Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
  • H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
  • H01L29/92—Capacitors with potential-jump barrier or surface barrier
  • H01L29/93—Variable capacitance diodes, e.g. varactors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J45/00—Discharge tubes functioning as thermionic generators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
  • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects

Definitions

• Thermionic energy conversion is a method of converting heat energy directly into electric energy by thermionic emission. In this process, electrons are thermionically emitted from the surface of a metal by heating the metal and imparting sufficient energy to a portion of the electrons to overcome retarding forces at the surface of the metal in order to escape. Unlike most other conventional methods of generating electric energy, thermionic conversion does not require either an intermediate form of energy or a working fluid, other than electric charges, in order to change heat into electricity.
• a conventional thermionic energy converter consists of one electrode connected to a heat source, a second electrode connected to a heat sink and separated from the first electrode by an intervening space, leads connecting the electrodes to the electric load, and an enclosure.
• the space in the enclosure is either highly evacuated or filled with a suitable rarefied vapor, such as cesium.
• the essential process in a conventional thermionic converter is as follows.
• the heat source supplies heat at a sufficiently high temperature to one electrode, the emitter, from which electrons are thermionically evaporated into the evacuated or rarefied- vapor- filled interelectrode space.
• the electrons move through this space toward the other electrode, the collector, which is kept at a low temperature near that of the heat sink.
• There the electrons condense and return to the hot electrode via external electric leads and an electric load connected between the emitter and the collector.
• FIG. 1 An embodiment of a conventional thermionic converter 100 is schematically illustrated in Fig. 1.
• These conventional devices typically comprise an emitter 110, or low electron- work-function cathode, a collector 112, or comparatively colder, high electron- work-function anode, an enclosure 114, suitable electric conductors 116, and an external load 118.
• Emitter 110 is exposed to heat flow 120 which causes this cathode to emit electrons 122, thus closing the electric circuit and providing an electric intensity to load 118.
• interelectrode space 130 in conventional thermionic converters is an evacuated medium or a rarified- vapor-filled medium. The flow of elecfrons through the electric load is sustained by the temperature difference between the electrodes. Thus, electric work is delivered to the load.
• Thermionic energy conversion is based on the concept that a low electron work function cathode in contact with a heat source will emit electrons. These elecfrons are absorbed by a cold, high work function anode, and they can flow back to the cathode through an external load where they perform useful work. Practical thermionic generators are limited by the work function of available metals or other materials that are used for the cathodes. Another important limitation is the space charge effect. The presence of charged electrons in the space between the cathode and anode will create an extra potential barrier which reduces the thermionic current. These limitations detrimentally affect the maximum current density, and thus present a major problem in developing large-scale thermionic converters.
• thermionic converters are typically classified as vacuum converters or gas-filled converters.
• Vacuum converters have an evacuated medium between the electrodes. These converters have limited practical applications.
• Embodiments in a first class of gas-filled converters are provided with a vaporized substance ,in the interelectrode space that generates positive ions.
• This vaporized substance is commonly a vaporized alkali metal such as cesium, potassium and rubidium. Because of the presence of these positive ions, liberated electrons can more easily travel from the emitter to the collector.
• the emitter temperature in these types of conventional devices is in part determined by the vaporization temperature of the substance that generates the positive ions. Generally, the emitter temperature should be at least 3.5 times the temperature of the reservoir of the positive ion generating substance if efficient production of ions is to be achieved in these conventional devices.
• Embodiments in a second class of gas-filled converters are provided with a third electrode to generate ions.
• the gas in the interelectrode space in these conventional devices is an inert gas such as neon, argon and xenon. ' Although these converters can operate at lower temperatures, such as about 1500 K, they are more complex.
• Typical conventional thermionic emitters are operated at temperatures ranging from 1400 to 2200 K and collectors at temperatures ranging from 500 to 1200 K. Under optimum conditions of operation, overall efficiencies of energy conversion range from 5 to 40%, electric power densities are of the order of 1 to 100 watts/cm 2 , and current densities are of the order of 5 to 100 A/cm 2 . In general, the higher the emitter temperature, the higher the efficiency and the power and current densities with designs accounting for radiation losses.
• the voltage at which the power is delivered from one unit of a typical converter is 0.3 to 1.2 volts, i.e., about the same as that of an ordinary electrolytic cell.
• Thermionic systems with a high power rating frequently consist of many thermionic converter units connected electrically in series. Each thermionic converter unit is typically rated at 10 to 500 watts.
• thermoelectric energy converters are advantageous for certain applications, but they are restrictive for others. This is because the required emitter temperatures are generally beyond the practical capability of many conventional heat sources. In contrast, typical thermoelectric converters are operable at heat source temperatures ranging from 500 to 1500 K. However, even under optimum conditions, overall efficiencies of thermoelectric energy converters only range from 3 to 10%, electric power densities are normally less than a few watts/cm 2 , and current densities are of the order of 1 to 100 A/cm 2 .
• thermoelectric devices are similar to thermionic devices. In both cases a temperature gradient is placed upon a metal or semiconductor, and both cases are based upon the concept that electron motion is electricity. However, the electron motion also carries energy. A forced current transports energy for both thermionic and thermoelecfric devices.
• the main difference between thermoelectric and thermionic devices is in the fransport mechanism: ballistic and diffusive transport for thermionics and ohmic transport for thermoelectrics. Ohmic flow is microscopically diffusive, but not microscopically so. The distinguishing feature is whether excess carriers are present. In thermoelectrics, the carriers normally present are responsible for current. In thermionics, the current is due to putting excess carriers in the gap.
• a thermionic device has a relatively high efficiency if the electrons ballistically go over and across the gap. For a thermionic device all of the kinetic energy is carried from one electrode to the other.
• the motion of electrons in a thermoelectric device is quasi- equilibrium and ohmic, and can be described in terms of a Seebeck coefficient, which is an equilibrium parameter.
• the current density is given by:
• the present invention was developed to fill a need for a device which efficiently converts thermal energy to electric energy at relatively low operating temperatures and with power densities and efficiencies high enough for commercial applications.
• the present invention also operates in reverse mode to provide efficient cooling.
• the present invention seeks to resolve a number of the problems which have been experienced in the background art, as identified above. More specifically, the apparatus and method of this invention constitute an important advance in the art of thermionic power conversion, as evidenced by the characteristics of embodiments of this invention.
• solid state converter comprising an emitter having at least a region comprising a first donor at a concentration N d * , a collector and a gap region between the emitter and the collector in electric and thermal communication with the emitter and the collector.
• the gap region comprises a semiconductor with a second donor at a concentration N d , which is selected so that the natural logarithm of the ratio N d * I N d is between 0 and about 7.
• a solid state thermionic converter utilizing semiconductor diode implementation comprising an emitter that comprises an r ⁇ *-type region; a gap region between the emitter and a collector, the gap region being adjacent to said r ⁇ *-type region; and a cold ohmic contact connected to said gap region, said cold ohmic contact having a recombination collector region formed between said cold ohmic contact and said gap region.
• a collector provides a recombination element and such collector is in electric communication with a cold ohmic contact.
• a hot ohmic contact is in electric communication with the emitter.
• the gap region may be n-type, p- ype, or intrinsic.
• the electric circuit is typically closed externally with an electric load connected to the hot ohmic contact and the cold ohmic contact.
• terms such as “electric communication”, “electric connection” and “electric contact” refer to a relationship between elements whereby electric current can flow between such elements, whether such elements are in direct contact or the electric current flow is facilitated by at least one conductor linking such elements.
• Still other embodiments of the present invention comprise a plurality of plates, each comprising an emitter and a collector with a gap region therebetween.
• carrier transport is assisted by an external electric field.
• a first ohmic contact on the emitter comprising in one embodiment an «*-type region, is connected to a thermal load that is cooled by heat flow from electrons leaving the emitter.
• electrons in refrigeration embodiments circulate from the emitter, preferably from a hot ohmic contact on the «*-type region, to the gap region.
• a gap region is in one embodiment adjacent to the emitter, and a second ohmic
• / contact having a recombination collector region is formed between the second ohmic contact and the gap region.
• the gap region in embodiments of this invention may be n- type, p-type, or intrinsic.
• a heat exchanger dissipates the heat from hot electrons on the second ohmic contact connected to the gap region.
• FIG. 1 schematically shows an embodiment of a conventional thermionic converter.
• FIG. 2 is a cross-sectional view of a thermal diode of the present invention.
• FIG. 3 is a plot of the normalized conductivity parameter ⁇ as a function of temperature for InSb, assuming that D ⁇ cm
• FIG. 4 shows electron and hole concentrations for an n*pn* thermionic structure in InSb, where the donor concentration in the emitter and collector regions is 10 20 cm' 3 , and the acceptor concentration in the gap region is 10 17 cm "3 .
• FIG. 5 A shows electron concentrations for an n*nn* thermionic structure in InSb, where the donor concentration in the emitter and collector regions is 10 20 cm “3 , and the donor concentration in the gap region is 10 14 cm “3 .
• FIG. 5B shows the normalized conductivity ⁇ as a function of temperature for several semiconductors.
• FIG. 6 shows electron and hole concentrations for an n*nn* thermionic structure in InSb, where the donor concenfration in the emitter and collector regions is 10 20 cm “3 , and the donor concentration in the gap region is 8 x 10 17 cm “3 .
• FIG. 7 shows the normalized barrier height ⁇ u as a function of the doping concentration.
• FIG. 9 shows current and voltage characteristic for a 625 ⁇ thick InSb design, with an emitter electron concenfration of 10 20 electrons/cm 3 , an emitter temperature T max - 600 K and a collector temperature T m!n - 300 K.
• FIG. 12 shows the efficiency as a function of voltage for a InSb design.
• FIG. 13 shows the results of a numerical optimization of efficiency as a function of gap doping over a wide range of doping densities at a fixed emitter ionized dopant concentration of 10 20 cm "3 .
• FIG. 15 shows the thermal and load power per unit area for thermal diode designs.
• FIG. 16 shows the efficiency of a design with an emitter electron concenfration of 10 20 electrons/cm 3 and a gap donor density of 7 x 10 17 cm "3 .
• FIG. 17 shows the optimized efficiency as a fraction of the thermodynamic limit.
• FIG. 18 shows the thermal power flow under conditions of optimum energy conversion at different temperatures.
• FIG. 19 is a cross-sectional view of a compensated thermal diode.
• FIG. 20 shows the current as a function of gap doping for an InSb thermal diode design.
• FIG. 21 shows optimization of efficiency as a function of gap doping with -type compensation using a concentrations of 7 x 10 17 , 10 18 , 2 x 10 18 and 3 x 10 18 cm “3 .
• FIG. 22 shows a cross-sectional view of a single compensated thermal diode with increasing temperature indicated by the arrow labeled T.
• FIG.23 A shows the efficiency under optimized conditions as a function of emitter temperature for different gap doping with perfect compensation.
• An InSb compensated thermal diode structure 625 ⁇ thick is assumed, with an emitter electron density of 10 20 cm "3 and a collector temperature of 300 K.
• FIG. 23B shows the efficiency normalized to the thermodynamic limit under optimized conditions as a function of emitter temperature for the different cases shown in Figure 23 A.
• FIG. 24 illustrates an embodiment having four stacked diodes.
• FIG.25 illustrates an embodiment having multiple stacked diodes having a curved boundary and forming a wedge-shaped geometry.
• FIG. 26 illustrates an embodiment of stacked diodes wherein the stack boundary approximates an ideal curve as shown in Figure 25.
• FIGS. 27A-27B show efficiency as a function of temperature for optimized embodiments of compensated thermal diodes wherein the collector temperature is about 300K according to this invention.
• FIGS. 28 and 29 show the dose needed to create a compensated layer over a wide range of ion energies in an n-type InSb diode doped to a concenfration n.
• FIG. 30 shows the results for an ohmic contact implantation dose required to achieve a 10 21 cm "3 shallow doping of Te for an InSb design.
• FIG. 31 shows the ion range for FIG. 30.
• FIG. 32 shows the results for Ag doping to achieve an ohmic contact.
• FIG. 33 shows the results for Ag doping to achieve an ohmic contact.
• FIG. 34 shows the temperature behavior of an InSb gap.
• FIG. 35 shows the temperature dependence on barrier height for an interface layer doped with Te to 3xl0 19 cm “3 deposited on InSb doped with Te to lxl0 18 cm “3 with an In emitter.
• FIG. 36A shows the surface states of a metal-semiconductor contact.
• FIG. 36B schematically illustrates an embodiment of the present invention comprising a metal-semiconductor-interface-barrier reduction layer.
• FIG. 37 shows the I-V curves for a single diode and a stack of three InSb diodes.
• FIG. 38 shows a graph of one plate efficiency for InSb as a function of Ar ion implantation dose for a sample whose size is 0.50 x 1.0 x 1.5 mm 3 .
• FIG. 39 shows a graph of the 4 He ion implantation range as a function of ion energy for an InSb target.
• FIG. 40 shows the results of a simulation for the number of vacancies per ion as a function of 4 He ion energy for the ion implantation referred to in FIG. 39.
• FIG. 41 shows a graph of output current density for an embodiment comprising a Hg 0 g6 Cd 0 14 Te sample as a function of the hot side temperature for the sample with a Cu emitter layer and for the sample with an In-Ga emitter layer.
• FIG. 42 shows a graph of output current density for an embodiment comprising a Hg 086 Cd 0 14 Te sample as a function of the hot side temperature for the sample with an Al substrate and for the sample with an In-Ga substrate.
• FIG. 43 shows a graph of the absolute efficiency as a function of temperature for an embodiment of a thermal diode without compensation comprising a Hg 0 86 Cd 0 14 Te sample.
• FIG.44 shows a graph of the efficiency, expressed as a percentage of ideal Caniot cycle efficiency, as a function of temperature for the same embodiment referred to in
• FIG. 45 shows a graph of the absolute efficiency for an embodiment of a sandwich converter as a function of hot plate temperature.
• FIG. 46 shows a graph of the efficiency, expressed as a percentage of ideal Carnot cycle efficiency, as a function of hot plate temperature for the same embodiment referred to in FIG. 45.
• FIG. 47 shows a graph for the Kg ⁇ Cd-le normalized figure of merit relative to that of InSb as a function of x.
• FIG. 48 illustrates a thermal diode for providing cooling.
• FIG. 49 shows a compensated thermal diode for providing cooling.
• FIG. 50 shows the coefficient of performance as a function of temperature for refrigeration embodiments.
• the present invention embodies a solid state thermionic energy converter 10, generally illustrated in Figure 2, and is directed to a method and apparatus for the conversion of energy.
• One embodiment of the inventive solid state thermionic energy converter 10 comprises a semiconductor diode having an n*-type region 14 as an emitter, a gap region 16 adjacent to the ⁇ *-type region 14, a hot ohmic contact 12 connected to said «*-type region 14, and a cold ohmic contact 20 being a collector and connected to said gap region 16.
• the cold ohmic contact 20 has a recombination collector region 18 formed between said cold ohmic contact 20 and said gap region 16.
• the recombination region in some embodiments of this invention comprises a distinct layer.
• the recombination region is obtained by treating and/or damaging the surface of an ohmic contact or collector. Forming a recombination region in the context of this invention thus includes procedures for inco ⁇ orating a recombination layer and procedures for treating and/or damaging the surface of an ohmic contact or collector.
• r ⁇ *-region are used herein to refer to an ⁇ -region which has a higher electron concentration than an rc-region.
• Illusfrative embodiments of materials comprised in n*-regions are given below.
• a general characterization of the «*-region and «-region in terms of their relative donor number densities N d * and N d is provided hereinbelow.
• n-type regions are provided by regions that include InSb doped with Te at a concentration from about 10 16 cm “3 to about 10 19 cm “3 . Concentrations in the order of 10 20 cm “3 are also envisaged as characterizing the dopant concentration of materials in n- type regions in embodiments of this invention.
• Examples of «*-type regions are provided by regions that include InSb doped with Te at a concentration from about 10' 9 cm “3 to about 3-10 19 cm “3 . Concentrations of about 3-10 20 cm “3 are also envisaged as characterizing the dopant concentration of materials in «*-type regions in embodiments of this invention.
• dopants in some other embodiments of the present invention include at least one of S, Se, and Sn. Furthermore, the symbol n** is used herein to refer to an ⁇ -region which has a higher electron concentration than an n *-region.
• regions that include a material such as In, Te, Ga, and Fe are provided by regions that include a material such as In, Te, Ga, and Fe.
• An electric load R L connected to hot ohmic contact 12 and to cold ohmic contact 20 is provided with the electric intensity generated by an embodiment of a converter according to this invention.
• the emitter may be a metal.
• the gap region 16 may be either moderately doped n-type, -type, or intrinsic. Electrons are collected in the recombination collector region 18. The heated emitter relative to the collector generates an EMF which drives current through a series load.
• inventive principle works for hole conductivity, as well as for elecfrons.
• reference to metals herein includes alloys.
• embodiments of converters according to the present invention are solid-state devices. The prior art, however, teaches devices that rely on an evacuated interelectrode space or on a gas-filled interelectrode space. General characteristics of these conventional devices have been summarized above.
• embodiments of the present invention incorporate a semiconducting material.
• Semiconductors are valuable, not for their conductivity, but for two unusual properties.
• the concenfration of free carriers, and consequently the conductivity increases exponentially with temperature (approximately 5% per degree Celsius at ordinary temperatures).
• the conductivity of a semiconductor can be increased greatly, and to a precisely controlled extent, by adding small amounts of impurities in the process called doping. Since there are two types of mobile charge carriers (electrons and holes), of opposite sign, extraordinary distributions of charge carriers can be created.
• the semiconductor diode utilizes this property.
• Semiconductors pure or doped, p-type, or n-type, are bilateral; current flows in either direction with equal facility. If, however, a p-type region exists in close proximity to an n-type region, there is a carrier density gradient that is unilateral; current flows easily in one direction only.
• the resulting device a semiconductor diode, exhibits a very useful control property of carrier transport that can be utilized for energy conversion.
• the following written description and graphic material refer to models and/or simulations of phenomena that are associated with working embodiments of the present invention. References to these models and/or simulations are not meant to be limiting explanations of the present invention. It is understood that the present invention is not limited or restricted to any single explanation of its underlying physical processes.
• Models and/or simulations are intended to highlight relevant variables that can be used to design additional embodiments envisaged within the scope of the present invention, even though such embodiments are not explicitly referred to in the context of this written description. With these design tools, the teachings of this written description, and ordinary skill in the art, additional embodiments that are within the scope of the present invention and claims can be designed. Accordingly, the following written description and graphic material describe embodiments of the present invention and provide models that can be used for designing additional embodiments envisaged within the scope of the present invention.
• Compensation includes return current suppression. Methods for forming ohmic contacts in embodiments of the present invention are subsequently described.
• Examples of embodiments of the present invention that comprise InSb with a compensation layer include InSb wafers with a w-type dopant, such as Te, and an emitter layer of Te implanted by a technique such as magnetron sputtering.
• the compensation layer in these embodiments is formed by p-type impurity implantation.
• This -type impurity comprises at least one type of ions such as Ar and He ions, which compensate for the «-type dopant.
• Another material to build an n*/n emitter comprises Hg,. x Cd x Te.
• a Hg o.s ⁇ d 0 . ⁇ Te wafer is used in embodiments of this invention to build a n*/n emitter by reacting Hg o.s ⁇ Cd 0 . ⁇ Te with a r ⁇ -type impurity substrate such as Al and In-Ga thus creating an electron injecting n* region.
• a r ⁇ -type impurity substrate such as Al
• In-Ga One form of an In-Ga material for this purpose is In o. 75 ⁇ a ⁇ 25 .
• Embodiments with this emitter exhibit an output electric current density that increases as a function of the hot side temperature. It is shown below that these embodiments attain efficiencies that are above
• Hg Lx Cd x Te is part of a multi-plate, or sandwich configuration in other embodiments of this invention.
• an embodiment of these sandwiches comprises an InSb plate doped with an «-type material such as Te and an emitter layer of InSb sputtered with Te and coated with a material such as In-Ga, more specifically, such as In 075 Gao 25 .
• a second plate in this sandwich material comprises Hg ⁇ . x C(LTe, where x is in one embodiment 0.14.
• converters according to the present invention include converters to convert thermal energy to electricity and refrigeration embodiments.
• two types of embodiments include the same main components, whether they operate as thermionic converters for refrigeration or as thermal diodes for converting thermal energy into electricity.
• Hg ⁇ _ x Cd x Te with x being from about 0.08 to about 0.15 exhibits a high thermionic figure of merit while remaining semiconductor and allowing an n* emitter layer/compensation layer design and behavior as described herein with respect to other materials. Furthermore, it has also been discovered in the context of this invention that Hg 092 Cd 0 8 Te behaves as an excellent thermoelectric material. 1. The Solid State Thermionic Converter
• a highly doped n* region 14 in embodiments of the present invention can serve as an emitter region, from which carriers can be boiled off into gap region 16.
• the n* region comprises a semiconductor doped with a high concentration of donor (providing electrons) impurity.
• donor providing electrons
• InSb can be doped with Te or S. It has been found in the context of the present invention that energy conversion is a function of the semiconductor normalized conductivity ⁇ , which in turn is a function of the material parameters and peak emitter doping.
• the normalized conductivity is seen to decrease at higher temperature.
• the normalized conductivity decreases in the presence of background carriers, since the mobility of elecfrons in InSb decreases with increasing doping density.
• Figure 5B shows the normalized conductivity ⁇ for a number of semiconductors.
• Hgj.,. Cd.. Te is another semiconductor and it exhibits a normalized conductivity parameter of about half the value of the same parameter for HgSe.
• concentrations in the emitter and gap regions can be related to the emitter-gap potential barrier. More specifically, the potential barrier between the emitter and a p-type gap relative doping concentrations was found
• ⁇ u is the emitter-gap potential barrier
• N d + and N a ⁇ are the ionized donor and acceptor concentrations
• n,- is the intrinsic carrier density
• _r max is the maximum emitter temperature
• the barrier in embodiments of this invention is up to about 7, preferably in the range from about 1.5 to about 7, and more preferably from about 3 to about 7. Unfortunately, it is not possible to achieve this for InSb in the absence of an independent gap bias for a p-type gap region in the vicinity of room temperature.
• the barrier height was determined to be
• a normalized barrier height of 5-7 corresponds to a doping ratio of e 5 - e 7 , which evaluates numerically to 150 - 1100. If the n* region is doped to a level of 10 20 cm “3 , then the gap region doping should be in the range of 9 x 10 16 cm “3 to 7 x 10 17 cm '3 . 2. Results for the InSb Thermal Diode a. Carrier injection
• the emitter is the hot n* region 14 to the left.
• the gap region 16 is a thick region in the center, which may be either ⁇ ?-type or p-type (although it was found that the efficiency is higher if the gap is n-type).
• the collector is depicted here as a recombination collector region 18 and metal contact 20 that is cold.
• a premise of designs of the present invention is that carriers are boiled off from a hot emitter region
• Electron injection into ap-type gap region would result in a much simpler problem to analyze, but there exists a significant barrier which occurs in the depletion region. The optimum efficiency occurs when the barrier is on the order of 4 k B T. The barrier between an n* emitter and ap-type gap is closer to 8-9 k B T. Consequently, to inject a larger number of carriers, a lower barrier is needed. Lower barriers occur with moderate n-type gap regions, but then one must understand carrier injection of a majority carrier.
• Figure 4 illustrates numerical solutions for charge emission from a hot «*-type emitter into ap-type gap region. It is seen that electrons are emitted into the gap region and screened by the majority carrier holes, and the minority carrier transport occurs primarily through diffusion. The holes act to screen the field in the gap region.
• FIG. 4 shows electron and hole concentrations for an n*pn* thermionic structure in InSb.
• the donor concentration in the emitter and collector regions is 10 20 cm “3
• the acceptor concenfration in the gap region is 10 17 cm “3 .
• the emitter is at 600 K
• the collector is at 300 K.
• FIG. 5 shows electron concentrations for an n*nn* thermionic structure in InSb.
• the donor concentration in the emitter and collector regions is 10 20 cm “3
• the donor concentration in the gap region is 10 14 cm “3 .
• the emitter is at 600 K
• the collector is at 300 K.
• Figure 6 shows electron and hole concentrations for an n*nn* thermionic structure in InSb.
• the donor concentration in the emitter and collector regions is 10 20 cm “3
• the donor concentration in the gap region is 8 x 10 17 cm “3 .
• the emitter is at 600 K
• the collector is at 300 K.
• FIG. 7 illustrates the normalized barrier height for the example considered above as a function of the gap doping.
• Figure 7 shows the normalized barrier height ⁇ u as a function of the doping concentration.
• the emitter is assumed to be doped to have 10 20 electrons/cm 3 .
• Figure 9 plots the magnitude of both current and voltage.
• the thermal power per unit area dissipated by the device for the conditions used in the previous examples is illustrated in Figure 11.
• Figure 12 shows the efficiency as a function of voltage for the InSb example considered above. Calculations are shown for gap donor densities of 10 17 (the lowest curve on the plot), 3 x 10 17 , 5 x 10 17 and 7 x 10 17 (the highest curve on the plot) in units of cm "3 . The dots are the efficiencies at the optimum points.
• the emitter-gap barrier increases at higher emitter doping since the gap doping was kept fixed; and the electron mobility decreases at higher carrier concenfration. Both of these effects combine to reduce the beneficial impact of a larger emitter doping. It is possible to implant Te (which is the lowest ionization energy donor) in the emitter at concentrations on the order of 10 20 cm '3 . Simulation by utilizing the TRIM-91 code indicates that such a high dopant density will lead to the development of an amorphous emitter layer. Such a layer will have a different band gap, effective mass, and mobility than what we have modeled. In addition, one would expect that the recombination rate would be very high. Some consequences of this can be anticipated.
• Electron injection into the gap will be limited to emitter densities that are available on the order of one recombination length into the emitter as measured from the gap side. This will be the case down to spatial scales that are on the mean free path of the electron.
• the emitter region were crystalline at high doping levels, then the associated conduction band density of states would not be particularly large, so that the ionization balance of the donors will likely favor significant occupation of the donors.
• Data for the donor ionization energy is available (Te appears to have a donor ionization energy of 50 meV in InSb), so that the ionization fraction can be estimated.
• the optimum efficiency should be independent of the gap length or that this independence is nearly maintained for a gap thickness ranging between 200 ⁇ and 2 mm.
• the thermal power is found to be proportional to the inverse gap thickness in any of the models considered in the context of this invention, as illustrated in Figure 15 for a thermal diode.
• Figure 16 shows the efficiency of a design with an emitter electron concenfration of 10 20 electrons/cm 3 and a gap donor density of 7 x 10 17 cm “3 . The results are plotted as a function of the emitter temperature assuming that the collector temperature is 300
• This device uses a highly doped emitter region, a gap region which can be either p-type or n-type, and an ohmic metal collector with a sufficiently large work function arranged so as to have a negligible thermionic injection current above the ohmic contribution due to canier equilibrium at the collector contact.
• an n* region can inject elecfrons into an n-type gap region, and the transport is more or less diffusive in the gap region.
• the thermal diode is capable of operation as an energy converter based on thermionic emission from the emitter into the gap, and subsequent transport to the collector. It has also been shown above how to optimize embodiments of the present invention as a function of gap donor concentration. The optimum efficiency of the thermal diode can be as high as 5.5%> with a 600 K emitter, assuming that an electron density of 10 20 cm "3 can be developed in the emitter.
• Thermionic energy conversion efficiency in embodiments such as those schematically illustrated in Figure 2 is ultimately limited by the presence of an ohmic return cunent due to the thermoelecfric response of the semiconductor. If this return current could be suppressed, then a substantial increase in efficiency would be obtained. This section shows that it is possible to increase the efficiency by roughly a factor of 2 when the return cunent is reduced.
• One scheme for reducing the return current involves compensating the n-type substrate with p-type doping to produce a nearly intrinsic layer in front of the collector contact in embodiments of the present invention, thus reducing dramatically the supply of available elecfrons that would initiate an ohmic return cunent. A trade-off is apparent in this approach because too much p-type compensation can restrict the flow of thermionic current to the collector.
• thermodynamic limit 10%o of the thermodynamic limit.
• a compensation is implemented as follows. As noted above, it might be possible to increase the efficiency by suppressing the ohmic return current of opposite sign to the thermionic cunent. One way to do this is to use p-type doping to produce a compensated layer on the inside of the collector contact, which would prevent injection of electrons from the collector side of the device (see Figure 19).
• Figure 19 schematically shows an embodiment of a compensated thermal diode according to this mvention.
• the emitter is the hot n* region 14 to the left.
• the gap region 16 is a thick region in the center, which is n-type.
• the collector is depicted here as a metal contact 20 that is cold.
• the hot ohmic contact 12 is adjacent to the hot n* region 14.
• a compensated region 19 created through the addition of p-type doping that suppresses the electronic return current.
• the addition of p-type doping can produce a layer of p-type semiconductor if not precisely matched to the substrate doping, which can inhibit the thermionic electron current from reaching the collector.
• a small region is found to exist in parameter space around perfect compensation in which design numbers can be chosen that allow simultaneous collection of the thermionic cunent and rejection of the ohmic return cunent. The efficiency computed for such a device was found to be substantially increased over that of the basic diode structure. This section considers this device and associated issues. a.
• Figure 20 shows the current as a function of gap doping for the illustrative InSb thermal diode design considered in the last section.
• the current is computed under conditions of optimum efficiency.
• thermoelectric regime which conesponds to positive cunent (electrons moving from the collector to the emitter)
• the cunent is taken under conditions where the voltage is half of the thermally induced EMF, which is roughly where the optimum is in the thermionic regime.
• the thermally induced cunent is observed to change sign.
• gap doping there is not enough conductivity for the gap to sustain an ohmic component large enough to compete with the thermionic injection.
• the gap doping increases, at some point the ohmic cunent surpasses the thermionic cunent in magnitude, and thermionic energy conversion is no longer possible.
• This ohmic return current is made up of electrons that originate on the collector side of the device, and transport primarily by drift to the emitter.
• Figure 21 shows optimization of efficiency as a function of gap doping with p-type compensation using a concentrations of 7 x 10 17 , 10 18 , 2 x 10 18 and 3 x 10 18 cm "3 .
• the dotted line indicates the efficiency obtained in the absence of a blocking layer. The maximum efficiency is obtained when the acceptor concentration of the compensation layer is adjusted to match the substrate donor concentration. A substantial increase in the optimum efficiency is obtained over the uncompensated case.
• the shape of the efficiency curves shown in Figure 21 can be understood qualitatively from simple considerations.
• the efficiency is maximized under conditions where the blocking layer is intrinsic, which simultaneously allows transmission of the tl ⁇ ermionic current from the emitter, while producing a minimal return current.
• the compensation layer produces ap-type region, which in this application behaves more or less as a reverse biased diode in rejecting the thermionic current.
• the compensation is insufficient to eliminate excess electrons.
• a return cunent is initiated, with a magnitude that is roughly linear in the electron concentration in the blocking layer. Consequently, a linear decrease is seen in the efficiency on the high side of the optimum.
• the capacity of the electrical cunent leads limits the cunent densities to 10 2 - 10 3 A/cm 2 . Otherwise, the voltage drop in the wires becomes unacceptable. Moreover, there is a temperature drop across the diode of 200-300°C. For the given thermal conductivity of InSb, this translates into a gap thickness of about 1cm.
• This thickness presents challenges such as the recombination length being comparable with the gap thickness and technological problems with polishing thick wafers. For example, most wafer processing equipment is designed for a thickness less than 1mm.
• a typical approach to achieving thick gaps is to stack the diodes. Because the cunent through the diodes stacked in series is the same, this means that stacked diodes should be cunent matched. One diode producing a larger cunent results in a voltage drop across the other diodes and reduced performance due to additional potential baniers.
• the following example assumes an InSb diode material with all diodes having the same geometry and with a heat source temperature of 530 K and a heat sink temperature of 460 K.
• a single diode configuration is shown in Figure 22.
• the anow in Figure 22 indicates that the temperature T of the hot ohmic contact 12 is higher than the temperature of collector 20.
• four diodes may be stacked as shown in Figure 24, where the first diode (D,) has a gap dopant concentration of 5- 10 17 cm "3 , D 2 ⁇ 7- 10 17 cm “3 , D 3 ⁇ 10 18 cm “ 3 , and D_ ! ⁇ 2-10 18 cm “3 .
• stacked diodes according to the present invention comprise diodes whose respective elements are manufactured with the same materials for each diode, it is understood that embodiments of stacked diodes in the context of this mvention are not limited to such stacks. Some embodiments of stacked diodes according to the present invention comprise diodes whose respective elements are manufactured with different materials. For example, in some embodiments of stacked diodes the emitters in different diodes comprise different materials, and/or the gap regions in different stacked diodes comprise different materials, and/or the collectors in different stacked diodes comprise different materials.
• the compensated thermal diode design has been optimized to operate with maximum efficiency with a hot emitter at 600 K. It is of interest to determine the efficiency of the device at other emitter temperatures. Numerical results for the efficiency are illusfrated in Figure 23 A for different substrate dopings assuming perfect compensation. Figure 23 A shows the efficiency under optimized conditions as a function of emitter temperature for different gap doping with perfect compensation.
• An InSb compensated thermal diode structure 625 ⁇ thick is assumed, with an emitter electron density of 10 20 cm "3 and a collector temperature of 300 K.
• Gap donor concentrations and matched acceptor concentrations are (in order of increasing efficiency as plotted) 7 x 10 17 , 10 18 , 2 x 10 18 and 3 x 10 18 cm "3 .
• FIG. 23B shows the efficiency normalized to the thermodynamic limit under optimized conditions as a function of emitter temperature for the different cases shown in Figure 23 A.
• the compensation layer is effective at high emitter temperature.
• optimization at high temperature appears to produce relative optima at other temperatures such that separate designs optimized for different temperature regimes is not required. More advanced designs that work best around their design temperature, and not as well at other temperatures, will be discussed below.
• Examples Figures 27A-27B show efficiency as a function of temperature for optimized embodiments of compensated thermal diodes according to this invention.
• FIGS 27A-27B are labeled according to the gap material, and numbers within brackets represent the canier concentration.
• the efficiency shown in Figure 27B is given relative to that of a Carnot cycle.
• a compensated layer in an n-type semiconductor can be made by, including but not limited to, introducing acceptors.
• the donor ionization energy is 50 meV.
• the same ionization energy is characteristic for acceptors created by vacancies.
• a compensated layer exists if the number of vacancies matches the initial donor concentration (ri).
• Ion implantation creates a vacancy concentration profile which is more pronounced at the last 20-30%) of the ion range. This 20-30%) of the ion range can be decreased to less than the tunneling distance in InSb, which is typically between 100- 150 A, to 1 avoid the formation of additional baniers.
• compensated thermal diodes are characterized by high efficiencies, such that a larger compensation extent leads to a higher efficiency.
• the peak efficiency computed for the compensated thermal diode is competitive with the best thermoelectrics. 4. Ohmic Contact
• An ohmic contact is defined as a metal-semiconductor contact that has a negligible contact resistance relative to the bulk or spreading resistance of the semiconductor. (See Sze, S.M., Physics of Semiconductor Devices. N.Y., John Wiley & Sons, 1981, pp: 304-311, the contents of which are specifically incorporated herein.) This section describes ohmic contacts and methods for making such contacts according to this invention. Metal-semiconductor interfaces introduce local potential baniers, which are known under the generic name of Schottky baniers.
• ⁇ m the metal electron work function
• ⁇ s the semiconductor electron affinity.
• the Schottky barrier values are 0.70 eV for GaAs and 0.18 eV for InSb.
• the operating voltage range is lower than the Schottky barrier height. This will destroy the effect or at least bring down operating currents.
• W ]oss to be less than 1% of the total power, ⁇ b must be less than lmeV.
• the banier is often expressed in terms of a contact resistance. Therefore, at the stated currents, the contact resistance must be less than 10 "5 - 10 '6 ohm.
• a dopant level conesponding to 10 "6 ohm/cm 2 is 10 20 -10 21 (Te in InSb) at 300°C.
• the electron effective mass for tunneling increases with temperature, and at 500°C the required concentration is 10 21 rather than 10 20 .
• a high dopant concentration layer must be sufficiently thin so it does not introduce its own barrier on the contacting semiconductor interface. The Shannon reference cited above estimates this thickness as less than 150 A. This approach applies to both n-type andp- type doping, while keeping in mind that the current sign is reversed when going from an n-type region to ap-type region.
• the implantation dose required to achieve a 10 21 cm "3 shallow doping was calculated by using the TRIM-91 computer code (G. Ziegler, G. Biersack. IBM (1991)).
• the ion range and required dose were calculated separately for In and Sb.
• the calculation results were averaged to approximate InSb.
• the difference between In and Sb in this energy range was no more than 20%.
• Te was utilized as an n-type dopant because Te has the lowest known ionization energy (50 meV).
• Figure 30 shows the calculation results for this dose, while Figure 31 shows the ion range.
• the calculations for Ag doping are shown in Figures 32 and 33. The ion implantation process creates vacancies which subsequently must be annealed.
• an ohmic contact for a diode comprising InSb may be formed by annealing indium layers on InSb wafers. The following procedure was performed in an acid cleaned quartz ampule. The ampule was baked for more than one hour in a high vacuum at 800°C. The InSb samples having an indium coating were loaded into the quartz ampules, which was pumped down and filled with 10-100 ton of helium. Helium, which has a high thermal conductivity, provides for quick cooling. After annealing at various temperatures, I vs. V curves were measured on the samples to confirm that ohmic contacts existed. Positive results were obtained in the temperature range of 250-400°C with an annealing time of 10-60 minutes. At temperatures exceeding 500°C the indium dissolved completely rendering the samples unusable, even though the samples showed ohmic behavior. 5. Examples a. Design parameters
• intermediate, thermally conducting layers may be placed in other embodiments of this invention between the ohmic contacts (12, 20) and heat sinks to ensure thermal contact.
• a deposited layer of In or the like may be used on the hot side and a deposited layer of In-Ga eutectic or the like may be used on the cold side. These materials are sufficiently malleable to ensure adequate thermal contact at low compression (0.1 - 1.0 MPa).
• materials that can be used for these layers according to this invention are malleable thermal conductors, although other materials can be used in other embodiments.
• Another method of providing thermal contact is the application of paste, glue, a low temperature soldering alloy, or equivalents thereof.
• An electrically and thermally conducting layer is then added to serve as a diffusion banier between a thermally conducting layer and a semiconductor.
• the thermally and electrically conducting layer is used as an emitter without an additional semiconductor emitting layer.
• this layer includes, but are not limited to, the following: (1) conducts heat; (2) conducts electricity; (3) emits electrons; (4) creates a Schottky banier at the metal-semiconductor interface; (5) creates a diffusion banier; (6) prevents a chemical reaction of a semiconductor with a subsequent layer; (7) matches the thermal expansion of a semiconductor to prevent delamination; (8) is thermally stable within the range of operation of the thermal diode; and (9) has a high resistance to oxidation if not vacuum encapsulated or encased in an inert environment.
• InSb has a thermal expansion coefficient of 5.2 - 5.4 x 10 "6 K "1 in the temperature range of 300-500 K.
• Other possible materials include, but are not limited to, Mo, Cr, W, Ta, Re, Os, Ir, lanthanoids and nickel alloys, Pt and soft metals such as In, Au, Cu or the like. From this list, Ta and the lanthanoids are prone to oxidation, and In has a low melting temperature.
• Highly doped semiconductors and semi-metals may also be used.
• a thin layer of Si has a sufficiently high thermal and electric conductivity.
• certain precautions should be observed, and, in particular, it should be noted that a large forbidden gap when compared to InSb ensures the formation of an internal barrier which impedes current transport.
• the thickness of embodiments of the thermally and electrically conducting layer is designed as follows.
• the thermal conductivity is preferably higher than that of a semiconductor gap. With a gap thickness of 100-1000 microns, the thickness of the layer is preferably less than about a few microns since it will increase thermal losses.
• the layer thickness there are a few considerations that define the layer thickness.
• metal layers are preferably thicker than the electron mean free path in order to maintain its bulk properties. Since the layer is in close proximity to another metal (intermediate layer), it can affect its Fermi level position and change the electron emission into the semiconductor. This effect is known to be significant at metal layer thicknesses below 1000 A. This number is at least a few electron mean free path lengths and can be regarded as a low practical limit in order to avoid unnecessary complications. Similar thickness considerations apply to the semiconductor emitter region n*. .
• a prefened situation for the emitter-gap interface is when the region has matched crystallography, i.e., when the emitter region is grown epitaxially on top of the gap region.
• This can be achieved by maintaining the deposition temperature above
• the epitaxial growth is more complex. Scattering and decreased converter performance occurs when the emitter-gap interface is mismatched.
• metalJ metal 2 InGa eutectic (bulk)/Cr or Ni (1000-4000 AVlnSb (360 microns; doped with l.lxlO 18 Te, orientation 100)/Pt (1500 A)/ In (bulk).
• the thickness of wet ⁇ / cannot be less than the mean free path of electrons for the specific metal at a specific temperature, e.g., for Ag the mean free path is about 400 A.
• metal j /n**/n/n ⁇ */metsd 2 InGa eutectic (bulk)/Cr (1500 A)/In (100 AYfriSb (360 microns; doped with l.lxlO 18 TeVIn (100 A)/Pt (1500 A)/ In (bulk).
• metal j ln**/nln**/ eM 2 InGa eutectic (bulkVCr (1500 A)/In
• metaljn **/n*/n/n**/metal 2 InGa eutectic (bulkVCr (1500 A)/In (100 A)/InSb (400 A; doped with 3.0xl0 20 Te)/TnSb (500 microns; doped with l.lxlO 18 Te)/Tn (100 A)/Ni (1500 A)/ In (bulk).
• metal j ln **lnln **/metal 2 InGa eutectic (bulkVCr (1500 A)/In (100 AVlnSb (500 microns; doped with 1.9xl0 17 Te)/In (100 A)/Pt (1500 A)/ In (bulk).
• metal 1 / ⁇ **// ⁇ */ «/p//j**/metal 2 InGa eutectic (bulkVCr (1500 A)/In (100 A)/InSb (400 A; doped with 3.0xl0 19 Te)/InSb (500 microns; doped with lxlO 20 Te; 2° from (100))/p-InSb (2000 A; doped with 3.1xl0 14 Te)/In
• metal 1 / «**/ «*/M/p/w**/metal 2 InGa eutectic (bulk)/Cr (1500 A)/In (100 A)/TnSb (400 A; doped with l.OxlO 20 Te)/InSb (500 microns; doped with lxlO 18 Te)/p-InSb (400 A; where p-type region is ion implanted with Ar or NeVIn (10 ⁇ A)/Pt (1500 A).
• Figure 34 shows the temperature behavior of the InSb gap (see Landolt-B ⁇ rnstein, Numerical Data and Functional Relationships in Science and Technology, Group III:
• Schottky barrier values can be determined by the slope change of the curve taken ' from external I vs. V curve measurements. At room temperature the barrier height was 175-180 meV, irrespective of the dopant concentration (Te) in InSb up to 10 20 cm “3 (in contact).
• Figure 35 shows the banier height as a function of temperature for a 2000 A interface layer doped with Te to 3xl0 19 cm “3 deposited on InSb doped with Te to lxlO 18 cm “3 (500 ⁇ ) for an In emitter. Since the banier height decreases with temperature at a faster rate than E g , it means that the neutral level ⁇ 0 is higher than E F , and the surface density of states increases with temperature.
• Figures 34 and 35 provide for ⁇ 0 to be estimated at 15-20 meV at around 300°C.
• This type of banier is illustrated in Figure 36 A.
• the insulating film (oxide) shown in Figure 36A is so thin that carriers tunnel through without giving an appearance of an actual banier, even if it is present. It has been found in the context of this invention that the implementation of this type of diode increases operating temperatures of embodiments of this invention. a. Experimental results
• Samples were manufactured on the basis of InSb wafers doped with Te to lxlO 18 cm “3 .
• the wafer thickness was about 500 microns and polished on both sides.
• an emitter layer of 2000 A of InSb doped with Te to 3x10 19 cm “3 concenfration was deposited on a wafer by magnetron sputtering.
• the sample size ranged from lxl to 3x3 mm 2 squares that were painted with InGa eutectic (T Period, - 35°C) on both sides.
• the painting process involved the application of some pressure to destroy any surface oxide layer.
• Figure 36B schematically illustrates an embodiment of the present invention comprising a hot ohmic contact 12, an emitter 14, a gap region 16, a compensated region
• Region 15 is formed in some embodiments on the emitter side that faces hot ohmic contact 12 to reduce the metal-semiconductor interface barrier.
• This metal-semiconductor-interface-banier-reduction layer is formed in some embodiments by magnetron sputtering.
• Region 17 is formed in some embodiments on the gap region side that faces the collector cold metal contact 20, and its effect is to reduce the metal- semiconductor interface barrier. This region is formed by techniques analogous to those employed to form region 15. Other embodiments of the present invention comprise only region 15, and still other embodiments of the present invention comprise only region 17. As indicated above, the presence of at least one of regions 15 and 17 in embodiments of the present invention, including compensated and uncompensated embodiments, increases their operating temperatures.
• the test apparatus included a cartridge heater rated at 400 W in a massive silverized copper block, and a water cooled cold plate (silverized copper) mounted on a micrometric linear stage.
• the electric leads were massive flexible copper strands ( ⁇ 10 "4 ohms).
• the temperature was controlled with Omega RTD's with a Keithly 2001 display.
• a custom made resistor bank was provided for loads from 10 "4 ohms and higher.
• the voltage was measured with 0.01% accuracy, and the cunent with 1%> accuracy.
• the samples were installed on a hot plate and compressed with the cold plate on a linear positioning stage. Argon gas was introduced between the plates to prevent oxidation of the materials at elevated temperatures.
• the hot side was thermally insulated from the mounting plate and ambient air.
• Figure 37 illustrates an example output I vs. V curve for a single sample indicated by line 42 and a stack of three samples indicated by line 44 for an emitter temperature of 200°C.
• the output difference is less than 20% when the decrease in the heat flow is at least three times. This means that the efficiency in a stack configuration increases dramatically.
• each interface introduces thermal resistance due to the non-ideal contact and the phonon mismatch effect.
• the minimal numbers for phonon mismatch are around 4% (See Swartz, E.T., Thermal Boundary Resistance, Vol. 61, No. 3 (July 1989), which is incorporated herein by reference).
• Each sample introduces two additional boundaries.
• Testing devices were designed on the basis of standard mechanical parts for laser applications, including a Coherent® stainless steel bread board. Micrometric linear stage and laser optical stands allowed for 100 mm of vertical linear travel.
• the hot side was mounted with a Macor ceramic ring on the linear stage and consisted of a massive copper block with a 400 W Ogden Scientific cartridge heater.
• the copper block was thermally insulated with porous ZrO 2 ceramics and fiberglass fabric.
• Interchangeable copper rods made of oxygen-free copper that had a 2-micron coating of silver were used to deliver heat to the sample.
• Each rod had at least two holes configured for receiving temperature sensors. By measuring temperature at two points along the rod and knowing the thermal conductivity and cross-section of the rod, the heat flow to the sample was determined.
• a silver coated water-cooled cold plate was mounted on the top of the optical stand with a Newport three axis "Ball and Socket" stage, which allowed the parallel alignment of the cold and hot plates.
• the electric cunent lead comprised silver coated braided copper wires having a resistance of about 10 "4 ohm.
• Load resistors in the range of about 10 "5 ohm to about 10 "1 ohm were made of copper and stainless steel and were connected to the cunent leads by massive bolts.
• Power to the heater was supplied by a Xanfrex 300-3.5 DC power supply. Voltage across the load and sample resistance were measured with a HP34420A NIST- traceable nanovolt/microohmeter in a 4- wire configuration. Keithley 2001 multimeters were used as readouts for Omega thermocouples and RTD temperature sensors. Electric cunent was measured by an Amprobe® A- 1000 transducer. Load and leads resistance allowed independent cunent determination. On all measured parameters except cunents below 1 A, the accuracy was better than 1%.
• argon gas was introduced between the hot and cold plates using a Capton foil skirt.
• Material for the sample preparation comprised InSb wafers (WaferTech, U.K.) of about 2" in diameter and 500 ⁇ in thickness. The wafers were polished to about 20 A RMS (root mean square) on both sides. Standard dopant (Te) concenfration was about
• the emitter layer was deposited by magnetron sputtering. An InSb target doped with 3xl0 19 cm “3 Te was also used.
• the emitter layer thickness was in the range from about 400 A to about 15000 A. Emitter thickness in embodiments of the present invention was at least about 400 A. Furthermore, principles in the context of this invention do not impose any limitation to the emitter thickness and therefore embodiments of this invention are not limited by constraints in an upper bound for such thickness.
• Fig. 38 compare of the maximum efficiency for the compensated samples shown therein with the efficiency of the non-compensated sample reveals that the compensation layer leads to about 80%> perfonnance improvement.
• Fig. 38 also shows the computed efficiency that is predicted at a given implantation dose.
• the range for Ar + at 40 keV in InSb is approximately 400 A, which is sufficient for creating a compensation layer.
• a 400 A layer is prone to fast diffusion loss of vacancies at elevated temperatures.
• He ion implantation is performed in other embodiments.
• the He ion layer thickness in these embodiments is of the order of a few microns, which increases the effective life of the implantation layer.
• the estimated diffusion half life of vacancies in InSb at 1 micron thickness is approximately 1 year at 200°C. Because the compensation layer is located on the cold side of embodiments of this invention, diffusion problems are typically avoided when the compensation layer is a few microns thick. Computed ion ranges and vacancy formation for 4 He ions in InSb are shown in Figs. 39-40. b. Embodiments with Hg,. K Cd x Te
• Hg,_ x Cd x Te semiconductors (herein refened to as "MCT") have very good thermionic figure-of-merit values when 0.08 ⁇ x ⁇ 0.15, where the upper and lower bounds are given approximately.
• a prefened value of x is about 0.14.
• Embodiments of this invention comprised a 500 micron thick Hg 086 Cd 0 M Te wafer (Lockheed Martin IR
• MCT Reacts with various substrates, creating heavily doped donor (reacting with metals such as In, Fe, Ga and Al) or acceptor (reacting with metals such as Ag, Au, and Bi) layers, with the reaction rate depending on the material and temperature.
• donor reacting with metals such as In, Fe, Ga and Al
• acceptor reacting with metals such as Ag, Au, and Bi
• P. Caper Properties of Narrow Gap Cadmium-based Compounds, INSPEC, 1994, which is incorporated herein by reference.
• MCT metal-organic chemical vapor deposition
• InSb is less reactive and requires the implementation of a more complex technique for creating an n* region.
• InSb is limited to dopant concentrations of about 2-3xl0 19 cm "3 .
• the performance of embodiments of the present invention shows that substrates that form donor impurities are prefened because they generate higher current densities. As shown in Fig. 41 , a thermoelectric response without a carrier injection layer generates a current density that exhibits little or no change with respect to temperature. For example, copper forms an acceptor impurity and should not form an n* region.
• Figure 41 shows electric cunent density as a function of temperature for Hg 086 Cd 0 14 Te samples, one of them with a Cu emitter layer and another with an In-Ga emitter layer with substrate composition In 075 Ga 025 .
• Contact resistance was monitored in both cases to ensure that oxide layers do not play a significant role in the observed results.
• In-Ga makes a slightly better contact than copper (about 92 m ⁇ for In-Ga compared to about 103 m ⁇ for copper).
• the electric cunent density as a function of temperature for the sample with copper flattens out.
• the MCT sample was allowed to cool down and a layer of In-Ga about 20-50 micron thick was placed on top of the copper substrate.
• the electric cunent density exhibited a change with temperature that was similar to that exhibited by the sample with copper only at temperatures up to about 70°C.
• the same figure shows that above this point the electric cunent density clearly increased with temperature. This is attributed to the acceptor-type impurity being swamped by n-type impurity, thus causing the sample to exhibit a canier injection mode with many times higher cunent output.
• Output voltage in both cases was approximately the same, from about 290 to about 350 ⁇ V/K, and is consistent with the known thermoelectric Zeebeck coefficient for MCT.
• Figure 42 shows the electric cunent density as a function of temperature for two Hg 086 Cd 0 14 Te samples, one of them with an Al substrate and the other sample with an In-Ga substrate.
• a prefened composition of this substrate is embodied by
• the In-Ga substrate forms a better emitter than Al because the electric cunent density as a function of temperature is consistently higher for the sample with In-Ga over the entire temperature range.
• In forms a better emitter than Ga, particularly with pure In substrate.
• Substrates such as
• Al, In and Ga are examples of substrates that form n-type impurities in MCT that create electron injecting n* regions.
• Figure 43 shows the absolute efficiency exhibited by an embodiment of a MCT converter according to the present invention in which the n* emitter layer was formed by reacting MCT with In 075 G 025 eutectic.
• Absolute efficiency is defined as the ratio of an electric power output to the heat flow through the sample.
• Fig. 43 was recalculated in terms of a percentage of an ideal Carnot cycle efficiency, which are shown in Fig. 44.
• embodiments of the present invention comprise a diffusion banier.
• An ytterbium layer of up to about 10 A is an example of such diffusion banier.
• a thickness of up to about 10 A is prefened because such metal layer does not significantly affect electron transport properties.
• embodiments of this invention that comprise stacked InSb plates with an emitter on a hot side configuration, display a significantly enhanced efficiency.
• Efficiency for these types of embodiments was determined as follows. InSb and MCT exhibit best performances at different temperatures: from about
• MCT small thermal conductivity of MCT makes the direct measurement of heat flow difficult, especially when the measurements have to be taken with small samples.
• the dimensions of some of the samples used in embodiments of the present invention were at most a few square millimeters and, because of these reduced dimensions, were not suitable for contact temperature measurements with available temperature sensors.
• the small size of these samples did not permit the use of standard IR imaging cameras because of the limited spacial resolution of such IR imaging cameras. A methodology that relies on custom optics IR cameras avoids this problem.
• ⁇ Tcan be measured as a temperature difference between the cold and the hot plates, and the first equation can be iterated using ⁇ T ,, ⁇ j (T) and ⁇ 2 (T) values.
• the heat flow and the temperature drop across each plate are estimated according to this iterative procedure.
• the converter efficiency is computed by taking the ratio of the electric power output to the heat flow through the device.
• the thickness of the InSb plate was adjusted to vary the converter operating temperature range from less than 150°C to more than 300°C with substantially the same fraction of Carnot cycle efficiency at over 30%. Direct measurements with infrared imaging equipment showed slightly lower heat flow through the converter, probably due to non-ideal contacts, resulting in 3%-4%» higher efficiency.
• Figure 45 shows the efficiency of an embodiment of a sandwich converter according to the present invention.
• An about 1-mm thick InSb plate was used in this embodiment and the dopant (Te) concentration was about 10 18 cm "3 .
• the emitter layer was about 2000 A and it comprised a sputtered InSb layer with about 3x10 19 cm “3 Te.
• the plate was coated with a layer containing In-Ga.
• a prefened composition of this In- Ga material is embodied by In 0 _ 75 Ga 0-25 .
• the thickness of this layer was from about 30 microns to about 50 microns.
• a second plate was made of Kg ⁇ C-a ⁇ Te, with x preferably satisfying 0.08 ⁇ x ⁇ 0.15, with the upper and lower bounds given approximately.
• a more preferred form of this compound has an approximate stoichiometry given by Hg 086 Cd 0 14 Te, with a thickness of about 0.51 mm.
• the average stack cross section was about 1.70x1.52 mm 2 .
• the fraction of an ideal Carnot cycle efficiency as a function of the hot plate temperature for this embodiment is shown in Fig. 46. T cold regarding Fig. 45-46 was 20°C. As shown in Fig. 46, the percentage of an ideal Carnot cycle efficiency for this embodiment at maximum performance is about the same as that displayed in Fig. 44, but this embodiment exhibits it at a significantly higher temperature.
• the figure of merit for the HgTe is about 2.5 times better than that for InSb. Addition of Cd to HgTe improves canier mobility and reduces thermal conductivity.
• FIGS 48 and 49 are essentially the same as those of a thermal diode 10 for converting heat to electricity, as set forth above (see Figures 1 and 19). Accordingly, the terms “solid state thermionic converter of thermal energy” generically refer herein to embodiments of converters of thermal energy into electricity according to this invention, and to refrigeration embodiments according to this invention.
• Figure 48 illustrates the uncompensated thermal diode and Figure 49 the compensated thermal diode.
• the essential difference between the heat to electricity and refrigeration embodiments is that canier transport is assisted by an external electric field, E a hail and the n*-type region 14 is connected to a thermal load that is cooled by heat flow to the first ohmic contact 52 on the n*-type region 14.
• the n*-type region 14 is thermally insulated by means of an insulating material 54. Rather than a heated n *-type region 14, as is the case in the heat to electricity embodiment, a thermal load is cooled by heat flow, Q Lm ⁇ to the n*-type region 14 in the thermal diode 50 illustrated in Figure 48.
• a gap 16 region is adjacent to the n*-type region 14, and a second ohmic contact 53 having a recombination collector region 56 is formed between the second ohmic contact 53 and the gap region 16.
• the gap region 16 may be n-type, p-type or intrinsic.
• a compensated region 19 is on the inside of the metal contact, which is created through the addition of p-type doping that suppresses the electronic return cunent.
• the back surface of the second ohmic contact 53 acts as a heat exchanger, and heat flow ⁇ &c ⁇ nge dissipates the heat from hot electrons.
• Figure 50 shows the coefficient of performance (CoP, relative to a reversed
• Figure 50 Carnot cycle) as a function of temperature for compensated diodes as refrigeration embodiments of the present invention.
• the coefficient-of-performance curves in Figure 50 are labeled with the different gap materials in each embodiment.
• Figure 50 also shows that embodiments of the present invention are operational at temperatures well below 200 K, in contrast with conventional devices that generally cannot operate at temperatures below about 200 K.
• heat exchangers recognizes there are many means for accomplishing heat exchange including, but not limited to, air and liquid cooling, or equivalents thereof.
• the heat source may either be in the form of fossil fuel or solar concentrators.
• Solar concentrators can also be in the form of solar heated water pools, utilizing day/night temperature differences.
• a few hundred cubic meters of water with a hundred square meters of surface in conjunction with embodiments of the present invention could provide the electricity supply for a house in areas with a temperature differential of about
• a thermal diode according to the present invention in combination with a conventional engine driving an electric generator and an electric motor would substantially increase mileage.
• Direct energy conversion has tremendous application in electric cars.
• One application involves using thermionic devices according to the present invention with operating temperatures up to about 150 to 200°C as overall efficiency boosters.
• Another application is an automobile with an electric drive and a conventional engine coupled with an electric generator having a converter anay according to the present invention as an intermediate radiator.
• Automotive and propulsion applications are also applicable to maritime applications.
• solar concentrators may be used in a sail-type fashion.
• a combination of light and inexpensive plastic Fresnel lenses with thermal diode converters according to the present invention may be incorporated into modern rigid wing-type sails, providing for the use of wind and sun energy to propel a boat with about 100-200 W/m 2 of the sail solar component.
• embodiments of the converter according to the present invention can utilize very small temperature gradients in a self-sustaining mode, a temperature gradient between the heat sinks will be created with asymmetric heat exchange on the surface (e.g., one heat sink can be thermally insulated). Also, the system will run until something malfunctions, cooling the environment and producing electricity.
• the method and apparatus disclosed herein is a significant improvement from the present state of the art of energy conversion.

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