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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Energy Res.</journal-id>
<journal-title>Frontiers in Energy Research</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Energy Res.</abbrev-journal-title>
<issn pub-type="epub">2296-598X</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="publisher-id">787237</article-id>
<article-id pub-id-type="doi">10.3389/fenrg.2021.787237</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Energy Research</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>An Ultra-High Temperature Stable Solar Absorber Using the ZrC-Based Cermets</article-title>
<alt-title alt-title-type="left-running-head">Wang et&#x20;al.</alt-title>
<alt-title alt-title-type="right-running-head">ZrC-Based Solar Absorber</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Wang</surname>
<given-names>Jian</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Wu</surname>
<given-names>Zuoxu</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Liu</surname>
<given-names>Yijie</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Hou</surname>
<given-names>Shuaihang</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Ren</surname>
<given-names>Zhikun</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Luo</surname>
<given-names>Yi</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Liu</surname>
<given-names>Xingjun</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Mao</surname>
<given-names>Jun</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1421093/overview"/>
</contrib>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Zhang</surname>
<given-names>Qian</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/724122/overview"/>
</contrib>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Cao</surname>
<given-names>Feng</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1214983/overview"/>
</contrib>
</contrib-group>
<aff id="aff1">
<label>
<sup>1</sup>
</label>School of Science, And Ministry of Industry and Information Technology Key Lab of Micro-Nano Optoelectronic Information System, Harbin Institute of Technology, <addr-line>Shenzhen</addr-line>, <country>China</country>
</aff>
<aff id="aff2">
<label>
<sup>2</sup>
</label>School of Materials Science and Engineering, And Institute of Materials Genome and Big Data, Harbin Institute of Technology, <addr-line>Shenzhen</addr-line>, <country>China</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/988977/overview">K. Sudhakar</ext-link>, Universiti Malaysia Pahang, Malaysia</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1118050/overview">Kumaran Kadirgama</ext-link>, Universiti Malaysia Pahang, Malaysia</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1510591/overview">Xiang-Hu Gao</ext-link>, Lanzhou Institute of Chemical Physics (CAS), China</p>
</fn>
<corresp id="c001">
<sup>&#x2a;</sup>Correspondence: Qian Zhang, <email>zhangqf@hit.edu.cn</email>; Feng Cao, <email>caofeng@hit.edu.cn</email>
</corresp>
<fn fn-type="other">
<p>This article was submitted to Solar Energy, a section of the journal Frontiers in Energy Research</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>03</day>
<month>11</month>
<year>2021</year>
</pub-date>
<pub-date pub-type="collection">
<year>2021</year>
</pub-date>
<volume>9</volume>
<elocation-id>787237</elocation-id>
<history>
<date date-type="received">
<day>30</day>
<month>09</month>
<year>2021</year>
</date>
<date date-type="accepted">
<day>20</day>
<month>10</month>
<year>2021</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2021 Wang, Wu, Liu, Hou, Ren, Luo, Liu, Mao, Zhang and Cao.</copyright-statement>
<copyright-year>2021</copyright-year>
<copyright-holder>Wang, Wu, Liu, Hou, Ren, Luo, Liu, Mao, Zhang and Cao</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these&#x20;terms.</p>
</license>
</permissions>
<abstract>
<p>Exploring the spectrally selective absorbers with high optical performance and excellent thermal stability is crucial to improve the conversion efficiency of solar energy to electricity in concentrated solar power (CSP) systems. However, there are limited reports on the selective solar absorbers utilized at 900<sup>o</sup>C or above. Herein, we developed a selective absorption coating based on the ultra-high temperature ceramic ZrC and the quasi-optical microcavity (QOM) optical structure, and experimentally achieved the absorber <italic>via</italic> depositing an all-ceramic multilayer films on a stainless steel substrate by magnetron sputtering. The prepared multi-layer selective absorber demonstrates an excellent high solar absorptance of &#x223c;0.964 due to the multi absorptance mechanisms in the QOM, and a relatively low thermal emittance of &#x223c;0.16 (82&#xb0;C). Moreover, the coating can survive at 900<sup>o</sup>C in vacuum for 100&#xa0;h with a superior spectral selectivity of 0.96/0.143 (82&#xb0;C) upon annealing, resulting from the introduction of ultra-high temperature ceramic ZrC in the QOM structure. Under the conditions of a stable operating temperature of 900&#xb0;C and a concentration ratio of 1,000 suns, the calculated ideal conversion efficiency using this absorber can reach around 68%, exceeding most solar selective absorbers in previous reports.</p>
</abstract>
<kwd-group>
<kwd>solar selective absorption coatings1</kwd>
<kwd>ultra-high temperature ceramics2</kwd>
<kwd>ZrC-Al<sub>2</sub>O<sub>3</sub> composite3</kwd>
<kwd>thermal stability4</kwd>
<kwd>total efficiency5</kwd>
</kwd-group>
<contract-num rid="cn001">51871081 51971081</contract-num>
<contract-num rid="cn003">GXWD20201230155427003-20200801190929005 JCYJ20200109113418655</contract-num>
<contract-num rid="cn004">KQTD20200820113045081</contract-num>
<contract-sponsor id="cn001">National Outstanding Youth Science Fund Project of National Natural Science Foundation of China<named-content content-type="fundref-id">10.13039/100014717</named-content>
</contract-sponsor>
<contract-sponsor id="cn002">Natural Science Foundation of Guangdong Province for Distinguished Young Scholars<named-content content-type="fundref-id">10.13039/501100018540</named-content>
</contract-sponsor>
<contract-sponsor id="cn003">Shenzhen Fundamental Research Program<named-content content-type="fundref-id">10.13039/501100017607</named-content>
</contract-sponsor>
<contract-sponsor id="cn004">Shenzhen Science and Technology Innovation Program<named-content content-type="fundref-id">10.13039/501100017610</named-content>
</contract-sponsor>
</article-meta>
</front>
<body>
<sec id="s1">
<title>Introduction</title>
<p>Over the past decades, to alleviate the increasingly severe fossil energy crisis, the capture and utilization of abundant solar energy have evolved into a hot research topic (<xref ref-type="bibr" rid="B37">Wu et&#x20;al., 2021</xref>; <xref ref-type="bibr" rid="B15">Jiasheng 1996</xref>; <xref ref-type="bibr" rid="B35">Weinstein, Loomis, and Chen 2015</xref>). The photothermal conversion is a potential way to efficiently utilize the solar energy among various solar energy utilization methods including photoelectric (<xref ref-type="bibr" rid="B7">Chirumamilla et&#x20;al., 2021</xref>; <xref ref-type="bibr" rid="B34">Wei et&#x20;al., 2020</xref>; <xref ref-type="bibr" rid="B31">Wang S.&#x20;et&#x20;al., 2021</xref>), photothermal conversion (<xref ref-type="bibr" rid="B14">Hoch et&#x20;al., 2016</xref>; <xref ref-type="bibr" rid="B1">Azad et&#x20;al., 2016</xref>) and photobiological conversion (<xref ref-type="bibr" rid="B25">Rosenbaum et&#x20;al., 2005</xref>; <xref ref-type="bibr" rid="B28">Turon et&#x20;al., 2021</xref>). Compared with commercialized photovoltaic technologies, concentrated solar power (CSP) systems can overcome the problem of intermittent sunlight, but the high cost still hinders the large deployment (<xref ref-type="bibr" rid="B41">Yushchenko et&#x20;al., 2018</xref>). The solar selective absorption coatings (SSACs), the core component of the CSP system, can substantially improve the solar to power conversion efficiency and enable the reduction of the levelized cost of energy (LCOE) of CSP systems&#x20;(<xref ref-type="bibr" rid="B16">Kan et&#x20;al., 2021</xref>) when the reliable operating temperature can reach or even exceed 750&#xb0;C (<xref ref-type="bibr" rid="B33">Wang X.&#x20;et&#x20;al., 2021</xref>). Furthermore, the ultra-high solar absorptance in solar spectrum range and low thermal emittance in the thermal infrared regime are beneficial to realize high efficiency and low LCOE of CSP system (<xref ref-type="bibr" rid="B29">Vidal and Klammer 2019</xref>).</p>
<p>Various attempts (<xref ref-type="bibr" rid="B12">He et&#x20;al., 2021a</xref>; <xref ref-type="bibr" rid="B39">Yang et&#x20;al., 2020</xref>; <xref ref-type="bibr" rid="B13">He et&#x20;al., 2021b</xref>) have been made but fulfilling the reliable operation of the absorber at high temperatures remains a challenge. So far, cermet-based absorbers composed of high-loss and refractory metals such as W, Ni, and Ta and the ceramic matrix have been extensively excavated (<xref ref-type="bibr" rid="B19">Liu et&#x20;al., 2019</xref>; <xref ref-type="bibr" rid="B22">Ning et&#x20;al., 2016</xref>; <xref ref-type="bibr" rid="B4">Cao et&#x20;al., 2014</xref>). However, the thermal diffusion behavior of metal atoms at high temperatures will affect the light absorption of the coating and lead to optical degradation of the absorber. The strategy of metal alloying can effectively suppress the thermal diffusion phenomenon and then boost the stability of the absorber. Yang et&#x20;al. utilized the TiW-SiO<sub>2</sub> as absorption layers to prepare SSACs on the quartz substrate. The experimental results showed that incorporating the second phase Ti could effectively improve the stability of the absorber (<xref ref-type="bibr" rid="B40">Yang et&#x20;al., 2021</xref>). In addition, a series of binary alloys (WTa, WNi, TiC, etc) based selective absorbers were proposed and their stable operating temperatures were further enhanced (<xref ref-type="bibr" rid="B2">Cao et&#x20;al., 2015a</xref>; <xref ref-type="bibr" rid="B3">Cao et&#x20;al., 2015b</xref>; <xref ref-type="bibr" rid="B32">Wang et&#x20;al., 2017</xref>; <xref ref-type="bibr" rid="B38">Wu et&#x20;al., 2020</xref>). However, the reliable stable temperatures of these absorbers are below 750&#xb0;C due to the limination of intrinsic material properties. In recent years, all-ceramic based absorbers have shown great potential for high-temperature applications, especially for absorbers with transition metal nitrides (<xref ref-type="bibr" rid="B17">Li et&#x20;al., 2021</xref>; <xref ref-type="bibr" rid="B20">Meng et&#x20;al., 2017</xref>; <xref ref-type="bibr" rid="B18">Liang et&#x20;al., 2018</xref>) and their ceramic composites (<xref ref-type="bibr" rid="B21">Meng and Zhou 2019</xref>; <xref ref-type="bibr" rid="B42">Zhang et&#x20;al., 2016</xref>; <xref ref-type="bibr" rid="B5">Cao et&#x20;al., 2017</xref>) as the main absorption units realized by different optical designs and absorption mechanisms. Together with transition metal nitrides, transition metal carbides and borides also belong to the UHTCs, which are endowed with high melting temperature (&#x2265;3,000&#xb0;C), good thermal and electrical conductivity (<xref ref-type="bibr" rid="B6">Chen et&#x20;al., 2021</xref>), and chemical inertness (<xref ref-type="bibr" rid="B27">Tang and Hu 2017</xref>; <xref ref-type="bibr" rid="B8">Fahrenholtz and Hilmas 2017</xref>). Gao et&#x20;al. utilized the UHTCs as the main absorption unit to design the selective absorbers, which can only maintain thermal stability below 600&#xb0;C in vacuum (<xref ref-type="bibr" rid="B9">Gao et&#x20;al., 2019b</xref>). The sophisticated optical design may hold promise in maximizing the material&#x2019;s advantages at high temperatures. Wu et&#x20;al. raised a QOM structure based on W-SiO<sub>2</sub> cermet, which can enable the near-perfect light absorption by the interaction of multiple absorption mechanisms (<xref ref-type="bibr" rid="B36">Wu et&#x20;al., 2019</xref>). However, the stable operating temperature is only 600<sup>o</sup>C. It is a feasible way to enhance the working temperature through incorporating the UHTCs in the QOM structure.</p>
<p>Herein, to overcome the thermal diffusion of metal atoms in the QOM structure at high temperature, we proposed a spectrally selective solar absorber based on the QOM optical structure and UHTCs. Combined with the optical properties of the materials, the solar selective absorbers with an ultra-high absorptance were obtained by the precise optimization design of the optical structure. Moreover, the prepared absorbers exhibit excellent thermal stability up to 900&#xb0;C in vacuum, which is attributed to the introduction of ZrC in the QOM structure and the optimal design of ZrC in the composite ceramic layer. Near-perfect absorption over the broad solar spectrum and relatively low mid-IR emission could guarantee an ideal conversion efficiency of 68% in the CSP system. This developed strategy will also pave the way to designing the other ultra-high temperature absorbers.</p>
</sec>
<sec sec-type="materials|methods" id="s2">
<title>Materials and Methods</title>
<p>A commercial software (Essential Macleod) was used to optimize the optical structure. The different thresholds and weighted coefficients within the optimization region of 0.25&#x2013;2.5&#xa0;&#x3bc;m were set to realize the high solar absorptance. The optical constants of the individual layer involved in the optical design were measured by a spectroscopic ellipsometer (J.&#x20;A. Woollam Co, Inc.). The designed ZrC-based spectral selective absorbers (CAA) were prepared by a high vacuum multi-target magnetron sputtering system (Beijing Technol Co. LTD, JCPY650) equipped with three high purity targets. Prior to the deposition, the polished stainless (SS304) substrates were cleaned successively with acetone and alcohol. More details about the used materials have been tabulated in the <xref ref-type="table" rid="T1">Table&#x20;1</xref>. All the coatings in this paper were carried out in an Ar environment under a pressure of 0.4&#xa0;Pa using a radio frequency (RF) power at room temperature after the substrate bias cleaning for 10&#xa0;min in the main chamber with the based pressure of below 4&#x20;&#xd7; 10<sup>&#x2013;4</sup>&#xa0;Pa. By adjusting the sputtering power of ZrC target, three ZrC-Al<sub>2</sub>O<sub>3</sub> composite ceramic layers (C1, C2, and C3) with different volume ratios of ZrC in composite layer were prepared <italic>via</italic> co-sputtering of ZrC and Al<sub>2</sub>O<sub>3</sub>. More details about the deposition parameters were summarized in <xref ref-type="table" rid="T2">Table&#x20;2</xref>.</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>The basic information about the used targets and substrate in the QOM-based absorber (CAA).</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Materials</th>
<th align="center">ZrC target</th>
<th align="center">Al<sub>2</sub>O<sub>3</sub> target</th>
<th align="center">SiO<sub>2</sub> target</th>
<th align="center">SS 304</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">Size</td>
<td align="center">&#x3a6;50.8&#xa0;mm &#xd7; 4&#xa0;mm</td>
<td align="center">&#x3a6;50.8&#xa0;mm &#xd7; 4&#xa0;mm</td>
<td align="center">&#x3a6;50.8&#xa0;mm &#xd7; 4&#xa0;mm</td>
<td align="center">20&#xa0;mm &#xd7; 20&#xa0;mm &#xd7; 1&#xa0;mm</td>
</tr>
<tr>
<td align="left">Purity</td>
<td align="center">99.95%</td>
<td align="center">99.99%</td>
<td align="center">99.99%</td>
<td align="center">_</td>
</tr>
</tbody>
</table>
</table-wrap>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>The deposition parameters of the coatings including composite ceramic layers (C1, C2, and C3) with different ZrC volume ratios in Al<sub>2</sub>O<sub>3</sub>, ZrC infrared (IR) layer, Al<sub>2</sub>O<sub>3</sub>, SiO<sub>2</sub>, and CAA<xref ref-type="table-fn" rid="Tfn1">
<sup>a</sup>
</xref>.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Sample</th>
<th align="center">Substrate</th>
<th align="center">ZrC</th>
<th align="center">C1, C2 or C3</th>
<th align="center">ZrC</th>
<th align="center">C3</th>
<th align="center">SiO<sub>2</sub>
</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">C1</td>
<td align="center">Si</td>
<td align="center">-</td>
<td align="center">(C1) 96&#xa0;nm</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
</tr>
<tr>
<td align="left">C2</td>
<td align="center">Si</td>
<td align="center">-</td>
<td align="center">(C2) 110&#xa0;nm</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
</tr>
<tr>
<td align="left">C3</td>
<td align="center">Si</td>
<td align="center">-</td>
<td align="center">(C3) 103&#xa0;nm</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
</tr>
<tr>
<td align="left">CAA</td>
<td align="center">Si or SS</td>
<td align="center">100&#xa0;nm</td>
<td align="center">(C3) 30&#xa0;nm</td>
<td align="center">25&#xa0;nm</td>
<td align="center">40&#xa0;nm</td>
<td align="center">70&#xa0;nm</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn id="Tfn1">
<label>a</label>
<p>All the work in this paper was carried out in an Ar environment under a pressure of 0.4&#xa0;Pa using the RF sputtering at room temperature.</p>
</fn>
</table-wrap-foot>
</table-wrap>
<p>The annealing tests were performed in a vacuum tube furnace at different target temperatures for 100&#xa0;h with a heating rate of 5&#xb0;C/&#xa0;min. The vacuum pressure is about 4&#x20;&#xd7; 10<sup>&#x2013;2</sup>&#xa0;Pa. The ultraviolet-visible-near infrared (0.28&#x2013;2.5&#xa0;&#x3bc;m) reflection spectra of the coatings were measured by a spectrophotometer (Agilent Cary 5,000) equipped with an integrating sphere, while the mid-IR reflection spectra in the wavelength range of 2.5&#x2013;20&#xa0;&#x3bc;m were collected by a Fourier transform infrared spectrometer (Nicolet IS50) equipped with a Pike Au integrating sphere at room temperature. The solar absorptance (&#x3b1;) and thermal emittance (&#x3b5;) were calculated by the weighted integration of reflection spectra with the standard solar spectra and the black body emissive spectra, respectively (<xref ref-type="bibr" rid="B30">Wang J.&#x20;et&#x20;al., 2021</xref>).</p>
<p>The surface topographies were detected by an atomic force microscope (Oxford Instruments Asylum Research, Inc.) with a scanning area of 5&#xa0;&#x3bc;m &#xd7; 5&#xa0;&#x3bc;m. The phase analysis of the samples was characterized by Raman spectra collected on a Raman spectrometer with a 532&#xa0;nm laser excitation (Renishaw in <italic>Via</italic>) and XRD patterns obtained by a Rigaku diffractometer (LX-57B) with Cu-K&#x3b1; radiation (40&#xa0;kV, 200&#xa0;mA, <italic>&#x3bb;</italic> &#x3d; 0.15406&#xa0;nm).</p>
</sec>
<sec sec-type="results|discussion" id="s3">
<title>Results and Discussion</title>
<sec id="s3-1">
<title>Optical Simulation and Absorption Mechanism Analysis of Solar Selective Absorption Coatings</title>
<p>To optimize the optical response of the CAA structure, we first measured the optical constants (n and k) of the materials used in the structure, as shown in <xref ref-type="fig" rid="F1">Figure&#x20;1</xref>. The Cauchy dispersion model was picked to fit the transparent material SiO<sub>2</sub>, while Gen-Osc dispersion model including Cody-Lorentz and Gaussian oscillators was used to analyze the metallic ZrC and cermets (C1, C2, and C3). The larger extinction coefficient of ZrC confirms the intrinsic absorption due to the in-band contribution and the interband contribution of electrons (<xref ref-type="bibr" rid="B23">Okuhara et&#x20;al., 2018</xref>). The SiO<sub>2</sub> demonstrates a near-constant refractive index and a near-zero extinction coefficient, which determines it can be used as the top anti-reflection coating. The composite ceramic layers (C1, C2, and C3) with different volume ratios of ZrC in Al<sub>2</sub>O<sub>3</sub> matrix possess the optical constants with the values between SiO<sub>2</sub> and ZrC and present an increasing trend from 1.98 (C1) to 2.27 (C3), which indicates a substantial controlling space on the optical property <italic>via</italic> the modulation of the volume ratios of ZrC and Al<sub>2</sub>O<sub>3</sub>.</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>Refractive index (n) and extinction coefficient (k) of ZrC, SiO<sub>2</sub>, and ZrC-Al<sub>2</sub>O<sub>3</sub> ceramic composites (C1, C2, and C3) with different volume ratios.</p>
</caption>
<graphic xlink:href="fenrg-09-787237-g001.tif"/>
</fig>
<p>The QOM optical structure on the stainless-steel (SS) substrate with the coatings of ZrC/C3/ZrC/C3/SiO<sub>2</sub> from the bottom layer (layer 1) to the top layer (layer 5) was designed and shown in <xref ref-type="fig" rid="F2">Figure&#x20;2A</xref>. The calculated reflectance spectra of the layer-added coatings (<xref ref-type="fig" rid="F2">Figure&#x20;2A</xref>) demonstrate that the individual ZrC (layer 1) possesses moderate absorption due to the intrinsic spectral selectivity, and the absorption increases with adding more layers except for the bottom two layers (layer 1&#x2013;2), which is ascribed to the introduction of ZrC middle layer (layer 3) enhancing the reflection on the coatings without another Z3 layer (layer 4) and the top ARC layer (layer 5). Eventually, the CAA (layer 1&#x2013;5) exhibits a low reflectance of less than 5% in the wavelength range of 0.3&#x2013;1.38&#xa0;&#x3bc;m, indicating a superior absorptance. Therefore, we deposited the optimized CAA on the SS304 substrate, and the corresponding optical image and the reflectance spectra were shown in <xref ref-type="fig" rid="F2">Figure&#x20;2B</xref>. The coating displays a blue appearance and a pretty low reflection across the solar spectrum range matched well with the calculated data. Multiple absorption mechanisms in the QOM structure contribute to the low reflectance in the solar spectrum region, while the bottom ZrC leads to high infrared reflectance, which jointly determines the excellent selective absorption of the prepared CAA coating. The reflectance minimum at 0.62&#xa0;&#x3bc;m is attributed to the destructive interference of the interfaces (<xref ref-type="bibr" rid="B24">Qiu et&#x20;al., 2020</xref>). In order to further analyze the absorption mechanism of the CAA, we calculated the electromagnetic loss distribution of the designed optical structure at three specific wavelengths &#x3bb; &#x3d; 0.62&#xa0;&#x3bc;m, &#x3bb; &#x3d; 1.11&#xa0;&#x3bc;m and &#x3bb; &#x3d; 2.5&#xa0;&#x3bc;m, and visualized in <xref ref-type="fig" rid="F2">Figure&#x20;2C</xref>. It can be noted here that the overall loss of electromagnetic wave is distributed in the main absorption structure of C3/ZrC/C3, especially in the middle ZrC layer, and with the increase of incident wavelength, the electromagnetic wave would penetrate into the underlying layer resulting in the partial loss in the bottom ZrC&#x20;layer.</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>
<bold>(A)</bold> Simulated reflectance spectra of the layer-added coatings and the schematic of the optical structure. <bold>(B)</bold> The measured a reflection spectrum (gray line) the optical image of the CAA coating together with solar spectrum (AM 1.5, polychromatic block). <bold>(C)</bold> The distribution of electromagnetic power loss of the CAA at the wavelengths of 0.62, 1.11, and 2.5&#xa0;&#x3bc;m, where &#x3bb; &#x3d; 0.62&#xa0;&#x3bc;m is connected with the reflectance minimum.</p>
</caption>
<graphic xlink:href="fenrg-09-787237-g002.tif"/>
</fig>
</sec>
<sec id="s3-2">
<title>High-Temperature Properties of Selective Absorption Coatings</title>
<p>Enhancing the operating temperature of the spectrally selective absorber used in the CSP system would boost the conversion efficiency of solar energy to electricity. The as-deposited absorbers were treated in vacuum at different temperatures, and the reflectance spectra of the coatings before and after annealing were shown in <xref ref-type="fig" rid="F3">Figure&#x20;3A</xref>. Compared with the CAA before annealing, only negligible variations are observed in its reflectance spectra before the cutoff wavelength after annealing at 800&#xb0;C and 900&#xb0;C for 100 h, which testifies the superior thermal stability of the CAA even upon annealing in 900<sup>o</sup>C. Moreover, the calculated &#x3b1; and &#x3b5;<sub>82</sub>&#xa0;<sub>&#xb0;C</sub> of the CAA before and after annealing were summarized in <xref ref-type="fig" rid="F3">Figure&#x20;3B</xref>. The CAA upon annealing still possesses a pretty high solar absorptance greater than 0.96. The improved reflectance of the CAA upon annealing in the thermal IR range is beneficial to the suppression of thermal emittance, which is due to the better crystallinity of the bottom infrared reflection layer ZrC after annealing. So, thermal emittance decreases from 0.160 to 0.143 with the increase of the annealed temperature. The photothermal conversion efficiency (&#x3b7;<sub>thermal</sub>) of solar-to-heat and the total efficiency (&#x3b7;<sub>total</sub>) of solar-to-electricity based on the CAA were calculated under different operating temperatures and optical concentrations using the following <xref ref-type="disp-formula" rid="e1">Eqs 1</xref>&#x2013;<xref ref-type="disp-formula" rid="e3">3</xref>:<disp-formula id="e1">
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<label>(3)</label>
</disp-formula>where <italic>T</italic>
<sub>W</sub> is the working temperature of the coating, <italic>T</italic>
<sub>Amb</sub> the ambient temperature, C the optical concentration factor, &#x3c3; the Stefan-Boltzmann constant, and <italic>B</italic> (<italic>&#x3bb;</italic>,<italic>T</italic>) the black body emissive power at a certain temperature and wavelength. It should be noted here that the &#x3b5; in <xref ref-type="disp-formula" rid="e1">Eqs 1</xref>, <xref ref-type="disp-formula" rid="e2">2</xref> is calculated by <xref ref-type="disp-formula" rid="e3">Eq. 3</xref> considering the temperature dependence of thermal emission. As shown in <xref ref-type="fig" rid="F3">Figure&#x20;3C</xref>, the photothermal conversion coefficient increases with elevating the temperatures and can reach up to 91.4% under 1,000 suns and at 900&#xb0;C, indicating the potential applications at high-temperature CSP system. <xref ref-type="fig" rid="F3">Figure&#x20;3D</xref> depicts the total conversion efficiency including the photothermal conversion of the CAA and an ideal Carnot efficiency under different working temperatures and optical concentrations. There is an optimal total efficiency at the same optical concentration. A record-high total efficiency of 68% (1,000 suns) can be achieved at a reliable stable temperature (900<sup>o</sup>C) of the&#x20;CAA.</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>
<bold>(A)</bold> Reflection spectra of the coatings before (gray line) and after annealing in vacuum at 700<sup>o</sup>C (orange line), 800<sup>o</sup>C (yellow line), and 900<sup>o</sup>C (green line) for 100&#xa0;h. <bold>(B)</bold> The solar absorptance and thermal emittance of the absorber under different heat treatment conditions. <bold>(C)</bold> Temperature-dependent photothermal efficiency with different optical concentrations. <bold>(D)</bold> Temperature-dependent total efficiency with different optical concentrations. The vertical red dotted line represents the temperatures of 900<sup>o</sup>C.</p>
</caption>
<graphic xlink:href="fenrg-09-787237-g003.tif"/>
</fig>
</sec>
<sec id="s3-3">
<title>Surface Morphology and Phase Analysis</title>
<p>In order to thoroughly comprehend the evolution behavior of the coating at high temperatures, the three-dimensional surface topography of the CAA before and after annealing at different temperatures was obtained and demonstrated in <xref ref-type="fig" rid="F4">Figure&#x20;4</xref>. The grooves structure of the as-deposited CAA coating, shown in <xref ref-type="fig" rid="F1">Figure&#x20;1A</xref> is attributed to the polished SS304 substrate and disappears after thermal treatment. Compared with the substrate, the roughness of the deposited coating increases but also remains at a low level of 1.62&#xa0;nm, indicating excellent uniformity. As seen from <xref ref-type="fig" rid="F4">Figure&#x20;4B</xref> to <xref ref-type="fig" rid="F4">Figure&#x20;4D</xref>, when the coating CAA was respectively annealed at 700&#xb0;C, 800&#xb0;C, and 900&#xb0;C for 100 h, the agglomeration phenomena appear and intensify with increasing the annealing temperature, together with the roughness increasing from 1.62 to 11.3&#xa0;nm. More details on the coating roughness were summarized in <xref ref-type="table" rid="T3">Table&#x20;3</xref>. The change of the surface topography would affect the optical absorption of the absorber to a certain extent.</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Three-dimensional AFM images of the absorber CAA before annealing <bold>(A)</bold> and after annealing at 700<sup>o</sup>C <bold>(B)</bold>, 800<sup>o</sup>C <bold>(C)</bold>, and 900<sup>o</sup>C <bold>(D)</bold> in vacuum for 100&#xa0;h.</p>
</caption>
<graphic xlink:href="fenrg-09-787237-g004.tif"/>
</fig>
<table-wrap id="T3" position="float">
<label>TABLE 3</label>
<caption>
<p>Surface roughness of the absorber treated at different temperatures in vacuum.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Sample</th>
<th align="center">SS</th>
<th align="center">CAA</th>
<th align="center">CAA-700</th>
<th align="center">CAA-800</th>
<th align="center">CAA-900</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">Temperature</td>
<td align="center">_</td>
<td align="center">_</td>
<td align="center">700&#xb0;C</td>
<td align="center">800&#xb0;C</td>
<td align="center">900&#xb0;C</td>
</tr>
<tr>
<td align="left">Rq</td>
<td align="center">0.2&#xa0;nm</td>
<td align="center">1.62&#xa0;nm</td>
<td align="center">6.2&#xa0;nm</td>
<td align="center">9.1&#xa0;nm</td>
<td align="center">11.3&#xa0;nm</td>
</tr>
</tbody>
</table>
</table-wrap>
<p>XRD was used to disclose the phase changes of the absorber CAA after long-term annealing at different temperatures. <xref ref-type="fig" rid="F5">Figure&#x20;5A</xref> demonstrates XRD spectra of the CAA before and after heat treatment at 700&#xb0;C, 800&#xb0;C, and 900&#xb0;C for 100&#xa0;h. The pristine CAA (gray line) does not show any characteristic peaks of the coatings, except the peaks at 44&#xb0;, 52&#xb0;, and 77&#xb0; connected with the traditional austenitic stainless steel substrate (<xref ref-type="bibr" rid="B11">Gualtieri and Bandyopadhyay 2017</xref>). In addition, a new peak was found at 33&#xb0; on the annealed sample, which can be indexed to the ZrC (<xref ref-type="bibr" rid="B26">Schonfeld et&#x20;al., 2017</xref>). The better crystallization of ZrC in the absorber upon annealing could be the reason for decreased thermal emittance in the annealed coatings compared with the pristine one. Similar to XRD patterns, the Raman spectra of the deposited coating do not show the sample signal peaks. However, after the heat treatment, the characteristic peaks of amorphous carbon (D and G peaks) appear at 1,358&#xa0;cm<sup>&#x2212;1</sup> and 1,581&#xa0;cm<sup>&#x2212;1</sup> (<xref ref-type="bibr" rid="B10">Gao et&#x20;al., 2019a</xref>). The carbon aggregation from the substrate gradually strengthens with increasing the annealing temperatures. However, the aggregated carbons would not have a significant effect on the optical performances due to the introduction of the ultra-high temperature ceramics ZrC and the novel QOM structure. It can be predicted that choosing the stable dielectric substrate in the structure would further improve the thermal stability of the absorber at higher temperatures.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>XRD patterns <bold>(A)</bold> and Raman spectra <bold>(B)</bold> of CAA coatings deposited on stainless steel substrates before and after annealing at different temperatures in vacuum.</p>
</caption>
<graphic xlink:href="fenrg-09-787237-g005.tif"/>
</fig>
</sec>
</sec>
<sec sec-type="conclusion" id="s4">
<title>Conclusion</title>
<p>In summary, we designed and fabricated a heat-resisting and high-performance solar selective absorber CAA based on the ultra-high temperature ceramic ZrC on polished SS substrates. The as-deposited absorber exhibits outstanding spectral selectivity with a high absorptance of 96.4% and an IR emittance of 16%, which may be attributed to the sophisticated optical design coupled with multiple absorption mechanisms in the QOM structure and the introduction of ZrC. The absorbers can survive at 900&#xb0;C for 100&#xa0;h in vacuum, indicating superior thermal stability. The solar absorptance of the absorbers goes through a negligible change and remains at above 96% upon annealing, while thermal emittance decreases due to the better crystallization of ZrC beneficial for the suppression of heat loss. The photothermal efficiency of the absorber can reach 91.4% at the reliable operating temperature of 900&#xb0;C and 1,000 suns. Eventually, a record-high total efficiency of 68% can be achieved when considering the ideal Carnot efficiency.</p>
</sec>
</body>
<back>
<sec id="s5">
<title>Data Availability Statement</title>
<p>The original contributions presented in the study are included in the article/Supplementary Material, further inquiries can be directed to the corresponding authors.</p>
</sec>
<sec id="s6">
<title>Author Contributions</title>
<p>JW: Investigation, Fabrication, Characterization, Formal Analysis, Writing Original Draft, and Reviewing. ZW: Methodology and Investigation. YL: Conceptualization and Investigation. SH: Reviewing. JM: Resources and Writing&#x2013;Reviewing. XL: Writing&#x2013;Reviewing. QZ: Resources and Writing&#x2013;Reviewing. FC: Resources, Conceptualization, Editing, Reviewing, and Supervision. All authors approved the final version of the manuscript.</p>
</sec>
<sec id="s7">
<title>Funding</title>
<p>This work was funded by the National Natural Science Foundation of China (51871081 and 51971081), the Cheung Kong Scholar Reward Program Young Scholar Program of China (Q2018239), the Natural Science Foundation for Distinguished Young Scholars of Guangdong Province of China (2020B1515020023), Shenzhen Fundamental Research Program (GXWD20201230155427003-20200801190929005, and JCYJ20200109113418655), and Shenzhen Science and Technology Program (KQTD20200820113045081).</p>
</sec>
<sec sec-type="COI-statement" id="s8">
<title>Conflict of Interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
</sec>
<sec sec-type="disclaimer" id="s9">
<title>Publisher&#x2019;s Note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
<ref-list>
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