Antireflection coated refractory metal matched emitters for...

Details Antireflection coated refractory metal matched emitters for... Antireflection coated refractory metal matched emitters for...

1999-09-28

2001-01-23

Diamond, Alan (Department: 1753)

Batteries: thermoelectric and photoelectric

Photoelectric

Cells

C136S262000, C428S689000, C428S690000, C428S913000, C428S446000, C428S448000, C428S457000, C428S469000, C428S472000

Reexamination Certificate

active

06177628

ABSTRACT:

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.


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