SEMICONDUCTOR-BASED SELECTIVE EMITTER FOR THERMOPHOTOVOLTAIC ENERGY CONVERSION AND METHOD FOR FABRICATING THE SAME
20230010741 · 2023-01-12
Assignee
Inventors
Cpc classification
H01L31/056
ELECTRICITY
H01L31/02168
ELECTRICITY
H01L31/028
ELECTRICITY
International classification
H01L31/028
ELECTRICITY
H01L31/056
ELECTRICITY
Abstract
A selective emitter for thermophotovoltaic energy conversion and method for fabricating the same is disclosed. The selective emitter includes a germanium wafer, and a reflective layer deposited on a first side of the germanium wafer. The reflective layer includes tungsten. The selective emitter also includes an anti-reflective layer deposited on a second side of the germanium wafer opposite the first side. The anti-reflective layer includes Si.sub.3N.sub.4. The method for fabricating a selective emitter for thermophotovoltaic energy conversion includes deposing a reflective layer on a first side of a germanium wafer, and deposing an anti-reflective layer on a second side of the germanium wafer, the first side being opposite the second side. The germanium wafer may be undoped. The reflective layer may be sputtered onto the germanium wafer. The anti-reflective layer may be deposited on the germanium wafer using plasma-enhanced chemical vapor deposition.
Claims
1. A selective emitter for thermophotovoltaic energy conversion, comprising: a germanium wafer, the germanium wafer being undoped and less than 500 μm thick; a reflective layer deposed on a first side of the germanium wafer, the reflective layer composed of tungsten and being at least 200 nm thick; and an anti-reflective layer deposed on a second side of the germanium wafer opposite the first side, the anti-reflective layer comprising Si.sub.3N.sub.4 and being at least 150 nm thick.
2. The selective emitter of claim 1, wherein the tungsten of the reflective layer is sputtered onto the germanium wafer.
3. The selective emitter of claim 1, wherein the Si.sub.3N.sub.4 of the anti-reflective layer is deposited on the germanium wafer using plasma-enhanced chemical vapor deposition.
4. A selective emitter for thermophotovoltaic energy conversion, comprising: a germanium wafer; a reflective layer deposited on a first side of the germanium wafer, the reflective layer comprising tungsten; and an anti-reflective layer deposited on a second side of the germanium wafer opposite the first side, the anti-reflective layer comprising Si.sub.3N.sub.4.
5. The selective emitter of claim 4, wherein the tungsten of the reflective layer is sputtered onto the germanium wafer.
6. The selective emitter of claim 4, wherein the Si.sub.3N.sub.4 of the anti-reflective layer is deposited on the germanium wafer using plasma-enhanced chemical vapor deposition.
7. The selective emitter of claim 4, wherein the germanium wafer is undoped.
8. The selective emitter of claim 4, wherein the germanium wafer is less than 500 μm thick.
9. The selective emitter of claim 4, wherein the reflective layer is at least 200 nm thick.
10. The selective emitter of claim 4, wherein the anti-reflective layer is at least 150 nm thick.
11. A method for fabricating a selective emitter for thermophotovoltaic energy conversion, comprising: deposing a reflective layer on a first side of a germanium wafer; and deposing an anti-reflective layer on a second side of the germanium wafer, the first side being opposite the second side.
12. The method of claim 11, wherein the germanium wafer is undoped.
13. The method of claim 11, wherein the germanium wafer is less than 500 μm thick.
14. The method of claim 11, wherein the reflective layer comprises tungsten.
15. The method of claim 11, wherein the reflective layer is at least 200 nm thick.
16. The method of claim 11, wherein the anti-reflective layer comprises Si.sub.3N.sub.4.
17. The method of claim 11, wherein the anti-reflective layer is at least 150 nm thick.
18. The method of claim 11, wherein deposing the reflective layer comprises sputtering the reflective layer onto the germanium wafer.
19. The method of claim 11, wherein the anti-reflective layer is deposed on the germanium wafer using plasma-enhanced chemical vapor deposition.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The disclosure will hereinafter be described in conjunction with the appended drawings, where like designations denote like elements, and:
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
DETAILED DESCRIPTION
[0024] This disclosure, its aspects and implementations, are not limited to the specific material types, components, methods, or other examples disclosed herein. Many additional material types, components, methods, and procedures known in the art are contemplated for use with particular implementations from this disclosure. Accordingly, for example, although particular implementations are disclosed, such implementations and implementing components may comprise any components, models, types, materials, versions, quantities, and/or the like as is known in the art for such systems and implementing components, consistent with the intended operation.
[0025] The word “exemplary,” “example,” or various forms thereof are used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” or as an “example” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Furthermore, examples are provided solely for purposes of clarity and understanding and are not meant to limit or restrict the disclosed subject matter or relevant portions of this disclosure in any manner. It is to be appreciated that a myriad of additional or alternate examples of varying scope could have been presented, but have been omitted for purposes of brevity.
[0026] While this disclosure includes a number of embodiments in many different forms, there is shown in the drawings and will herein be described in detail particular embodiments with the understanding that the present disclosure is to be considered as an exemplification of the principles of the disclosed methods and systems, and is not intended to limit the broad aspect of the disclosed concepts to the embodiments illustrated.
[0027] Thermophotovoltaic (TPV) devices convert thermal radiation from a high-temperature emitter to electricity via a narrow-bandgap photovoltaic (PV) cell. Since the emitter can be heated by any kind of heat source (e.g., combustible fuel, solar energy, waste heat, etc.), TPV technology has a wide range of applications. The theoretical efficiency of the TPV system has the Carnot limit. However, due to the mismatch between the thermal radiation spectrum of the emitter and the absorption spectrum of the cell, conventional TPV systems have low electric power output and poor efficiency. To overcome this problem, much work has been carried out on spectrally selective emitters that emit photons with energy just above the bandgap of the PV cell. An ideal selective emitter should have an emissivity of one over a certain bandwidth just above the bandgap of the PV cell, and an emissivity of zero elsewhere. Spectrally selective PV cells have been shown to enhance TPV efficiency exceeding 30% at 1455 K by recycling the unused photons to the emitter.
[0028] Previous efforts have shown that the spectrally selective emitters can be achieved and tuned using photonic crystals and metamaterial structures. However, the complex geometries and the difficult fabrication processes have prevented any significant low-cost fabrication. Furthermore, the high temperature stability of these nanostructures after long-term practical operation is another big concern. Difficult fabrication and limited operational lifespan make these conventional spectrally selective emitters too expensive for practical use.
[0029] Spectrally selective emitters can also be realized by multilayer structures based on the anti-reflection effect or cavity resonance, which are potentially much easier to fabricate on a large scale. Based on Kirchhoff's law of thermal radiation that absorptivity equals emissivity at every wavelength in thermal equilibrium, spectrally selective absorbers may also serve as spectrally selective emitters. A previous effort led to a multilayer selective solar absorber which had good spectral selectivity behavior and high temperature stability. However, the cutoff wavelength (i.e., the transition between the high emittance above the bandgap and the low emittance below the bandgap) was not sharp, still resulting in undesirable photons below the bandgap.
[0030] Contemplated herein is a semiconductor-based selective emitter for thermophotovoltaic energy conversion (hereinafter “TPV emitter”, “selective emitter”, or “emitter”). While most conventional semiconductor-based selective absorber/emitters have been built around silicon, the TPV emitter contemplated herein makes use of germanium, which has a lower energy bandgap (0.67 eV) and is well adapted for TPV application. Specifically, the contemplated TPV emitter is a germanium (Ge) semiconductor sandwiched between a reflective layer and an anti-reflective layer. In some embodiments, the contemplated emitter exhibits a nearly two-fold increase in TPV efficiency compared to a black emitter control.
[0031] The contemplated semiconductor-based selective emitter is well adapted for TPV applications since the bandgap edge provides a sharp cutoff wavelength and nearly zero sub-bandgap emission. This leads to a much more efficient device, eliminating undesirable photon emission below the bandgap and substantially limiting photon emission to the narrow bandgap absorption range of a PV cell.
[0032]
[0033] The reflective layer 108 (or rear layer) is used to ensure the opaqueness of the structure with high reflectivity below the bandgap of Ge. According to various embodiments, the reflective layer 108 may be made of tungsten 112, which is well-adapted for acting as a reflector below the bandgap of Ge. The anti-reflective layer 110 (e.g., the PV-facing side of the emitter 100) is used to reduce in-band reflection and enhance absorption or emission. According to various embodiments, the anti-reflective layer 110 may be composed of Si.sub.3N.sub.4 114.
[0034] It should be noted that while much of the discussion below will be done in the context of a specific, non-limiting embodiment of the selective emitter 100 having a reflective layer 108 comprising tungsten 112 and an anti-reflective layer 110 comprising Si.sub.3N.sub.4 114, other embodiments of the contemplated emitter 100 may employ other materials suitable for the anticipated operating temperatures. For example, in one embodiment, the reflective layer 108 hay comprise nickel. In other embodiments, the anti-reflective layer 110 may comprise other refractory oxides such as Al.sub.2O.sub.3 and HfO.sub.2.
[0035] According to various embodiments, the germanium wafer 102 may be undoped, which further simplifies the fabrication process. In other embodiments, the semi-conductor wafer of the contemplated emitter 100 may be doped. In some embodiments, the Ge wafer 102 may be 500 μm thick. In other embodiments, the Ge wafer 102 may be less than 500 μm thick. In still other embodiments, the Ge wafer 102 may be more than 500 μm thick.
[0036] In some embodiments, the reflective layer 108 may be 200 nm thick. In other embodiments, the reflective layer 108 may be less than 200 nm thick. In still other embodiments, the reflective layer 108 may be more than 200 nm thick. Furthermore, in some embodiments, the anti-reflective layer 110 may be 150 nm thick. In other embodiments, the anti-reflective layer 110 may be less than 150 nm thick. In still other embodiments, the anti-reflective layer 110 may be more than 150 nm thick.
[0037] The following discussion will be done in the context of a specific embodiment of the contemplated selective emitter 100 having a germanium wafer 102 that is 500 μm thick, a reflective layer 108 that is 200 nm thick and made of tungsten 112, and an anti-reflective layer 110 that is 150 nm thick and made of Si.sub.3N.sub.4 114.
[0038]
[0039] First, a 200-nm reflective layer 108 of tungsten 112 is sputtered (e.g., with a Lesker PVD75 Sputter Coater, etc.) on the first side 104 of the Ge wafer 102 at a rate of 1 ks, under a vacuum pressure of 1×10.sup.−6 Torr. See ‘circle 1’. Next, a 150-nm anti-reflective layer 110 of Si.sub.3N.sub.4 114 is deposited on the second side 106 of the Ge wafer 102 using a plasma-enhanced chemical vapor deposition (PECVD) method (e.g., with an Oxford Plasmalab100, etc.) at a rate of 290 Å/min under the temperature of 300° C. See ‘circle 2’. According to a specific embodiment, the root-mean-square surface roughness of the fabricated sample may be around 0.9 nm, as measured by an atomic force microscope. Those skilled in the art will recognize that the contemplated method for fabrication may be adapted for use in conjunction with other thin-film fabrication techniques known in the art.
[0040]
[0041] According to Kirchhoff's law, the spectral directional emittance is equal to the spectral directional absorptance as 1−R′.sub.λ from energy balance with zero transmittance due to the opaque reflective layer 108 of tungsten 112. As shown in
[0042] It should be noted that the spectral directional reflectivity and transmissivity shown in
R′.sub.λ=ρ.sub.a+ρ.sub.sρ.sub.a.sup.2ρ.sup.2/(1−ρ.sub.sρ.sub.bτ.sup.2)
where τ=exp (−4πκ.sub.sd.sub.s/λ cos θ.sub.s) is the internal transmissivity of the Ge wafer 102 with extinction coefficient κ.sub.s, thickness d.sub.s, free-space wavelength λ, and refraction angle θ.sub.s inside the Ge substrate calculated from incident angle θ.sub.1 with Snell's law.
[0043]
[0044]
[0045] According to various embodiments, the Brewster angle is about 75° for the undoped Ge wafer 102 used in the emitter 100, calculated by θ=tan.sup.−1(n.sub.2/n.sub.1), where n.sub.2 and n.sub.1 represent the refractive index of Ge and air, respectively. The reflectance at TM waves decreases with the incident angle from 0° to 75°, which explains the trend of emittance shown in
[0046]
[0047] To evaluate the spectral selectivity of the contemplated emitter 100, the spectrally averaged emittance was calculated for above-bandgap spectrum
where λ.sub.ge=1.85 μm is the bandgap wavelength of Ge,
is the blackbody spectral emissive power with Plank's constant h, the speed of light in vacuum co, Boltzmann constant k.sub.B, and absolute temperature T.
[0048]
[0049] According to various embodiments, the spectral efficiency can be defined as the percentage of the photons from the emitter 100 absorbed by the PV cell:
ƒ.sub.spectral=∫.sub.0.sup.λ.sup.
where λ.sub.gc is the bandgap wavelength of the PV cell,
is the spectral net radiative heat flux between the emitter and the cell with a view factor of 1, and the subscript e(c) represents the emitter (cell). ε.sub.e,λ is the spectral emissivity of the emitter and ε.sub.c,λ is the spectral emittance (or absorptance) of the PV cell, both of which are assumed to be diffuse. T.sub.e and T.sub.c are respectively the emitter temperature and the cell temperature.
[0050]
[0051] It should be noted that the theoretical Ge-based selective emitter 100 has higher spectral efficiency than the fabricated embodiment due to its lower sub-bandgap emittance. The contemplated Ge-based selective emitter 100 has higher spectral efficiency than a black emitter. At a temperature of 1200 K, the spectral efficiency of the theoretical Ge-based selective emitter 100 can achieve 34.0%, while that of a black emitter is only 12.0%.
[0052] To discuss the performance of the contemplated Ge-based selective emitter, the TPV efficiency ƒ can be calculated by
ƒ=P.sub.e/q.sub.in
where P.sub.e=J.sub.scV.sub.ocFF is the maximum output electric power density produced by the PV cell.
is the short-circuit current density. Note that E.sub.g is the bandgap of the PV cell, e is an elementary charge, and ƒ.sub.IQE,λ is the internal quantum efficiency of the PV cell. V.sub.oc=(k.sub.BT.sub.c/e)ln(J.sub.sc/J.sub.0+1) is the open-circuit voltage (V), in which J.sub.0 is the dark current calculated by J.sub.0=e[n.sub.i.sup.2D.sub.h/(L.sub.hN.sub.D)+n.sub.i.sup.2D.sub.e/(L.sub.eN.sub.A)]. n.sub.i is the intrinsic carrier concentration of the semiconductor, N.sub.D and N.sub.A are respectively the donor concentration and acceptor concentration, D.sub.h and D.sub.e are respectively the hole diffusion coefficient and electron diffusion coefficient, and L.sub.h and L.sub.e are respectively the hole and electron diffusion length. FF is the filling factor calculated by FF=(1−1/y)(1−ln y/y), in which y=ln(J.sub.sc/J.sub.0). g.sub.in=∫.sub.0.sup.∞q.sub.e-c,λdλ is the net radiative heat flux between the emitter 100 and the cell with the same area.
[0053]
[0054] With the fabricated Ge-based selective emitter 100 sample, the TPV efficiency was improved ranging from 0.8% to 8.2%, which is due to the good spectral selectivity of the Ge-based selective emitter 100 with low emittance below the bandgap, thus reducing the net radiative heat flux with almost the same power output.
[0055] With a theoretical Ge-based selective emitter 100, the TPV efficiency could be further improved, ranging from 1.2% to 11.2%. This is due to its lower sub-bandgap emittance, thus further reducing the net radiative heat flux. Note that these three emitters produce similar P.sub.e below 1000 K.
[0056] As the emitter 100 temperature increases, the black emitter will surpass the contemplated Ge-based selective emitter 100. P.sub.e depends on the net radiative heat flux above the bandgap of the cell. At low temperatures, the emissive power from the contemplated emitter 100 at short wavelengths (i.e., above the bandgap) is low, which causes similar power from these three emitter 100s.
[0057] As the temperature increases, the thermal emission spectrum shifts to shorter wavelengths. The black emitter has the highest emittance, resulting in the highest net radiative heat flux above the bandgap, thus producing the highest output power. As shown, this specific, fabricated Ge-based selective emitter 100 embodiment has the lowest emittance, resulting in the lowest net radiative heat flux above the bandgap and therefore producing the lowest power. In particular, at an emitter 100 temperature of 1200 K, the contemplated Ge-based selective emitter 100 can achieve a TPV efficiency of 11.2%, and an output power of 2.3 kW/m.sup.2, according to various embodiments.
[0058] Where the above examples, embodiments and implementations reference examples, it should be understood by those of ordinary skill in the art that other materials and fabrication methods could be intermixed or substituted with those provided. In places where the description above refers to particular embodiments of a selective emitter for thermophotovoltaic energy conversion and method for fabricating the same, it should be readily apparent that a number of modifications may be made without departing from the spirit thereof and that these embodiments and implementations may be applied to other selective emitters and fabrication methods as well. Accordingly, the disclosed subject matter is intended to embrace all such alterations, modifications and variations that fall within the spirit and scope of the disclosure and the knowledge of one of ordinary skill in the art.