier semiconductor material and conducting semiconductor material creating quantum wells within the thin layers of conducting semiconductor material. The conducting semiconductor material is doped to create conducting properties. The substrate preferably should be very thin, a very good thermal and electrical insulator with good thermal stability, strong and flexible.
In a preferred embodiment, the thin organic substrate is a thin polyimide film (specifically Kapton®) coated with an even thinner film of crystalline silicon. The substrate is about .3 mills (127 microns) thick. The crystalline silicon layer is about 0.1 micron thick. This embodiment includes on each side of the thin Kapton® substrate about 3,000 alternating layers of silicon and silicon- germanium, each layer being about 100 A and the total thickness of the layers being about 30 microns. Preferably, the silicon layer is applied in an amorphous form and heated to about 350°C to 375°C to crystallize it. In other preferred embodiments the substrate material is thin films of other organic materials or thin films of inorganic materials such as silicon.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a simple drawing showing an apparatus for making superlattice materials.
FIG. 2A is a top view of a preferred deposition chamber for fabricating thermoelectric film.
FIG. 2B is a side view of a preferred deposition chamber for fabricating thermoelectric film.
FIG. 3 shows an enlarged view of a section of Kapton® tape with alternating layers attached.
FIGS. 4A and 4B show the top and bottom views of how copper connections are made to put the elements in series.
FIG. 5 A shows how 12 elements could be connected in series to provide 12mV/°C.
FIG. 5B shows how the 12 elements could be connected to provide 6 mV/°C from the same 12 elements.
FIG. 6 shows an expanded view of a tape with 250 couples connected in series to produce a thermoelectric module for generating 12.5 milliwatts at a 5 volt potential from a 10 °C temperature difference.
FIG. 7 shows another deposition technique that will permit the copper connections to be made more easily. FIG. 8 shows the pattern from which thermoelectric elements are cut from the substrate on which grown and also shows a detailed enlarged view of the alternating layers.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Preferred embodiments of the present invention can be described by reference to the drawings.
Substrates for Quantum Well Thermoelectric Material As described in United States Patents 5,436,467 and 5,550,387, quantum well thermoelectric material is deposited in layers on substrates. For a typical substrate as described in those patents, heat loss through the substrate can greatly reduce the efficiency of a thermoelectric device made from the material. If the substrate is removed some of the thermoelectric layers could be damaged and even if not damaged the process of removal of the substrate could significantly increase the cost of fabrication of the devices. The present invention provides a substrate that can be retained. The substrate preferably should be very thin, a very good thermal and electrical insulator with good thermal stability and strong and flexible.
Kapton®
Kapton is a product of DuPont Corporation. According to DuPont bulletins:
Kapton® polyimide film possesses a unique combination of properties that make it ideal for a variety of applications in many different industries. The ability of Kapton® to maintained its excellent physical, electrical, and mechanical properties over a wide temperature range has opened new design and application areas to plastic films.
Kapton® is synthesized by polymerizing an aromatic dianhydride and an aromatic diamine. It has excellent chemical resistance; there are no known organic solvents for the film. Kapton® does not melt or burn as it has the highest UL-94 flammability rating: V-0. The outstanding properties of Kapton® permit it to be used at both high and low temperature extremes where other organic polymeric materials would not be functional.
Adhesives are available for bonding Kapton® to itself and to metals, various paper types, and other films.
Kapton® polyimide film can be used in a variety of electrical and electronic insulation applications: wire and cable tapes, formed coil insulation, substrates for flexible printed circuits, motor slot liners, magnet wired insulation, transformer and capacitor insulation, magnetic and pressure-sensitive tapes, and tubing. Many of these applications are based on the excellent balance of electrical, thermal, mechanical, physical, and chemical properties of Kapton® over a wide range of temperatures. It is this combination of useful properties at temperature extremes that makes Kapton® a unique industrial material.
Kapton® Substrate Applicants have demonstrated that superlattice layers Si8Ge2/Si can be deposited on very thin Kapton®. Applicants have discovered that thermoelectric material on these thin flexible substrates provides some important advantages for the design of thermoelectric elements and devices.
Thin Films on Kapton® Alternating layers of Si0.8Ge0. and Si were grown on Kapton® substrates by deposition from two targets in a magnetron sputtering system. The plasma from the Si and Si0 8Geo.2 target sources were separated, sensed and controlled to yield a total deposition rate of 100 A/min. Prior to deposition, Kapton® substrates were cleaned, then a 1000 A thick silicon layer was applied to the Kapton® substrates. The silicon layer was sputtered in situ and annealed at 350 °C - 375 °C to crystallize the silicon. Annealing and growth temperatures were measured directly by thermocouples. Then the Si and Sio. Ge0.2 layers were alternatively deposited on the initial crystalline Si layer to make Sio.8Ge0.2/Si superlattices with each layer being about 100 A thick. The actual deposition configuration is illustrated schematically in FIG. 1. Two Kapton® substrates 2 are mounted on the bottom of platen 4 that rotates at a rate of 1 revolution per minute. The platen is 20 cm in diameter and the substrates are each 5 cm in diameter. Two deposition sources 6 and 8 are mounted on a source flange 7 such that their deposition charges are about 10 cm from the axis 5. Deposition source 6 is pure silicon and deposition source 8 is silicon germanium doped to ~ 1019 carriers per cc. For p-type material we use boron for the dopant and for n-type material we use antimony for the dopant. (Phosphorous could also be used as dopant.) The rotating platen is positioned 20 cm above the sources. We alternate the plasma so layers of silicon only and silicon and germanium are deposited.
The apparatus could be computer controlled to evaporate the sources alternatively at intervals appropriate to achieve the desired thickness while the platen rotates above. Two electroluminescent deposition meters 9 at the side of platen 4 could monitor layer thickness. Layers will continue to build on the substrates until we have a wafer with about 300,000 layers and a thickness of about 0.3 cm, which is the thickness needed for a preferred thermoelectric device. (The Kapton® substrate is 0.5 mills or 0.0127 cm thick. The wafer is then diced into chips as indicated in FIG. 8.
Test Results The inventors have tested materials produced in accordance with the teachings of this invention. The tested thermoelectric properties of both n-type and p- type samples of Sio. Ge0.2/Si are compared in Table 1 with the properties of bulk material with the same ratios of Si and Ge.
The data reported in Table 1 was obtained with thin samples of about 500 alternating layers, each about lOOA thick (for a total layer thickness of about 0.0005cm) deposited on a 1 mill (0.00254cm) Kapton substrate coated with a lOOOA (0.00001cm) silicon layer. All measured values didn't need any correction for the insulating Kapton®. These Z values (in the range of 3 x 10"4 to 5 x 10"3) are amazingly high, approximately an order of magnitude higher than Si0.8Geo2- These results are also amazing in view of a prediction in 1991 that the maximum possible Z for bulk SiGe was about 1.7 x 10"3/K for p-type elements and about 1.9 x 10"3/K for n-type elements. (See Slack and Hussain, "The maximum possible conversion efficiency of silicon germanium thermoelectric generators", J. Appl. Phys. 70-5, 1 Sep. 1991.)
Figure imgf000009_0001
Typical samples comprised about 500 layers (250 each of Si and SiGe) for a total thickness of about 50,000A deposited on a Kapton® film. The samples were about 1 cm2 so that the element dimensions were about 1cm x 1cm x (0.00254cm + 0.0005cm + 0.00001cm) or about 1cm x 1cm x 0.003cm. Both p-type and n-type thermoelectric elements were prepared and the thermoelectric properties were measured. The test results provided about 1 millivolt per °C per 1cm x 1cm x 0.003cm element. The test results indicated Z values in the range of about 3 x 10"3/K to 5 x 10"3/K, which are about 10 times larger than Z values for bulk Si0 8Ge02.
Intermediate Crystalline Layer Applicants have shown that a crystal layer laid down between the Kapton substrate and the series of very thin conducting and barrier layers greatly improve thermoelectric performance especially for n-type layers. The preferred technique is to lay it on about 1000 A thick in an amorphous form then to crystallize it by heating the substrate and the silicon layer to about 350° C to 375° C. The crystalline layer could also be germanium or Group 3 - 5 compounds such as GaAs and GaP since these compounds have the same structures as silicon and germanium.
Substrates Other than Kapton® Kapton® is an excellent film for the practice of this invention since it has extremely low thermal conductivity and is a very good insulator. It is also strong so the film thickness can be very thin. Suppliers other than DuPont make thin films of polyimide, and substrates of these other polymides could be used. Many other organic materials such as Mylar, polyethylene, and polyamide, polyamide-imides and polyimide compounds could be used as substrates. Other potential substrate materials are Si, Ge and oxide films such as SiO2, Al2O3 and TiO2. Mica could also be used for substrate. As stated above, the substrate preferably should be very thin a very good thermal and electrical insulator with good thermal stability, strong and flexible.
Other Techniques for Making n-Type and p-Type Material Sputtering equipment for making the n-type and p-type layered material is commercially available from several suppliers such as Kurt J. Lesker Co. with offices in Clairton, Pa.
Molecular beam epitaxy is done in a manner similar to the techniques used for the fabrication of X-ray optics. Vacuum is established and maintained by a two-stage mechanical roughing pump and a high-capacity cryogenic pump. The system usually achieves base pressures of approximately 10"10 torr after bake-out and before deposition. Substrates are mounted on a rotating carousel driven by a precision stepper motor.
Well known chemical vapor deposition can also be utilized for laying down the layers of Si, SiGe, Ge and B-C alloys. Substrates can be heated or cooled by the carousel during sputtering. Heating of the substrate during deposition and subsequent annealing is used as a means of controlling the structure and orientation of individual crystalline layers, as well as means of reducing the number of defects in the films. (We can also control the temperature in order to enhance strain within the layers as a function of temperature as discussed later). One of the essential conditions for epitaxial film growth is a high mobility of condensed atoms and molecules on the surface of the substrate. Two lkW magnetrons, each having a 2-5 inch diameter target and a 1 kW power supply, are used to deposit films. The sputter sources are operated at an argon pressure between 0.001 and 0.1 torr. Argon is admitted to the system by a precision flow controller. All functions of the system, including movement of the carousel, rates of heating and cooling, magnetron power, and argon pressure, could be computer controlled.
Making Thermoelectric Elements with Thermoelectric Film Preferred techniques for preparation of thermoelectric film can be explained by reference to FIGS. 2 A and 2B through FIG. 7. FIG. 2 A is a top view of a preferred deposition chamber for fabricating thermoelectric film. FIG. 2B is a side view sketch. A roll 40 of plain .5 mill thick Kapton® film coated on both sides with a 1000 A thick layer of crystalline Si feeds take-up roll 42. Alternate layers (100 A thick) of Si and SiGe (P doped) are deposited on one side of the tape from sources 44 and 46 and alternate layers of Si and SiGe (n- type) are deposited on the other side from sources 48 and 50. Stepper table 52 steps the tape back and forth so that 1500 layers of Si and 1500 layers of SiGe are deposited to form each thermoelectric element. After the 3000 layers are deposited on each side the tape is advanced toward take up roll 42 to permit a copper connection to be provided at the top and bottom of the top from copper targets 54 and 56. Masks 60 are provided to limit the deposition areas. The completed thermoelectric material includes the 0.5 mil substrate that results in bypass losses of about 5 to 10 percent. This shows the importance of choosing a substrate film as thin as feasible with good thermal and electrical insulating properties.
FIG. 3 shows an enlarged view of a section of tape. Elements 62A and 62B are completed and elements 64A, 64B, 66A and 66B are in the deposition process.
FIG. 4A is the top view of the tape showing how the top copper connections are made and FIG. 4B is a bottom view showing how the bottom copper connections are made to put the elements in series.
FIG. 5 A shows how 12 elements could be connected in series to provide 12mV/°C. FIG. 5B shows how the 12 elements could be connected to provide 6 mV/°C from the same 12 elements.
FIG. 6 shows an expanded view of a tape with 250 couples connected in series to produce a thermoelectric module for generating 12.5 milliwatts at a 5 volt potential from a 10 °C temperature difference.
FIG. 7 shows another deposition technique that will permit the copper connections to be made more easily.
While the above description contains many specificites, the reader should not construe these as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. For example, the SiGe ratio could be any composition between about 5 percent Ge to 100 percent Ge; however, the preferred composition is between about 10 percent Ge and about 40 percent Ge. The barrier layer need not be pure silicon. It could be a SiGe solid solution. The overall rational is that the band gap of the barrier layer should be higher than the conducting layer and these band gaps may be adjusted by altering the Si-Ge ratios in the respective layers. Those skilled in the art will envision many other possible variations within its scope. Persons skilled in thermoelectric art are aware of many different dopants other than the ones discussed above which would produce similar effects. Examples of n- type dopants include antimony, nitrogen, phosphorus and arsenic. Examples of p-type dopants in addition to boron are aluminum, gallium and indium. Persons skilled in the are will recognize that it is possible to produce quantum layers having the same crystalline structures from materials having different crystal structures. For example, epitaxial layers of GeTe and PbTe could be fabricated even though PbTe and GeTe differ slightly in crystalline structure. Many film materials other than the ones identified could be used. Also, the principals of this invention could be used with an array of very small diameter threads, preferable of substrate materials identified such as Kapton®. Accordingly the reader is requested to determine the scope of the invention by the appended claims and their legal equivalents, and not by the examples which have been given.

Claims

We Claim:
1. A quantum well thermoelectric element for use in a thermoelectric device comprised of:
A) a substrate of electrically insulating material having a thickness of less than 20 mils, and
B) a plurality of very thin alternating layers deposited on said substrate, said layers comprising at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
2. A thermoelectric element as in Claim 1, wherein said substrate is a polyimide substrate.
3. A thermoelectric element as in Claim 2, wherein said polyimide substrate is Kapton®.
4. A thermoelectric element as in Claim 3, wherein said polyimide substrate is Kapton® film.
5. A thermoelectric element as in Claim 1 wherein said thickness of less than 20 mils is less than 1 mil.
6. A thermoelectric element as in Claim 1, and further comprising a layer of crystalline silicon at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
7. A thermoelectric element as in Claim 1, and further comprising a layer of germanium at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
8. A thermoelectric element as in Claim 1, and further comprising a layer of silicon-germanium at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
9. A thermoelectric element as in Claim 5, wherein said very thin alternating layers are each less than 1000 A thick.
10. A thermoelectric element as in Claim 5 wherein said very thin alternating layers are each about 100 A thick.
11. A thermoelectric element as in Claim 9 wherein said plurality of very thin alternating layers is at least 3000 layers.
12. A thermoelectric element as in Claim 1, wherein said barrier material is silicon and said conducting material is silicon-germanium.
13. A thermoelectric element as in Claim 1, wherein said barrier material is silicon and said conducting material is germanium.
14. A thermoelectric element as in Claim 1 1, wherein the concentration of germanium in said conducting material is between 10 percent and 40 percent.
15. A thermoelectric element as in Claiml, wherein said substrate is comprised of a metal oxide.
16. A thermoelectric element as in Claim 1, wherein said substrate is comprised of mica.
17. A thermoelectric element as in Claim 1, wherein said crystalline structures are alpha rhombohedral.
18. A thermoelectric element as in Claim 1, wherein at least one of said two different materials is an alloy of boron and carbon.
19. A thermoelectric material as in Claim 1, wherein at least two of said at least two different materials are both alloys of boron and carbon.
20. A thermoelectric device comprising a plurality of quantum well thermoelectric elements, each such element comprised of:
A) a substrate of electrically insulating material having a thickness of less than 20 mils, and
B) a plurality of very thin alternating layers deposited on said substrate, said layers comprising at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
21. A device as in Claim 20 wherein said substrate is a polyimide.
22. A device as in Claim 21 wherein said polyimide is Kapton®.
23. A device as in Claim 20 wherein said substrate is silicon.
24. A device as in Claim 20 wherein said plurality of elements comprise at least one p-type element and at least one n-type element.
25. A method of making thermoelectric elements comprising the steps of depositing on a thin substrate of electrically insulating material having a thickness of less than 20 mils, a plurality of very thin alternating layers of at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
26. A method of making thermoelectric devices comprising the steps of :
A) making a plurality of n-type and p-type thermoelectric elements by depositing on a thin substrate of electrically insulating material having a thickness of less than 20 mills, a plurality of very thin alternating layers of at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material, and
B) connecting said n-type and said elements to form said thermoelectric device.
27. A process as in Claim 26 wherein said substrate is comprised of a polyimide.
28. A process as in Claim 27 wherein said polyimide is Kapton®.
29. A quantum well thermoelectric element for use in a thermoelectric device comprised of:
A) a substrate of electrically insulating organic material, and B) a plurality of very thin alternating layers deposited on said substrate, said layers comprising at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
30. A thermoelectric element as in Claim 29, and further comprising a layer of crystalline silicon at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
31. A thermoelectric element as in Claim 29, and further comprising a layer of germanium at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
32. A thermoelectric element as in Claim 29, and further comprising a layer of silicon-germanium at least 1000 A thick located between said thin substrate and said plurality of alternating layers.
33. A thermoelectric element as in Claim 29, wherein said substrate is a polyimide substrate.
34. A thermoelectric element as in Claim 33, wherein said polyimide substrate is Kapton®.
35. A thermoelectric element as in Claim 33, wherein said polyimide substrate is Kapton® film.
36. A thermoelectric element as in Claim 30, wherein said very thin alternating layers are each less than 1000 A thick.
37. A thermoelectric element as in Claim 30 wherein said very thin alternating layers are each about 100 A thick.
38. A thermoelectric element as in Claim 37 wherein said plurality of very thin alternating layers is at least 3000 layers.
39. A thermoelectric element as in Claim 29, wherein said barrier material is silicon and said conducting material is silicon-germanium.
40. A thermoelectric element as in Claim 29, wherein said barrier material is silicon and said conducting material is germanium.
41. A thermoelectric element as in Claim 39, wherein the concentration of germanium in said conducting material is between 10 percent and 40 percent.
42. A thermoelectric element as in Claim 39, wherein said conducting material is doped with a dopant.
43. A thermoelectric element as in Claim 29, wherein said crystalline structures are alpha rhombohedral.
44. A thermoelectric element as in Claim 29, wherein at least one of said two different materials is an alloy of boron and carbon.
45. A thermoelectric material as in Claim 29, wherein at least two of said at least two different materials are both alloys of boron and carbon.
46. A thermoelectric device comprising a plurality of quantum well thermoelectric elements, each such element comprised of:
A) a substrate of electrically insulating organic material, and B) a plurality of very thin alternating layers deposited on said substrate, said layers comprising at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
47. A device as in Claim 46 wherein said substrate is a polyimide.
48. A device as in Claim 47 wherein said polyimide is Kapton®.
49. A device as in Claim 46 wherein said plurality of elements comprise at least one p-type element and at least one n-type element.
50. A method of making thermoelectric elements comprising the steps of depositing on a substrate of electrically insulating organic material, a plurality of very thin alternating layers of at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material.
51. A method of making thermoelectric devices comprising the steps of : A) making a plurality of n-type and p-type thermoelectric elements by depositing on a substrate of electrically insulating organic material a plurality of very thin alternating layers of at least two different semiconductor materials, the first of said two materials, defining a barrier semiconductor material and the second of said two materials defining a conducting semiconductor material, wherein said barrier semiconductor material and said conducting semiconductor material have similar crystalline structures, wherein said conducting semiconductor material is doped to create conducting properties, and wherein said layer arrangement of said at least two different materials creates quantum wells within said layers of said conducting semiconductor material, and B) connecting said n-type and said elements to form said thermoelectric device.
52. A method as in Claim 51 wherein said substrate is comprised of a polyimide.
53. A process as in Claim 52 wherein said polyimide is Kapton®.
PCT/US1999/026996 1998-11-13 1999-11-12 Quantum well thermoelectric material on very thin substrate WO2000030185A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000583095A JP4903307B2 (en) 1998-11-13 1999-11-12 Quantum well thermoelectric materials on ultrathin substrates
AU17238/00A AU1723800A (en) 1998-11-13 1999-11-12 Quantum well thermoelectric material on very thin substrate
EP99960340A EP1155460A4 (en) 1998-11-13 1999-11-12 Quantum well thermoelectric material on very thin substrate

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/192,098 US6096965A (en) 1998-11-13 1998-11-13 Quantum well thermoelectric material on organic substrate
US09/192,097 1998-11-13
US09/192,098 1998-11-13
US09/192,097 US6096964A (en) 1998-11-13 1998-11-13 Quantum well thermoelectric material on thin flexible substrate

Publications (2)

Publication Number Publication Date
WO2000030185A1 true WO2000030185A1 (en) 2000-05-25
WO2000030185A8 WO2000030185A8 (en) 2000-09-21

Family

ID=26887722

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/026996 WO2000030185A1 (en) 1998-11-13 1999-11-12 Quantum well thermoelectric material on very thin substrate

Country Status (4)

Country Link
EP (1) EP1155460A4 (en)
JP (1) JP4903307B2 (en)
AU (1) AU1723800A (en)
WO (1) WO2000030185A1 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004105146A1 (en) * 2003-05-23 2004-12-02 Koninklijke Philips Electronics N.V. Method of manufacturing a thermoelectric device and thermoelectric device obtained by means of such a method
WO2008005075A2 (en) * 2006-06-30 2008-01-10 Caterpillar Inc. System and method for treating a coating on a substrate
WO2008013584A2 (en) * 2006-07-21 2008-01-31 Caterpillar Inc. Thermoelectric device
WO2009045862A2 (en) * 2007-09-28 2009-04-09 Battelle Memorial Institute Thermoelectric devices
US7559215B2 (en) 2005-12-09 2009-07-14 Zt3 Technologies, Inc. Methods of drawing high density nanowire arrays in a glassy matrix
US7767564B2 (en) 2005-12-09 2010-08-03 Zt3 Technologies, Inc. Nanowire electronic devices and method for producing the same
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
US7851691B2 (en) 2003-12-02 2010-12-14 Battelle Memorial Institute Thermoelectric devices and applications for the same
FR2946798A1 (en) * 2009-06-12 2010-12-17 Commissariat Energie Atomique MICRO-STRUCTURE FOR THERMOELECTRIC GENERATOR WITH SEEBECK EFFECT AND METHOD FOR MANUFACTURING SUCH MICROSTRUCTURE
EP2381497A1 (en) * 2009-01-20 2011-10-26 Shenzhen University Thin film temperature-difference cell and fabricating method thereof
CN102881815A (en) * 2011-07-14 2013-01-16 索尼公司 Thermoelectric device
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
WO2013119293A2 (en) * 2011-11-22 2013-08-15 Research Triangle Institute Nanoscale, ultra-thin films for excellent thermoelectric figure of merit
US8658880B2 (en) 2005-12-09 2014-02-25 Zt3 Technologies, Inc. Methods of drawing wire arrays
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
CN111816753A (en) * 2019-06-18 2020-10-23 桂林电子科技大学 Preparation method of paper substrate bismuth telluride-based nanowire flexible thermocouple type temperature sensor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6987329B1 (en) * 2004-08-03 2006-01-17 Harris Corporation Fuel flexible thermoelectric micro-generator with micro-turbine
WO2010004360A1 (en) 2008-07-11 2010-01-14 Commissariat A L'energie Atomique Sige matrix nanocomposite materials with an improved thermoelectric figure of merit
DE102009045208A1 (en) * 2009-09-30 2011-04-14 Micropelt Gmbh Thermoelectric component and method for producing a thermoelectric component

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5436467A (en) * 1994-01-24 1995-07-25 Elsner; Norbert B. Superlattice quantum well thermoelectric material
US5550387A (en) * 1994-01-24 1996-08-27 Hi-Z Corporation Superlattice quantum well material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415699A (en) * 1993-01-12 1995-05-16 Massachusetts Institute Of Technology Superlattice structures particularly suitable for use as thermoelectric cooling materials
JPH09107129A (en) * 1995-10-09 1997-04-22 Sharp Corp Semiconductor device and its manufacturing method
DE29723309U1 (en) * 1997-03-06 1998-09-10 D T S Ges Zur Fertigung Von Du Compact low-power thermogenerator
US6060656A (en) * 1997-03-17 2000-05-09 Regents Of The University Of California Si/SiGe superlattice structures for use in thermoelectric devices
WO1998044562A1 (en) * 1997-03-31 1998-10-08 Research Triangle Institute Thin-film thermoelectric device and fabrication method of same
JPH11274581A (en) * 1998-03-26 1999-10-08 Toshiba Corp Thermoelectric conversion element and manufacture thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5436467A (en) * 1994-01-24 1995-07-25 Elsner; Norbert B. Superlattice quantum well thermoelectric material
US5550387A (en) * 1994-01-24 1996-08-27 Hi-Z Corporation Superlattice quantum well material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP1155460A4 *
STORDEUR M, STARK I: "LOW POWER THERMOELECTRIC GENERATOR - SELF-SUFFICIENT ENERGY SUPPLY FOR MICRO SYSTEMS", EIGHTEEN INTERNATIONAL CONFERENCE ON THERMOELECTRICS, 1999, XX, PISCATAWAY, NJ, USA, IEEE, US, 1 January 1997 (1997-01-01), Piscataway, NJ, USA, IEEE, US, pages 575 - 577, XP002926490 *

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100416878C (en) * 2003-05-23 2008-09-03 皇家飞利浦电子股份有限公司 Method of manufacturing a thermoelectric device and thermoelectric device obtained by means of such a method
WO2004105146A1 (en) * 2003-05-23 2004-12-02 Koninklijke Philips Electronics N.V. Method of manufacturing a thermoelectric device and thermoelectric device obtained by means of such a method
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
US7851691B2 (en) 2003-12-02 2010-12-14 Battelle Memorial Institute Thermoelectric devices and applications for the same
US7915683B2 (en) 2005-12-09 2011-03-29 Zt3 Technologies, Inc. Nanowire electronic devices and method for producing the same
US7767564B2 (en) 2005-12-09 2010-08-03 Zt3 Technologies, Inc. Nanowire electronic devices and method for producing the same
US7559215B2 (en) 2005-12-09 2009-07-14 Zt3 Technologies, Inc. Methods of drawing high density nanowire arrays in a glassy matrix
US8143151B2 (en) 2005-12-09 2012-03-27 Zt3 Technologies, Inc. Nanowire electronic devices and method for producing the same
US8658880B2 (en) 2005-12-09 2014-02-25 Zt3 Technologies, Inc. Methods of drawing wire arrays
WO2008005075A3 (en) * 2006-06-30 2008-12-04 Caterpillar Inc System and method for treating a coating on a substrate
WO2008005075A2 (en) * 2006-06-30 2008-01-10 Caterpillar Inc. System and method for treating a coating on a substrate
WO2008013584A2 (en) * 2006-07-21 2008-01-31 Caterpillar Inc. Thermoelectric device
WO2008013584A3 (en) * 2006-07-21 2008-09-04 Caterpillar Inc Thermoelectric device
WO2009045862A3 (en) * 2007-09-28 2009-11-05 Battelle Memorial Institute Thermoelectric devices
WO2009045862A2 (en) * 2007-09-28 2009-04-09 Battelle Memorial Institute Thermoelectric devices
EP2381497A1 (en) * 2009-01-20 2011-10-26 Shenzhen University Thin film temperature-difference cell and fabricating method thereof
EP2381497A4 (en) * 2009-01-20 2014-01-22 Shenzhen Caihuang Entpr & Dev Co Ltd Thin film temperature-difference cell and fabricating method thereof
FR2946798A1 (en) * 2009-06-12 2010-12-17 Commissariat Energie Atomique MICRO-STRUCTURE FOR THERMOELECTRIC GENERATOR WITH SEEBECK EFFECT AND METHOD FOR MANUFACTURING SUCH MICROSTRUCTURE
CN102449789A (en) * 2009-06-12 2012-05-09 原子能与替代能源委员会 Microstructure for a seebeck effect thermoelectric generator, and method for making such a microstructure
RU2521147C2 (en) * 2009-06-12 2014-06-27 Коммиссариат А Л'Энержи Атомик Э О Энержи Альтернатив Microcrystalline structure for thermoelectric generator based on seebeck effect, and method for manufacturing of such microcrystalline structure
US8962970B2 (en) 2009-06-12 2015-02-24 Commissariat A L'energie Atomique Et Aux Energies Alternatives Microstructure for a Seebeck effect thermoelectric generator, and method for making such a microstructure
WO2010142880A3 (en) * 2009-06-12 2011-02-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Microstructure for a seebeck effect thermoelectric generator, and method for making such a microstructure
CN102881815A (en) * 2011-07-14 2013-01-16 索尼公司 Thermoelectric device
WO2013119293A2 (en) * 2011-11-22 2013-08-15 Research Triangle Institute Nanoscale, ultra-thin films for excellent thermoelectric figure of merit
WO2013119293A3 (en) * 2011-11-22 2013-10-03 Research Triangle Institute Nanoscale, ultra-thin films for excellent thermoelectric figure of merit
CN111816753A (en) * 2019-06-18 2020-10-23 桂林电子科技大学 Preparation method of paper substrate bismuth telluride-based nanowire flexible thermocouple type temperature sensor
CN111816753B (en) * 2019-06-18 2022-07-12 桂林电子科技大学 Preparation method of paper substrate bismuth telluride-based nanowire flexible thermocouple type temperature sensor

Also Published As

Publication number Publication date
WO2000030185A8 (en) 2000-09-21
EP1155460A1 (en) 2001-11-21
JP4903307B2 (en) 2012-03-28
JP2002530874A (en) 2002-09-17
EP1155460A4 (en) 2006-12-06
AU1723800A (en) 2000-06-05

Similar Documents

Publication Publication Date Title
US6096964A (en) Quantum well thermoelectric material on thin flexible substrate
US6096965A (en) Quantum well thermoelectric material on organic substrate
US5550387A (en) Superlattice quantum well material
EP1155460A1 (en) Quantum well thermoelectric material on very thin substrate
US6828579B2 (en) Thermoelectric device with Si/SiC superlattice N-legs
US8455751B2 (en) Thermoelectric devices and applications for the same
WO2005098970A2 (en) IMPROVED THERMOELECTRIC MODULE WITH Si/SiC AND B4C/B9C SUPER-LATTICE LEGS
CA2233979C (en) Fabrication of thermoelectric modules and solder for such fabrication
KR101419331B1 (en) Multifilament superconductor having reduced ac losses and method for forming the same
WO2005097542A2 (en) IMPROVED THERMOELECTRIC MODULE WITH Si/SiGe AND B4C/B9C SUPER-LATTICE LEGS
US20100065417A1 (en) Methods for forming superconducting conductors
US20110100408A1 (en) Quantum well module with low K crystalline covered substrates
US20100269879A1 (en) Low-cost quantum well thermoelectric egg-crate module
US7445808B2 (en) Method of forming a superconducting article
US20130040820A1 (en) Fault current limiter incorporating a superconducting article and a heat sink
WO1994028364A1 (en) A peltier device
KR20150000365A (en) Thermoelectric structure, thermoelectric device and apparatus comprising same
CN101969096A (en) Nanostructured thermoelectric material and device and production method thereof
US20110062420A1 (en) Quantum well thermoelectric module
US20110284048A1 (en) Multi-layer superlattice quantum well thermoelectric material and module
Farmer et al. Sputter deposition of multilayer thermoelectric films: An approach to the fabrication of two‐dimensional quantum wells
Ghamaty et al. Thermal and electrical properties of Si/Si/sub 0.8/Ge/sub 0.2/and B/sub 4/C/B/sub 9/C films
WO2011121561A1 (en) Multi-layer superlattice quantum well thermoelectric material and module
Lee et al. Effects of substrate temperature on thermoelectric properties of amorphous Si/Ge thin films
JP2004265885A (en) Inclination structure material and functional element employing it

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 2000 17238

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: C1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT. BUL. 21/2000 UNDER (22) REPLACE 12.11.99" BY "15.11.99"

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 583095

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 1999960340

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999960340

Country of ref document: EP