Abstract:
Thermophotovoltaic (TPV) electric power generators have emitters with infrared (IR) outputs matched with usable wavelengths for converter cells. The emitters have durable substrates, optional refractory isolating layers, conductive refractory metal or inter-metallic emitter layers, and refractory metal oxide antireflection layers. SiC substrates have tungsten or TaSi 2  emitter layers and 0.14 micron ZrO 2  or Al 2 O 3  antireflection layers used as IR emitters for GaSb converter cells in TPV generators.

Description:
BACKGROUND OF THE INVENTION 
     This application claims the benefit of U.S. Provisional Application Ser. No. 60/113,353, filed Dec. 21, 1998 and Provisional Application Ser. No. 60/120,817 filed Feb. 19, 1999. 
    
    
     Recently, low bandgap photovoltaic cells such as the GaSb cell have made it possible to produce practical thermophotovoltaic (TPV) electric power generators. The low bandgap cells in these TPV generators convert infrared (IR) radiation from heated (IR) emitters into electric power. The IR emitters in these units operate at moderate temperatures between 900° C. and 1400° C. Baseline commercial TPV generators use gray-body SiC emitters with GaSb cells. The SiC emitter emits infrared energy at all wavelengths. However, the GaSb cells convert only infrared photons with wavelengths less than 1.8 microns to electric power. Infrared filters are used to reflect some of the non-useful longer wavelength photons back to the emitter. Unfortunately, the available filters are far from perfect. Some non-convertible infrared radiation still passes through the filters, and some of the reflected photons do not hit the emitter after reflection by the filter. 
     It is preferable to replace the gray-body emitter with a “matched” infrared emitter that emits only convertible infrared radiation. Mathematically, this perfect “matched” emitter has an emittance of 1.0 for wavelengths less than 1.8 microns and 0 for longer wavelengths. Several prior art infrared emitters have been proposed for use in TPV generators. 
     The oldest type of IR emitter proposed is the rare earth oxide selective emitter. Erbia is an example of this type of emitter. While the emittance at 1.5 microns can be as high as 0.5, the emittance for erbia falls to 0.1 at 1.4 and 1.6 microns and rises again beyond 3 microns. The result is that the emitted useful power is small because of the narrow emittance bandwidth. Furthermore, the spectral efficiency, defined as the in-band convertible power divided by the total emitted power, is low because a lot of power is emitted at wavelengths beyond 3 microns. 
     Refractory metal IR emitters, such as tungsten, have also been described. Those materials are somewhat selective in that the emittance at 1.5 microns (typically 0.3) is higher than the emittance at longer wavelengths (0.15 at 3 microns). Unlike the oxide emitters, the emittance stays low at long wavelengths (0.1 at 6 microns). Unfortunately, these metal emitters need to run very hot because of the low in-band emittance. They also produce volatile oxides when operated in air. 
     Recently, JX Crystals has described a cobalt doped spinel “matched” emitter. This “matched” emitter has an emittance of 0.7 at 1.5 microns with a large bandwidth. This emitter is selective, because the emittance falls off to 0.25 at 3 microns. Unfortunately, however, like all oxide emitters, the emittance rises again beyond 6 microns. 
     There are other disadvantages of the oxide emitters. Specifically, they are subject to cracking upon extensive thermal cycling, and they have poor thermal conductivity. 
     It is desirable to find an improved “matched” emitter with a high emittance at wavelengths below 1.8 microns and low emittance for all longer wavelengths. It is very desirable to find a “matched” emitter coating that may be applied to the current Sic emitter structures, since SiC is a proven material with good thermal conductivity and thermal cycle durability. 
     SUMMARY OF THE INVENTION 
     The invention provides a matched emitter which emits infrared radiation at 1.8 microns and less than 1.8 microns to match the wavelengths of photons that GaSb cells absorb and convert to electricity. 
     In one form, a refractory metal coating such as tungsten (W) having a thickness of about 4 microns or from about 1-6 microns is deposited on a durable high temperature substrate such as SiC. The W coating may be isolated chemically from the substrate by a refractory oxide coating, such as Ta 2 O 5 , ZrO 2  or Al 2 O 3 , so that it does not react with the substrate. The W coating is coated with a high index refractory oxide coating of a thickness such that a minimum reflectivity occurs in the center of the cell convertible wavelength band. This refractory oxide coating serves as an anti-reflection (AR) coating. The thickness of the oxide coating is specifically set to produce an absorption (emission) peak in the TPV cell conversion wavelength band. 
     In another embodiment, a refractory inter-metallic coating such as TaSi 2  is deposited on a durable high temperature substrate such as SiC. The metal silicide coating may be isolated chemically from the substrate by a refractory oxide coating, such as Ta 2 O 5 , so that it does not react with the substrate. In the case that the durable substrate is SiC, the inter-metallic coating can be a refractory compound containing a metal such as Ta along with Si and C. Alternative inter-metallic compounds may include Pd m (Si 1−x C x )or Pt m (S 1−x C x ) n . The metal silicide is coated with a high index refractory oxide coating of a thickness such that a minimum reflectivity occurs in the center of the cell convertible wavelength band. This refractory oxide coating serves as an anti-reflection (AR) coating. The thickness of the oxide coating is specifically set to produce an absorption (emmission) peak in the TPV cell conversion wavelength band. 
     Key elements in this concept are the reflecting metallic or inter-metallic coating, the AR coating, and the durable substrate. In the case of a TPV generator using GaSb cells, this AR wavelength is about 1.4 microns. 
     A typical thickness for the metal silicide is approximately 1.0 microns, while a typical thickness for the refractory oxide coatings is approximately 0.14 microns. Various substrates are possible including but not limited to SiC, Ta, NICHROME (alloys of nickel, chromium and iron), KANTHAL (heat resistant metal alloys) and stainless steel. Various metal silicides are possible including but not limited to TaSi 2 , NbSi 2 , TiSi 2 , and VSi 2 . Various refractory oxides are possible including, but not limited to, Ta 2 O 5 , Al 2 O 3 , TiO 2  and ZrO 2 . 
     Adding Si to the Ta has two beneficial effects. First, the emittance at 1.5 microns increases from 0.3 to 0.55. Second, the suicides are more resistant to oxidation. Adding an AR coating then amplifies on these same two beneficial effects. The AR coating increases the emittance again from 0.55 to 0.98 at 1.5 microns, and the refractory oxide AR coating protects the structure from oxidation. 
     The AR coated refractory silicide “matched” emitters of the present invention are useable with cells other than the GaSb cell. They are adaptable to cells that respond out to 2.3 microns by simply shifting the thickness of the AR coating. They may be used in various environments including air, vacuum, or various inert atmospheres. They may be used with various heat sources, including not just hydrocarbon flames but also nuclear heat sources. 
    
    
     These and further and other objects and features of the invention are apparent in the disclosure, which includes the above and ongoing written specification, with the claims and the drawings. 
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a side view of an AR coated refractory metal silicide matched emitter. 
     FIG. 2 is a graph of the reflection curves for Ta, TaSi 2  and AR coated TaSi 2 . 
     FIG. 3 is the emittance curve for the refractory metal silicide matched emitter. 
     FIG. 4 is a graph of the emissive power for the refractory metal silicide matched emitter and a SiC (blackbody) emitter. 
     FIG. 5 is a graph of 2 nk/λ vs wavelength for TaSi 2 . 
     FIG. 6 is a graph of 2 nk/λ vs wavelength for several pure metals. 
     FIG. 7 shows a vertical section through a thermophotovoltaic generator. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     FIG. 1 shows the structure of the refractory metal silicide “matched” emitter  1  of the present invention. A refractory metal or metal silicide emitter layer  2 , such as W or TaSi 2 , is deposited on a durable high temperature substrate  4 , such as SiC. The metal or metal silicide emitter layer  2  is isolated chemically from the substrate  4  by a refractory oxide  6 , such as Ta 2 O 5 , so that the emitter layer does not react with the substrate. Finally, the metal or metal silicide  2  is coated with a high index refractory oxide coating  8  of a thickness such that a minimum reflectivity occurs in the center of the cell convertible wavelength band. This refractory oxide coating  8  serves as an anti-reflection (AR) coating. In the case of a TPV generator using GaSb cells, this AR wavelength is about 1.4 microns. A typical thickness for the metal or metal silicide is approximately 4.0 microns for W or 1.0 micron for the TaSi 2 . A typical thickness for the refractory oxide coatings is approximately 0.14 microns. Various substrates 4 are possible including, but not limited to, SiC, Ta, NICHROME, KANTHAL, and stainless steel. Various refractory metal emitters  2  are possible, including, but not limited to, W, Ta, Nb and Mo. Various metal silicides  2  are possible including, but not limited to, TaSi 2 , NbSi 2 , TiSi 2 , and VSi 2 . Various refractory oxides  6  are possible including, but not limited to, Ta 2 O 5 , Al 2 O 3 , TiO 2 , and ZrO 2 . 
     The emitter structure  1  of FIG. 1 is effective as a “matched” emitter for TPV generators (shown in FIG.  7 ). This may be seen by reference to Tables 1 and 2, and to FIGS. 2,  3 , and  4 . Referring to table 1, the emittances for SiC, tungsten (W), and cobalt doped spinel at 1.5, 3, and 6 microns are given for reference. Refer now to the emittances of Ta, TaSi 2 , and AR coated TaSi 2 . The emittance of Ta by itself is similar to that of W. Adding Si to the Ta has two beneficial effects. First, the emittance at 1.5 microns increases from 0.3 to 0.55. Second, the suicides are more resistant to oxidation. Adding an AR coating then amplifies on these same two beneficial effects. The AR coating increases the emittance again from 0.55 to 0.98 at 1.5 microns, and the refractory oxide AR coating protects the structure from oxidation. 
     FIG. 2 shows the reflection curves for Ta, TaSi 2 , and AR coated TaSi 2  as a function of wavelength. Note that while the reflectivity decreases at 1.5 microns, the reflectivity at long wavelengths remains high for our refractory metal silicide “matched” emitter. 
     Since the absorptance and emittance for metals are simply 1 minus the refractivity, FIG. 3 shows the emittance curve for our refractory metal silicide “matched” emitter. 
     Referring again to Table 1, note that the refractory metal silicide “matched” emitter of the present invention has the highest in-band emittance relative to all of the available emitters. This means that more electric power is producible for a given emitter temperature. Also note that the ratio of in-band emittance to out-of-band emittance for our refractory metal silicide “matched” emitter is higher than for any other emitter. This leads to higher conversion efficiency. 
     FIG.  4  and Table 2 allow a comparison of a SiC emitter with our refractory metal silicide “matched” emitter. FIG. 4 shows the emissive power as a function of wavelength for an AR-coated TaSi 2  emitter and a blackbody emitter with both operating at 1400° C. Table 2 gives the calculated values for the in-band emitted power, the out-of-band emitted power, and the spectral efficiency for these two emitters. Note that the in-band power is nearly the same for each, while the out-of-band power is reduced by a factor of 3 for the AR-coated TaSi 2  emitter. The spectral efficiency is increased by nearly a factor of 2. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Emittance Values for Various TPV Emitter Materials 
               
             
          
           
               
                   
                 Material 
                 ε at 1.5 μm 
                 ε at 3 μm 
                 ε at 6 μm 
               
               
                   
                   
               
               
                   
                 SiC 
                 0.8 
                 0.85 
                 0.9 
               
               
                   
                 W 
                 0.3 
                 0.15 
                 0.1 
               
               
                   
                 Co/Spinel 
                 0.7 
                 0.25 
                 0.7 
               
               
                   
                 Ta 
                 0.3 
                 0.15 
                 0.1 
               
               
                   
                 TaSi 2   
                 0.55 
                 0.25 
                 0.15 
               
               
                   
                 AR/TaSi 2   
                 0.98 
                 0.28 
                 0.15 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Power densities and spectral efficiency at 1400° C. 
               
             
          
           
               
                   
                 Material 
                 P (0.7 to 1.8 μm) 
                 P (1.8 to 10) 
                 Efficiency 
               
               
                   
                   
               
               
                   
                 Blackbody 
                 12.2 W/cm 2   
                 31.1 W/cm 2   
                 0.28 
               
               
                   
                 AR/TaSi 2   
                 11.5 W/cm 2   
                 10.7 W/cm 2   
                 0.52 
               
               
                   
                   
               
             
          
         
       
     
     The AR coated refractory silicide “matched” emitters of the present invention are useable with cells other than the GaSb cell. They are adaptable to cells that respond out to 2.3 micron wavelengths by simply shifting the thickness of the AR coating. They may be used in various environments including air, vacuum, or various inert atmospheres. They may be used with various heat sources, including not just hydrocarbon flames but also nuclear heat sources. 
     The matched emitter concept described here can be restated in more general terms as follows. Three elements are required: a durable refractory substrate  4  (FIG. 1) with a refractory metallic (RM) coating  2  (FIG. 1) with a resonant antireflection (AR) coating  8  (FIG.  1 ). In this three element system, the metallic coating  2  must be carefully chosen such that the 2 nk/λ product for the material drops to 15 or lower at the desired resonant point and then rapidly rises for longer wavelengths. FIG. 5 shows a plot of 2 nk/λ vs λ for TaSi 2 , while FIG. 6 shows plots of 2 nk/λ vs λ for various pure metals. Referring to FIG. 6 suggests that pure Ta, W, Nb, or No could be used with an AR coating to create a matched emitter falling under the present invention. Pure Pd would not work because the AR coated resonance would be weak. 
     The best specific AR/RM to date consist of 4 microns of W on SiC followed by an AR coating of ZrO 2 . The second best is Al 2 O 3  AR on W on SiC. 
     Referring to FIG. 7, a thermophotovoltaic (TPV) generator  15  apparatus includes, in the order of energy flow, a heat source  3 , a matched coated infrared emitter  1 , an optional silica heat shield  7 , an infrared filter  9  and a low bandgap photovoltaic cell receiver  11 . The power band of the emitter  1  is matched with the energy conversion band of the TPV cells of the receiver  11 . The heat source  3  heats the infrared emitter  1 , which in turn emits infrared radiation. Low bandgap cells of the receiver  11  collect infrared radiation of a particular wavelength and convert the collected infrared radiation to electric power. 
     While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims.