The present invention relates to thermophotovoltaic energy conversion and, in particular, to a high temperature spectrally selective thermal emitter that can improve the thermodynamic efficiency of thermophotovoltaic energy conversion systems.
Thermophotovoltaic (TPV) energy conversion was first identified as a promising technology for converting waste heat into electricity in the 1960s. Since then, the potential of combustion-TPV systems to act as compact, portable power sources with energy densities nearly 10 times that of rechargeable batteries that are critical for a broad range of military and commercial applications has been demonstrated. See L. M. Fraas et al., Semiconductor Science and Technology 18, S247 (2003); and W. R. Chan et al., Proceedings of the National Academy of Sciences 110, 5309 (2013). TPV systems convert thermal radiation emitted from a high temperature source (the emitter) into electricity by means of a photovoltaic (PV) diode. If a TPV system is treated as a heat engine with hot (TBB) and cold sides (TPV), the theoretical thermodynamic (Carnot) efficiency limit can be calculated as ηCarnot=[TBB−TPV]/TBB. For TBB=1300 K, TPV=300 K, ηCarnot=0.77. In practice, the efficiencies of TPV systems have been fundamentally limited to ˜15% by the mismatch between the blackbody spectrum of the heated emitter and the external quantum efficiency (EQE) of the PV material. Other system considerations have reduced demonstrated efficiencies of full combustion-TPV systems to ·2.5%. Thus, a significant amount of work over the past 30 years has focused on improving the optical-to-electrical conversion efficiency by recycling out-of-band photons, using multiple bandgap cells, modifying the emissivity of an object away from the typical blackbody, or a combination of these techniques. See T. J. Coutts and James S. Ward, IEEE Transactions on Electron Devices 46, 2145 (1999); L. D. Woolf, Solar Cells 19, 19 (1986); R. A. Lowe et al., Applied Physics Letters 64, 3551 (1994); I. Celanovic et al., Applied Physics Letters 92, 193101 (2008); Y. Avitzour et al., Physical Review B 79, 045131 (2009); and Y. Xiang Yeng et al., Optics Express 21, A1035 (2013).
A selective emitter emits thermal radiation in a much narrower spectral range than a blackbody at the same temperature. Numerous geometries for modifying the emission spectrum have been studied, including metal (such as tungsten) photonic crystals, inverse opals, and metal-dielectric-metal (MDM) metasurfaces. See I. Celanovic et al., Applied Physics Letters 92, 193101 (2008); Y. Avitzour et al., Physical Review B 79, 045131 (2009); H. Sai et al., Applied Physics Letters 82, 1685 (2003); K. A. Arpin et al., Nature Communications 4 (2013); X. Liu et al., Physical Review Letters 107, 045901 (2011); and C. Wu et al., Journal of Optics 14, 024005 (2012). While the first two groups have shown promise regarding emissivity and survivability at operating temperatures, questions remain about the ability to scale these geometries beyond laboratory demonstrations. MDM metasurfaces, on the other hand, can easily be fabricated by standard foundry lithography techniques while exhibiting extremely tailorable emission spectra that can be made angle-independent when the layer thicknesses are significantly sub-wavelength. See Y. Avitzour et al., Physical Review B 79, 045131 (2009). However, the MDM metasurface geometry has been limited by delamination of the multilayer stack at high temperature due to differences in the coefficient of thermal expansion (CTE) generating interfacial stresses.
The present invention is directed to a spectrally selective thermal emitter, comprising an optically thick metallic backplane, a sub-wavelength dielectric layer deposited on the metallic backplane, and an array of metallic resonator elements having subwavelength periodicity deposited on the dielectric layer, wherein the metallic backplane, dielectric layer, and array of metallic resonator elements have similar coefficients of thermal expansion up to a high temperature and wherein the thermal emitter provides enhanced absorption of incident light at a resonance wavelength. The high temperature can be greater than 900 K, and preferably greater than 1300 K. For example, for an operating temperature above 1300 K, the metallic backplane and the array of metallic resonator elements can comprise platinum and the dielectric layer can comprise alumina. The resonator elements be any shape that is symmetric in the x and y directions, such as a cross, circle, ellipse, square, or rectangle. For a resonance wavelength in the infrared (e.g., 1.5 μm), the periodicity of the array of metallic resonator elements can typically be less than 600 nm, the thickness of the dielectric layer can be less than 100 nm, and the thickness of the metallic backplane can be greater than 100 nm. The metallic backplane can be deposited on a substrate, such as sapphire or alumina, having a similar CTE. The thermal emitter can further comprise a transparent encapsulant, such as alumina, deposited on the array of metallic resonator elements.
A TPV system can further comprise a thermophotovoltaic material to absorb the spectrally selective emission of the thermal emitter when heated to the high temperature and convert the absorbed emission into electricity by means of a photovoltaic diode. Preferably the spectrally selective emission is well matched with the most efficient conversion characteristics of the photovoltaic diode. For example, the thermophotovoltaic material can comprise InGaAs or InGaAsSb.
As an example, a spectrally-selective emitter based on a cross-over-a-backplane metasurface design was demonstrated which can survive temperature cycling at 1300 K and can demonstrate ηTPV>0.32, ηspec>0.40, and Pout>1.8 W/cm2 when coupled to a 0.6 eV InGaAs TPV cell at 1300 K. An Al2O3 encapsulation layer stabilized the cross-on-a-backplane geometry when raised to 1300 K. Because of its geometry and heterogeneous structure the invention can easily be scaled using nanoimprint or stepper lithography in order to cover large surfaces in a cost-effective manner, making it a viable candidate for future commercial TPV systems.
The detailed description will refer to the following drawings, wherein like elements are referred to by like numbers.
A metasurface comprises an array of two-dimensional (2D) metallic resonator elements with subwavelength periodicity. Despite having negligible thicknesses as compared to the incident wavelength, metasurfaces are characterized by the ability to strongly manipulate both the amplitude and phase of incident light near (plasmonic) resonances of the unit cell constituents. By itself, a metasurface can only control the phase in a limited range, from 0 to π (radians), due to the Lorentz-like polarizabilities of the resonant elements. Therefore, for full control of the phase space, an MDM metasurface places the array of metal nanostructures in dose proximity to a metal backplane, only separated by an optically thin dielectric spacer layer. The MDM metasurface couples to both the electric and magnetic components of incident electromagnetic radiation and enables the reflectance to be minimized at a certain frequency by impedance matching to free space.
According to the present invention, the problem of thermal delamination of an MDM metasurface can be mitigated by properly choosing the metals and dielectrics to be non-reacting and have similar CTE up to high temperature (>1300 K), thereby providing a robust, scalable metamaterial selective emitter. As an example of the invention, below is described the modeling, fabrication, and characterization of an MDM metasurface with a dielectrically symmetric geometry comprised of a platinum cross above a platinum backplane, an alumina spacer layer and alumina encapsulation on a sapphire substrate that can survive repeated temperature cycling to 1300 K. With this geometry, the model predicts at least 32% energy conversion efficiency, 40% spectral efficiency, and 1.8 W/cm2 of output power when coupled with a 0.6 eV strain-relaxed InGaAs PV material. See S. L. Murray et al., Semicond. Sci. Technology 18, S202 (2003); and J. G. Cederberg et al., J. Crystal Growth 310, 3453 (2008).
An exemplary emitter design is shown in
Other MDM materials can also be used.
A fabrication procedure for the exemplary thermal emitter comprising a platinum-alumina-platinum metasurface is shown in
The unencapsulated (
To test the multilayer MDM structure's robustness to high-temperature thermal cycling, the encapsulated samples were annealed in an argon atmosphere at 1300 K, in two, five, and five minute increments. After each annealing cycle, the emitter arrays were characterized with the FTIR spectrometer and an optical microscope.
For comparison, the same data are plotted for the unencapsulated structure in
Using the measured absorption spectra to represent the emissivity (εemit(ω)=1−R(ω)) of the metasurface, the behavior of the emitter in a TPV system was modeled and the TPV cell efficiency ηTPV and the generated power Pout were calculated, as shown in
where VOC is the diode's open circuit voltage, ISC is the diode's short circuit current, and FF is the fill factor, which are defined below. Since the emitter is at Temit=1300 K and the PV diode is at TPV=300 K, the amount of power radiated to the TPV cell, Prad, can be expressed as:
where c is the speed of light, k is the Boltzmann constant, is the reduced Planck constant, ω is the angular frequency, and the negligible radiation path from the PV cell to the emitter is ignored because Temit>>TPV and angle and polarization-independent emission is assumed. The integrand of Eq. 2 with ε=1, assuming a perfect blackbody, is drawn as the dashed line labeled “Blackbody spectrum” in
The amount of power generated by the PV cell (Pout) is proportional to the number of electron-hole pairs generated and thus is also proportional to the number of emitted, above-bandgap photons, nemit (as opposed to the emitted power density) which can be written as
The percentage of incident photons converted to electron-hole pairs is known as the external quantum efficiency (EQE) of the TPV material and is plotted as the solid line labeled “InGaAs EQE” against the left vertical axis of
The post-thermal cycling emissivity of all twenty five arrays was characterized and the highest ηTPVPout was found to corresponded to w=275 nm, l=250 nm, p=550 nm when paired with the 0.6 eV GaAs TPV material, generating 1.8 W/cm2 with ηTPV=0.32 and ηspec=0.40. The selective emitter of the present invention succeeds by significantly suppressing the emission of below-bandgap photons and having the peak of the emissivity align with the peak of the TPV EQE. The poor performance of a TPV system without a selective emitter can be seen in
Additional gains can be achieved by using a TPV material with lower band gap than the 0.6 eV material used in this example. The metrics of the emitter-TPV cell system using four different TPV materials can be seen in Table 1. For each emitter at both temperatures, the measured emission spectra for each of the 25 arrays was input into the model to maximize ηTPV. Because the exemplary emitter was not designed to overlap with the EQEs of these materials, it is possible that the optimal efficiencies and output powers are higher than what is shown in this table. The system at 1500 K was also evaluated to illustrate the potential benefits of higher temperature operation. The quaternary, 0.52 eV InGaAsSb material outperforms the other three materials due to its low band gap and high EQE (>95%). Further system modifications, such as a dielectric coating that highly reflects below-band gap photons, can further improve the efficiencies. See Y. Xiang Yeng et al., Optics Express 21, A1035 (2013).
See C. S. Murray et al., “Growth, Processing and Characterization of 0.55-eV n/p/n Monolithic Interconnected Modules,” Conference Record of the 28th Photovoltaic Specialists Conference (2000), 1238; S. Wojtczuk, “Comparison of 0.55eV InGaAs single-junction vs. multi-junction TPV technology”, in Thermophotovoltaic Generation of Electricity: TPV3, AIP Conf. Proc. 401, 205 (1997); and M. W. Dashiell et al., IEEE Transactions on Electron Devices 53, 2879 (2006).
The present invention has been described as a high temperature spectrally selective thermal emitter. It will be understood that the above description is merely illustrative of the applications of the principles of the present invention, the scope of which is to be determined by the claims viewed in light of the specification. Other variants and modifications of the invention will be apparent to those of skill in the art.
This application claims the benefit of U.S. Provisional Application No. 61/991,747, filed May 12, 2014, which is incorporated herein by reference.
This invention was made with Government support under contract no. DE-AC04-94AL85000 awarded by the U.S. Department of Energy to Sandia Corporation. The Government has certain rights in the invention.
Number | Date | Country | |
---|---|---|---|
61991747 | May 2014 | US |