Spectrally selective semiconductor dielectric photonic solar thermal absorber
10215447 ยท 2019-02-26
Assignee
Inventors
Cpc classification
F24S70/225
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F24S10/25
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02E10/44
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E10/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F24S70/30
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
Abstract
A solar thermal absorber including a spectrally selective filter comprising a stack of dielectric layers and one or more semiconductor absorber layers. The dielectric layers are transparent to infrared radiation and have a refractive index contrast, and the semiconductor absorber layers have a band gap, such that the semiconductor absorber layers absorb at least a portion of the solar spectrum and the stack reflects infrared radiation.
Claims
1. A solar thermal absorber, comprising: a stack of dielectric layers and one or more semiconductor absorber layers on a metal reflector, wherein: the dielectric layers are transparent to infrared radiation and have a refractive index contrast, and the semiconductor absorber layers comprise amorphous silicon or amorphous germanium and have a band gap, such that the semiconductor absorber layers absorb visible light and the stack reflects infrared radiation so as to suppress emission of black-body radiation.
2. The absorber of claim 1, wherein the layers are sputtered on the metal reflector.
3. The absorber of claim 2, wherein the metal reflector comprises Ag sandwiched between Cr layers.
4. The absorber of claim 1, wherein the dielectric layers comprise one or more ZnS layers and one or more CaF.sub.2 layers.
5. The absorber of claim 1, wherein: the dielectric layers comprise a ZnS layer, a first CaF.sub.2 layer, a second CaF.sub.2 layer, a third CaF.sub.2 layer, and a fourth CaF.sub.2 layer; the semiconductor absorber layers comprise a first semiconductor absorber layer, a second semiconductor absorber layer, and a third semiconductor absorber layer; the first semiconductor absorber layer is on the metal reflector; the first CaF.sub.2 layer is on the first semiconductor absorber layer; the second semiconductor absorber layer is on the first CaF.sub.2 layer; the second CaF.sub.2 layer is on the second semiconductor absorber layer; the third semiconductor absorber layer is on the second CaF.sub.2 layer; the third CaF.sub.2 layer is on the third semiconductor absorber layer; the ZnS layer is on the third CaF.sub.2 layer; and the fourth CaF.sub.2 layer is on the ZnS layer.
6. The absorber of claim 5, wherein: the first semiconductor absorber layer has a thickness of 20-80 nm, the second semiconductor absorber layer has a thickness of 20-100 nm, the third semiconductor absorber layer has a thickness of 1-70 nm, the first CaF.sub.2 layer has a thickness of 50-300 nm, the second and third CaF.sub.2 layers each have thicknesses between 10-70 nm, the fourth CaF.sub.2 layer has a thickness of 50-100 nm, and the ZnS layer has a thickness of 1-50 nm.
7. The absorber of claim 5, wherein the metal reflector is a silver reflector sandwiched between Cr layers.
8. The absorber of claim 1, wherein: the dielectric layers comprise a first CaF.sub.2 layer, a second CaF.sub.2 layer, a third CaF.sub.2 layer, a fourth CaF.sub.2 layer, a fifth CaF.sub.2 layer, and a ZnS layer; the semiconductor absorber layers are amorphous germanium layers comprising a first semiconductor absorber layer, a second semiconductor absorber layer, a third semiconductor absorber layer, and a fourth semiconductor absorber layer; the first semiconductor absorber layer is on or above metal layers comprising a silver layer sandwiched between chromium layers; the first CaF.sub.2 layer is on the first semiconductor absorber layer; the second semiconductor absorber layer is on the first CaF.sub.2 layer; the second CaF.sub.2 layer is on the second semiconductor absorber layer; the third semiconductor absorber layer is on the second CaF.sub.2 layer; the third CaF.sub.2 layer is on the third semiconductor absorber layer; the fourth semiconductor absorber layer is on the third CaF.sub.2 layer; the fourth CaF.sub.2 layer is on the fourth semiconductor absorber layer; the ZnS layer is on the fourth CaF.sub.2 layer; and the fifth CaF.sub.2 layer is on the ZnS layer.
9. A thermal absorber, comprising: a spectrally selective filter comprising a stack of dielectric layers transparent to infrared radiation and one or more semiconductor absorber layers, wherein: the filter receives electromagnetic radiation, the electromagnetic radiation comprising in-band electromagnetic radiation having wavelengths less than a critical wavelength and out-of-band electromagnetic radiation having wavelengths at or longer than the critical wavelength, the critical wavelength defined such that black body radiation, having wavelengths at or longer than the critical wavelength, is emitted from the semiconductor absorber layers with an intensity that exceeds an intensity of the out-of-band electromagnetic radiation absorbed by the semiconductor absorber layers; and the dielectric layers and the semiconductor absorber layers have a refractive index contrast, the semiconductor absorber layers have a band gap, and the dielectric layers have a transparency such that: absorptance of the stack decreases by at least 80% as wavelength of the electromagnetic radiation increases over a wavelength range of 500 nanometers centered on a boundary between an absorptance pass band and an absorptance stop band of the filter, reflectance of the stack increases by at least 80% as wavelength of the electromagnetic radiation increases over a wavelength range of 100 nanometers centered on a boundary between a reflectance pass band and an reflectance stop band of the filter, and the boundaries are no more than 500 nm less than the critical wavelength, thereby suppressing emission of the black-body radiation and allowing the semiconductor absorber layers to generate thermal energy by increasing in temperature in response to absorbing the in-band electromagnetic radiation.
10. The absorber of claim 9, wherein the in-band electromagnetic radiation comprises wavelengths of the solar spectrum and the out-of-band electromagnetic radiation includes infrared wavelengths.
11. The absorber of claim 9, wherein the critical wavelength is at least 1.6 micrometers.
12. The absorber of claim 9, wherein the stack comprises layers alternating between one of the dielectric layers and one of the semiconductor absorbing layers.
13. The absorber of claim 9, wherein the dielectric layers comprise one or more ZnS layers and one or more CaF.sub.2 layers.
14. The absorber of claim 9, wherein the dielectric layers comprise one or more first dielectric layers comprising a first dielectric material and one or more second dielectric layers comprising a second dielectric material, the absorber further comprising: a first region including one of the first dielectric layers between two of the second dielectric layers, and a second region including layers alternating between one of the second dielectric layers and one of the semiconductor absorbing layers, a metal reflector positioned such that the second region is between the first region and the metal reflector, and wherein the electromagnetic radiation is incident on the first region.
15. The absorber of claim 14, wherein: the first dielectric layer comprises at least one dielectric selected from ZnS and ZnSe, the second dielectric layer comprises at least one dielectric selected from CaF.sub.2 and KBr, and the semiconductor absorber layer comprises at least one semiconductor selected from amorphous silicon, amorphous germanium, and GaSb.
16. The absorber of claim 14, wherein: the semiconductor absorber layer closest to the metal reflector and the semiconductor absorber layer closest to the first region are both thinner than the remaining semiconductor absorber layers, and the dielectric layer closest to the metal reflector, and the dielectric layer closest to a top surface of the first region on which the electromagnetic radiation is incident, are both thicker than the remaining dielectric layers.
17. The absorber of claim 9, wherein the filter is a Fabry-Perot filter or a photonic bandgap filter.
18. A method of fabricating a thermal absorber, comprising: depositing a spectrally selective filter, including depositing a stack of dielectric layers and one or more semiconductor absorber layers on a metal reflector, wherein the dielectric layers comprise one or more ZnS layers and one or more CaF.sub.2 layers and the semiconductor absorber layers comprise amorphous silicon or germanium.
19. The method of claim 18, wherein the depositing comprises sputtering.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
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DETAILED DESCRIPTION OF THE INVENTION
(14) In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration a specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
(15) Technical Description
(16) As shown in
(17) The current state of the art employs metal-ceramic mixtures (cermets) or 2-D patterned metal-dielectric photonic crystals (MDPhCs) [1, 2]. Reference [7] describes a layered device where each layer is a metal (tungsten), a ceramic-metal mixture (cermets, WNiYSZ with two different compositions, where YSZ is Yttria-Stabilized Zirconia), or a ceramic (YSZ) (the device in [7] falls under the category of cermet selective surfaces). However, because metals are imperfect reflectors in the IR, these cermets and MDPhCs exhibit a rather gradual drop in absorptance as shown by the curves labelled [2] and [3] in
First Example
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Second Example (Using Amorphous Germanium)
(21) Considerable improvements are also made by using amorphous germanium instead of amorphous silicon, because amorphous germanium has an optical gap which is corresponds to a wavelength which is closer to the critical wavelength.
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Third Example
(24) In one or more embodiments, Cr layers can be added on both sides of/around the metal (e.g., Ag) layer.
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(28) Process Steps
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(30) Block 1200 represents the first, stage, designing the device structure. In one or more embodiments, the first stage comprises the computational simulation/optimization of a one-dimensional structure, e.g., wherein a needles method is used to optimize the relative order and thickness of each layer, and the transfer matrix method is used to calculate the total absorptance of the structure [6].
(31) The step can comprise selecting dielectric layers (comprising e.g., ZnS and CaF.sub.2) that are transparent to infrared radiation and have sufficient refractive index contrast, and selecting the semiconductor absorber layers (comprising e.g., amorphous silicon or germanium) having a band gap, such that the semiconductor absorber layers absorb at least a portion of the solar spectrum (including visible light) and the stack reflects infrared radiation. The semiconductor for the absorber layer can be selected such that its bandgap is close to the critical wavelength. For example, gallium antimonide (GaSb) would also work in theory. For IR transparent dielectrics, CaF.sub.2 is most likely irreplaceable. Potassium bromide (KBr) might work, but it is unstable in air. Zinc selenide (ZnSe) could replace ZnS.
(32) The step can comprise selecting a number (and material(s)) of the dielectric layers, one or more thicknesses of the dielectric layers, a number (and material(s)) of the semiconductor absorber layers, one or more thicknesses of the semiconductor absorber layers, refractive indices of the layers, and/or positioning of the semiconductor absorber layers and the dielectric layers relative to one another, such that: absorptance of the stack comprising the dielectric layers and the semiconductor absorber layers decreases by at least 80% as the wavelength of the incident electromagnetic radiation is increased over a wavelength range of at most 500 nanometers centered on an absorptance cut-off wavelength or boundary 704 between an absorptance pass band and absorptance stop band (see
(33) The filter can be designed so that at least some of the out-of-band wavelengths (having wavelengths at or longer than the critical wavelength) lie in the filter's stop band(s) and at least some of the in-band wavelengths (having the wavelengths shorter than the critical wavelength, e.g., visible wavelengths in a range of 390-700 nm) lie in the filter's pass band(s). For example, the filter can be a Fabry-Perot filter or a photonic bandgap filter. For example, the dielectric layers and semiconductor absorber layers can be dimensioned and structured to constructively phase-match reflection of the out-of-band electromagnetic radiation (having wavelengths greater than .sub.c) by the stack (so as to filter out and reflect the out-of-band electromagnetic radiation away from the semiconductor absorber layers).
(34) Versions of the device can comprise the following pattern: (1) region 1 (1 in
(35) The Cr does two things: 1) it is a sticky metal that helps bond the Ag to the Si substrate; and 2) it protects the Ag and the Ge from one another. Ag and Ge diffuse well within one another but do not diffuse well through Cr. Another material that might work would be Titanium (Ti), which is also kind of sticky, but Cr is better at reflecting IR light than Ti.
(36) The semiconductor absorber layer closest to the metal reflector 200a and/or the semiconductor absorber layer 200c closest to the first region can both be thinner than the remaining semiconductor absorber layers 200b, as illustrated in
(37) In one or more embodiments (e.g., as illustrated in
(38) In one or more further embodiments (e.g., as illustrated in
(39) Block 1202 represents the next stage, depositing the layers, which can comprise sputtering the materials. Due to limitations in availability, the initial prototypes incorporated SiO.sub.2 instead of CaF.sub.2, although one or more embodiments of the invention have successfully fabricated a device with CaF.sub.2. The deposition rates for Ag, aSi, SiO.sub.2 and ZnS are largely constant, so it is a straightforward matter to develop a sputtering schedule to achieve the desired profile. The dielectrics and semiconductors are sputtered using radio-frequency (RF) power and the metals are sputtered using direct current (DC). The CaF.sub.2 is sputtered at low power (50 Watts (W)) since the CaF.sub.2 target is fragile. The other materials are sputtered at powers ranging from 90 W to 150 W.
(40) Block 1204 represents the end result, a thermal absorber comprising a spectrally selective filter comprising a stack of dielectric layers and one or more semiconductor absorber layers.
(41) Advantages and Improvements
(42) Building off of modern photonics and developments in thin-film deposition, the semiconductor dielectric photonic solar thermal absorber according to one or more embodiments of the invention improves upon previous devices in at least two critical areas: 1) By incorporating IR-transparent dielectrics with sufficient refractive index contrast, such as ZnS and CaF.sub.2, the device can better absorb visible light while still reflecting the infra-red (this is critical, devices according to one or more embodiments show unprecedented low thermal emittance, meaning the devices can be used in systems with un-concentrated sunlight); and
(43) 2) using a direct optical-gap semiconductor, such as amorphous silicon, allows for a much steeper decrease in absorptance at the critical wavelength, as the absorption coefficient is of the form
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which drops sharply to zero near the band gap Eg (h is Planck's constant, c is speed of light, and is wavelength). However, results [7] have also achieved a sharp drop in absorptance without using a direct-gap semiconductor.
REFERENCES
(45) The following references are incorporated by reference herein. 1] F. Cao et al. A review of cermet-based spectrally selective solar absorbers. Energy & Environmental Science, 7(5):1615-1627, 2014. [2] Jeffrey B. Chou et al. Enabling ideal selective solar absorption with 2d metallic dielectric photonic crystals. Advanced Materials, 26(47):8041-8045, 2014. [3] Y. Yin et al. Direct current reactive sputtering CrCr.sub.2O.sub.3 cermet solar selective surfaces for solar hot water applications. Thin Solid Films, 517(5):1601-1606, 2009. [4] D. C. Booth et al. Stabilized CVD amorphous silicon for high-temperature photothermal solar-energy conversion. Solar Energy Materials, 2(1):107-124, 1979. [5] D. E. Ackley et al. Silicon films as selective absorbers for solar energy conversion. Applied Optics, 16 (11):2806-2809, 1977. [6] Alexander V. Tikhonravov et al. Application of the needle optimization technique to the design of optical coatings. Applied Optics, 35(28):5493-5508, 1996. [7] Cao, F., et al. Energy & Environmental Science 8(10): 3040-3048, 2015.
CONCLUSION
(46) This concludes the description of the preferred embodiment of the present invention. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.