1 s2.0 S0038092X2030709X Main

Solar Energy 207 (2020) 247–269
Contents lists available at ScienceDirect
Solar Energy
journal homepage: www.elsevier.com/locate/solener
A materials perspective on radiative cooling structures for buildings T

a b a,⁎
Wenxin Li , Yanru Li , Kwok Wei Shah
a
Department of Building, School of Design and Environment, National University of Singapore, Singapore 117566, Singapore
b
College of Architecture and Urban-Rural Planning, Sichuan Agricultural University, Chengdu, China
ARTICLE INFO ABSTRACT
Keywords: As a promising climate change mitigation technology, radiative cooling presents an economical and environ-
Radiative cooling mental-friendly approach to alleviate cities from overheating and urban heat island. Based on the fundamental
Nano/microstructures theory, this study comprehensively reviews the materials composition and nano/microstructures underlying the
Nanomaterials radiative cooling technology. The study summarizes the primary six properties of the selective emitting material,
Building cooling
reflecting material, back-mirror material, matrix material, insulation material and dynamic switching material,
Selective emitters
Passive thermal management
in terms of their morphologies, substrates, properties, and performances. The configuration of radiative cooling
systems mostly follows the two essential designs, namely “multi-layered structures” composed of multiple
continuous nano/micro-layers or “nano/micro-particle structures” consisting of discrete nano/microparticles or
a combination of both. Cooling potential and end-applications on buildings were reviewed, including cool roofs,
PV cooling and water cooling. At the end of this review, we present our recommendations on the combining
“multilayer” and “nanostructure” designs for better design radiative cooling composites from a materialistic
perspective. Unlike previous studies, our review provides a unique overview of nanomaterials and composite
structures, leading to better design configuration and optimisation of radiative cooling end-applications.
1. Introduction wavelength ranging from 8 μm to 13 μm, without external energy input

and production of environmental pollutants (Grant, 1990; Vinnikov and
Nowadays, the extreme global warming, caused by urban heat is- Grody, 2003). Since the earth surface temperature is generally around
land effects, lead to a rapid increase in ambient temperature, unseen 300 K while the universe one is only 2.7 K, their significant temperature
hikes in more cooling energy demands, severe indoor and outdoor heat- difference provides incredible potential for the free cooling. For ex-
related human discomfort and elevated urban air pollutions ample, the Contiguous United States is estimated to have an average
(Santamouris et al., 2001). The rapid overheating of buildings is typi- cooling potential of 50.5 m−2 per year (Li et al., 2019a).
cally tackled by air-conditioning, heating, and ventilation (HVAC) RC technology is achieved by materials with high emissivity in the
systems, which accounts for more than half of the total building energy spectral wavelength of 8–13 µm. These materials are usually grouped
(Pérez-Lombard et al., 2008). Conventional HVAC systems rely heavily based on their performances during night-time and daytime. In com-
on vapour compression-based cooling technologies which consume parison, the daytime RC is more complicated since it needs to cool the
massive fossil energy and emits huge amounts of greenhouse gases. surface to a temperature below ambient under sunlight due to the in-
Recently, a promising “sky window” cooling solution in the form of tense solar radiation. It requires materials to have low absorptivity
radiative cooling (RC) technology which can provide alternative “true” within solar spectrum of 0.3–2.5 μm while a high emissivity in other
passive cooling for buildings was highlighted (Feng et al., 2019). This wavelengths, especially within 8–13 µm. At the early stage, active re-
economic and environmental-friendly approach has aroused great at- searches have been conducted on the night-time RC materials and de-
tention from researchers. vices, and the theoretical studies on performance improvement and its
Radiative cooling (RC) was first investigated systematically as a potential to achieve daytime RC. Raman et al. (2014) first experimen-
natural phenomenon in the 1960s, basically to understand its funda- tally obtained the daytime RC under direct solar radiation below the
mental and apply techniques for practical utilisations (Clark and ambient temperature in 2014, which follows by more daytime RC de-
Berdahl, 1981). It is a ubiquitous process of dissipating terrestrial heat signs of the materials and devices.
to outer space via the atmospheric sky window with thermal The rapid development of RC technology mainly depends on the
⁎
Corresponding author.
E-mail address: [email protected] (K.W. Shah).
https://doi.org/10.1016/j.solener.2020.06.095
Received 21 April 2020; Received in revised form 6 June 2020; Accepted 26 June 2020
Available online 07 July 2020
0038-092X/ © 2020 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
W. Li, et al. Solar Energy 207 (2020) 247–269
Nomenclature PEA Polyethylene aerogel

RC Radiative cooling
A Area of the radiative cooling emitter, m2 TEM Transmission electron microscopy
a Solar albedo TiO2 Titanium dioxide
c Speed of light, m/s TPX Microsphere-Poly-4-methyl-1-pentene
E Thermal emissivity SEM Scanning electron micrograph
h Heat transfer coefficient, W/(m2·K) SiO2 Silica, silicon dioxide
hp Planck’s constant, J⋅s UHI Urban heat island
kB Boltzmann constant, J/K VO2 Vanadium dioxide
l Wavelength, m
P Radiation power, W Subscripts
T Temperature, °C
θ Angle, ° atm Atmospheric
AM Air mass c Combined conduction and convection heat coefficient
ASA Poly(acrylonitrile-styrene-acrylate) cond Conduction
CNT Carbon nanotube conv Convection
FTO Fluorine-doped tin oxide cool Net cooling
HfO2 Hafnium dioxide cool-night Nighttime net cooling
ITO Indium tin oxide rad Terrestrial radiation
LWIR Longwave infrared sun Solar
PE Polyethylene
careful selection and design of its materials and structures, and re- significantly enhances the temperature drop and cooling power for the
searchers discovered new materials with appropriate thermal emis- night-time RC. Besides the silicon-based materials, other materials such
sivity/absorption spectrum. From single SiO2 film (Granqvist and as carbon-based materials (Suryawanshi and Lin, 2009) and Al2O3
Hjortsberg, 1981) to silicon oxynitride multilayers (Diatezua et al., (Kecebas et al., 2017) also show high potentials in emissivity en-
1996), the broadened absorption peak within the atmospheric window hancement. Later, the multi-layer structure is commonly adopted to
Fig. 1. Overview of the review paper.
248
optimize RC performance through additional function layers (Hu et al., systems (Zeyghami et al., 2018; Zhao et al., 2019f). Some focused on
2020a; Kou et al., 2017) or repetitive high-low index periodic layers the more challenging one, daytime RC technology (Feng and
(Kecebas et al., 2017; Raman et al., 2014). Meanwhile, since the Santamouris, 2019; Feng et al., 2019; Li et al., 2020). For various RC
spectral characteristics decrease with the increasing size of nano- devices, they are typically grouped by their performances as nighttime
particles (Cheng et al., 2019), the morphology of nanomaterials and and daytime RC; by their specific products as films, paints, etc. (Hossain
their micro/nanostructures have been optimized to enhance the cooling and Gu, 2016; Li et al., 2020); by working mechanism as nanophotonic
effects (Hossain et al., 2015; Zhu et al., 2013, 2015). The rapid devel- and others (Sun et al., 2017). As future widespread application and
opments of RC materials and structures prompt more practical appli- optimization of RC technology rely heavily on the new materials and its
cations in buildings, such as the cool roof, RC painting, PV cooling, composites (Vall and Castell, 2017), and the advent of novel materials
water cooling, etc. preludes to the further development of this promising technology (Lu
Since the summary of RC technology is necessary for its application et al., 2016).
reference, several researchers have reviewed the fundamental princi- So far, related review papers represent about 5% of the total amount
ples of RC (Li et al., 2020; Zhao et al., 2019b, 2019f) and its applica- of papers, and very few summarize from a material perspective by
tions on buildings, especially those integrated with other energy considering the RC nano/microstructures. Therefore, this study aims to
Fig. 2. (a) Schematic of solar energy balance (Zhao et al., 2019f) and their (b) spectrum distributions (Lim, 2020).
249
give a comprehensive review of RC technologies from a materials per- Prad (T ) = A d cos d IBB (T , ) ( , ) (2)
spective (as shown in Fig. 1). Specifically, Section 2 introduces the 0
fundamental theory of RC technology and depicts the ideal materials; where d =2 0

d sin is the angular integral over a hemisphere;
Section 3 summarizes the materials used in the RC structures according 2hc 2
IBB (T , ) = 5 hp c/( KB T ) is the spectral radiance of a blackbody at
1
to their functions; Section 4 highlights the design principles of these e 1

temperature T; hp is Planck’s constant; kB is the Boltzmann constant; c is
micro/nanostructures; Section 5 presents the cooling potential and the speed of light; l is the wavelength.
applications of RC with nano/micro-structures in buildings. The mate- The absorbed power due to incident atmospheric thermal radiation
rials perspective will provide a novel summary of materials and their (Patm) is:
structures for RC technology, offering potential material selections for
RC performance optimization. Patm (Tamb) = A d cos d IBB (T , ) ( , ) atm ( , ) (3)
0
2. Fundamental theory of radiative cooling technology where atm ( , ) = 1 t ( , t(λ) is the atmospheric transmittance
)1/ cos
in the zenith direction.
2.1. Heat transfer theory Assuming the structure is facing the sun at a fixed angle θSun, the
incident solar power absorbed by the structure (Psun) is calculated by:
Fig. 2(a) shows the interaction of solar irradiation and the infrared Psun = A d ( , sun ) IAM 1.5 ( ) (4)
radiation emitted from the earth’s surface. The blackbody sun emits at a 0
temperature of 5800 K, and the sunlight attenuated when it travels where IAM1.5(λ) is the AM1.5 spectrum.
through the atmosphere due to the reflection, absorption and scattering The power lost due to convection and conduction (Pcond+conv) is:
of aerosols, atmospheric constituents and clouds. Within a specific
Pcond+ conv (T , Tamb) = Ahc (Tamb T) (5)
spectral wavelength, higher atmospheric absorptivity can significantly
attenuate the sunlight intensity (Fig. 2b). Such solar radiation intensity where hc = hcond + hconv is a combined non-radiative heat coefficient.
after sun rays directly passing through the atmospheric air layer can be During the nighttime, the building surface is only affected by the
characterized by the air mass (AM) coefficient. The solar irradiation convective and conductive heat transfer from the ambient environment
mainly concentrates in the short wavelength region (0.3–2.5 μm) with (Fig. 3). The building surface is cooled by the terrestrial radiation; thus,
values peaking around ~0.5 μm within the visible spectrum. the building surface temperature should be lower than the ambient
Meanwhile, the earth’s surface also irradiates the atmosphere and temperature. The nighttime net cooling power (Pcool-night) is calculated
encounters absorption and scattering. The terrestrial radiation con- by the terrestrial radiation (Prad) and convection and conduction power
centrates at wavelengths ranging from 2.5 to 50 μm, where most in- loss (Pcond+conv):
frared wavelengths are absorbed except those between 8 and 13 μm
Pcool night (T ) = Prad (T ) Pcond + conv (8)
(Fig. 1b). The 8–13 μm band is so-called the transparent window of the
atmosphere or the atmosphere window, which allows the heat releasing To achieve a higher cooling ability, the RC structures should exhibit
through longwave radiation to exceed the radiation absorption to en- maximal emissivity through the transparent atmospheric window,
able passive cooling. especially for the daytime cooling (Baranov et al., 2019). According to
Fig. 3 simplifies the heat flows on the building surface during the energy balance Eq. (1), higher terrestrial radiation (Prad), lower
daytime and nighttime. The building surface temperatures depend on solar irradiation (PSun) and atmospheric radiation absorption (Patm) are
the solar radiation, terrestrial thermal radiation, and convection and essential to achieve daytime RC. Therefore, the device must emit
conduction heat transfer between the ambient air and surface. Given an strongly and selectively only through the transparent atmospheric
RC area A at temperature T, the radiative cooler oriented a daylight sky window while reflecting at the other wavelengths. In practice, more
is affected by the atmospheric thermal radiation and solar irradiance. than 94% of sunlight must be redirected via reflection to achieve
For this radiative cooler, its net cooling power (Pcool) can be calculated meaningful daytime RC, especially for the varying atmospheric condi-
by (Raman et al., 2014): tions (Raman et al., 2014). Since these parameters in Eq. (1) are sus-
ceptible to the environmental conditions, such as the weather condition
Pcool (T ) = Prad (T ) Patm (Tamb) Psun Pcond + conv (1)
(Liu et al., 2019b), sky condition (Zhao et al., 2019c) and climate zone
In Eq. (1), the power radiation from the structure (Prad) is: (Feng et al., 2020), etc. For areas with clear skies, dry climates and high
Fig. 3. The heat balance of building surfaces.
250
altitudes, the atmosphere has higher transmittance within the atmo- vanadium dioxide (Ji et al., 2018) and other metallic oxides (Kecebas
spheric window, therefore, a more significant RC effect. et al., 2017; Yang et al., 2019), etc.
2.2. Ideal materials

3.1.1. Silicon-based materials
The optical phonon can be used in ionic dielectrics to achieve higher
The perfect RC performance can be achieved by structures with
emissivity in the “atmospheric sky window”. Silicon-based materials
minimum absorptivity of direct sunlight and maximum emissivity
were widely adopted in RC technologies. At the early stage of the re-
through atmospheric sky window, which needs the nanophotonic op-
search (mainly for the nocturnal RC), Granqvist and Hjortsberg (1981)
timization of the materials. Fig. 4 shows the ideal emissivity spectrum
introduced an infrared-selective surface combining SiO films and Al,
of materials used for daytime or nighttime RC at temperatures higher
which yielded a temperature 14 °C lower than the ambient one during
(above-) or lower (sub-) than the ambient temperature. Nighttime and
clear nights in Sweden. Diatezua et al. (1996) developed a three-layer
daytime applications concern the wavelength ranges of 2.5–50 μm and
silicon oxynitride deposited Al-coated glass substrate. The structure has
0.3–50 μm, respectively. The emissivity needs to approach 100% in the
a broader absorption peak in the atmospheric window, showing a
atmosphere’s sky window (8–13 μm) for sub-ambient applications and
maximum temperature drop of 56 °C and cooling power of 125 W/m2.
be around zero within the solar spectrum range (0.3–2.5 μm) for the
Superior optical properties make silicon oxynitride an attractive RC
daytime applications. It is clear that different materials are needed for
material, and the silicon oxynitride multilayers have broader absorp-
different RC: daytime RC materials should have excellent emissivity
tion range within wavelengths of 8–13 μm (Diatezua et al., 1996,
through reflectivity in the solar spectrum and atmospheric sky window,
1995). Synthesized from Si and SiO2 powders via the heat treatment
while the nighttime RC only requires high emissivity.
method, Si2N2O particles were coated on Al substrates to form an RC
The ideal cooling effects are achieved by optimization of the na-
device (Miyazaki et al., 2016). Average differences between ambient
nophotonic characteristics of these RC materials and structures. For a
temperature and the structure were −0.82, −0.44 and +0.83 °C for
simple nanoparticles-doped RC structure (Fig. 5), part of the spectral
Si2N2O film with thicknesses of 6.5 μm, 13.2 μm and 35.2 μm, re-
radiation is emitted through infrared radiation. Partial scattering en-
spectively, while only the previous two observed the RC effects.
ergy will be reflected, and the others will be absorbed by the substrate.
Nanoparticles (e.g. SiC) which emit solely within 8–13 μm with no
To achieve more infrared radiation and reflection, the RC structures can
absorption from the prominent zone can cool temperatures below am-
be optimized by adopting novel materials, metasurface, multi-layers,
bient effectively. An optimized radiative cooler design consisting of SiC
etc.
and quartz was proposed by Rephaeli et al. (2013) to achieve daytime
With the development of RC technology, more structures attempt to
RC for outdoor environments. The metal-dielectric photonic structure
be multi-function with the multi-layer structure to enhance the RC ef-
could reflect the solar light and emit actively through the atmospheric
fects or achieve additional functions such as adaptive control. Thus, this
sky window in the mid-IR, with a cooling energy rate of over 100 W/
study summarizes the nanomaterials with a “multi-layer structure”, and
m2. These cooling effects still exist under conditions with non-ideal
each layer is supposed to have different features. It should be noticed
atmospheric and significant conductive/convective heat exchange.
that the RC effects may be generated via different layers rather than a
Quartz and SiC are very weak absorbers for the visible and IR lights
single one. Based on the representative materials used in RC structures,
while desirable for daylight operation, ensuring thermally emitting
these materials can be grouped as a selective emitting material (com-
layers absorb a minimal amount of solar power. If the SiC nanoparticles
bined with matrix material), reflection material, back-reflection mate-
are placed on the top of SiC film with certain periodicities, the emission
rial, insulation material and dynamic switch layers (Fig. 6). Specifically,
can be significantly enhanced, particularly at the far-infrared (Didari
the selective emitting material layer should have the desired emissivity
and Mengüç, 2015).
in “sky window”, and its emitting performance can be affected by the
Zhao et al. (2019c) experimentally investigated the daytime RC
matrix material. The reflective material layer aims to reflect solar ra-
performance of a silica (SiO2) mirror emitter, which deposited SiO2 and
diation efficiently. Most structures adopt the back-reflection material,
Ag layers on a thin SiO2 substrate. The sub-ambient cooling
usually the mirror, to reflect the heat simply. Insulation material layer
is generally placed on the top to reduce direct solar irradiance. In the
self-adaptive RC structures, the dynamic switch could be phase change
material, electrochromic and thermochromic materials, etc. Most ex-
isting RC structures have single or multiple aforementioned layers, and
their sequence could be different to satisfy different design require-
ments. Moreover, the cooling effects of these structures can also be
enhanced by the nanostructures, especially for the selective emitting
layer. The emitting performance can be significantly improved by the
techniques of (1) repetitive layers in the multi-layer structure; (2)
morphology optimization in the nano-sized structure.
3. Materials used in radiative cooling technology
These materials are summarised based on their primary functions:

the selective emitting material, reflection material, back-reflector, ma-
trix material, insulation material and dynamic switch. Table 1 presents
the materials used in literature.
3.1. Selective emitting material

Fig. 4. Ideal emissivity spectrum of radiative cooling materials during daytime
Selective emitter aims to efficiently dissipate heat through the at- above-ambient (black solid), daytime sub-ambient (red dashed), nighttime
mosphere window at 8–13 μm wavelength to outer space. The typical above-ambient (orange dashed) and nighttime sub-ambient (blue solid), re-
materials include silicon-based material (Diatezua et al., 1996; Zhai spectively (Zhao et al., 2019f). (For interpretation of the references to color in
et al., 2017), carbon-based material (Suryawanshi and Lin, 2009), this figure legend, the reader is referred to the web version of this article.)
251
Fig. 5. Schematic of radiative transfer for RC nanomaterials (Cheng et al., 2019).
performance of RC decreases rapidly with higher solar radiation and surrounding air temperature by ~5 °C under direct solar irradiation
humidity even with a clear sky. Zhai et al. (2017) demonstrated a (Fig. 7b).
productive diurnal and nocturnal RC structure with randomized, micro For metamaterial RC films consisting of SiO2, microsphere-Poly-4-
SiO2 spheres - polymer metamaterial. The silver-coated metamaterial methyl-1-pentene (TPX) and fluorine-doped tin oxide (FTO) substrates,
film (6% microspheres) showed a ~96% of solar irradiance reflection their transmittance and scattering effects are determined by the amount
and averaged infrared emissivity > 0.93. The silica microspheres can of SiO2 microspheres (Yang et al., 2019). Poorer optical transmittance
easily be polarised and interact strongly with the infrared light. The will be found in the near-infrared visible band if the SiO2/TPX volu-
metamaterial can mainly emit through the full atmospheric window metric ratio and film thickness increase or the microsphere size de-
and keep transparent to the solar spectrum. The glass-polymer meta- creases. The hybrid film with 5% ratio of SiO2/TPX has an emissivity of
material is lossless in the solar spectrum, and it won’t be heated up ~0.91 in a daytime test, and it can provide surface temperatures 20 °C,
under direct solar irradiance. 12 °C and 8 °C lower than those of the black body, Ag-coated glass and
To achieve the daytime RC, stronger emitting through “atmosphere FTO sample, respectively. Meanwhile, the structure can cool the am-
sky window” is in need. Gentle and Smith (2010) mixed SiC and SiO2 bient temperature by up to 4.5 °C in a nocturnal test.
nanoparticles and doped in polyethylene combing aluminium plate.
Since crystalline SiC nanoparticles stand out at wavelength ranging
3.1.2. Carbon-based material
from 10.5 to 13 µm, and resonant SiO2 nanoparticles absorb from 8 to
Carbon black can efficiently absorb radiations like a blackbody
10 µm, their mixture was experimentally proved for good cooling
(Howell et al., 2010), its high abundancy and absorptivity make it a
performance at low cost with entire “transparent window” covered. As
good choice of emitting material. Huang and Ruan (2017) proposed a
shown in Fig. 7(a), Raman et al. (2014) introduced a composited
double-layer structure of titanium dioxide and carbon black particles,
thermal emitter and reflector, the 7-layer SiO2 and HfO2 structure can
where the carbon black layer responded for emitting heat through “the
obtain 97% incident sunlight reflectivity and emit through the sky
transparent window”. The structure can reflect solar irradiation over
window. The seven alternating layers of SiO2 and HfO2 have varying
90% and show an averaged emissivity of 0.9 in most directions, which
thicknesses, deposited on the layers of Ag and silicon wafer. The solar
further contribute to a diurnal net cooling load at the ambient tem-
reflection performance was optimized with the lowest four layers of
perature of more than 100 W/m2.
HfO2 and SiO2. As a high-index material, HfO2 shows low ultraviolet
Suryawanshi and Lin (2009) dispersed nanodiamond powder,
absorption. The optically transparent SiO2 serves as the low-index
carbon black and multiwall carbon nanotube (CNT) in an acrylate
layer. HfO2 can be replaced with more economical material such as
emulsion as composite materials. Their order of lattice quantization is
TiO2. To radiate the heat from the cooler, the top three layers are much
multiwall CNT > carbon black > nanodiamond powder, which cor-
thicker. The experiment demonstrates that RC could decrease the
related well with the surface emissivity enhancement. The 1% loading
Fig. 6. Design and optimization of the radiative cooling material structures.
252
Table 1
Nano/microstructures in literature.
W. Li, et al.
No. Nanomaterial Radiative cooling Morphology Substrate Solar reflectivity & emissivity Diurnal/ Temperature Cooling power Reference
structure Nocturnal reduction
1 SiO2 SiO2 microspheres- SiO2 spheres with ~4 mm TPX + Ag Emissivity > 0.93 (8–13 μm) Diurnal – Average cooling (Zhai et al.,
TPX-Ag (200 nm) radius power: > 110 W/ 2017)
m2; Average
noontime: 93 W/m2
2 SiO2 Double layer SiO2 microspheres with size Ag Emissivity: 0.94 ± 0.03 (8–13 μm Diurnal 4.6 ± 0.2 °C (3 wt% 47 W/m2 (same foil (Fan et al., 2019)
about 7.1 μm wavelengths); 0.92 ± 0.03 (2.5–25 μm) FPI@SiO2/Ag foil) surface & ambient
temperatures,
100 μm thick foil)
3 SiO2 SiO2 submicron Average pore size between – – - (textile) 1.0–2.5 °C – (Xiao et al.,
spheres randomly PA6 nanofibers > 0.95 μm 2019)
distributed in
polyamide 6
nanofibers
4 SiO2 Nanocoating 2D square lattice of silica Al Emissivity is veryclose to unity Diurnal 18.3 °C – (Zhu et al., 2014)
pyramids, with 4 μm
periodicity and 20 μm height,
on top of a 100 μm-thick
uniform silica layer.
5 SiO2, HfO2 7 layers Nanolayers 7 layers of HfO2 and SiO2 with Si wafer Reflectivity = 97%Emissivity > 0.9 Diurnal 4.9 °C 40.1 W/m2 (Raman et al.,
different thicknesses (8–13 μm) 2014)
6 Silicon Silicon nanowires Nanowire thickness: 0.1 μm Al Emissivity > 0.9 (8–13 μm) Diurnal 31.4 °C – (Zhu et al., 2013)
7 SiO Nanofilm SiO thicknesses Al Emissivity = 0.9 Nocturnal 13.8 °C 25 W/m2 (Granqvist and
0.1 < t < 2.4 pm (optimal Hjortsberg,
1 μm) 1981)
253
8 SiC & Quartz Nanolayer Layer thickness: 8 μm (SiC), Ag – Diurnal – 100 W/m2 (Rephaeli et al.,
2.5 μm (Quartz) 2013)
9 SiC & SiO2 Nanoparticles ~50 nm in diameter and PE + Al Emissivity = 0.95 Diurnal 18–25 °C reduction – (Gentle and
spherical Smith, 2010)
10 Si2N2O Nanofilm Sub-rounded particle size: Al – – 0.44 °C and 0.82 °C – (Miyazaki et al.,
20–80 nm 2016)
11 Silicon oxynitride Nanolayers Layer thickness: 1.4/1.6 μm Al – Nocturnal Up to 56 °C Up to 125 W/m2 (Diatezua et al.,
1996)
12 TiO2 Nanocrystalline TiO2 Commercial TiO2 crystals size: Polyethylene foils – Nocturnal – – (Mastai et al.,
films 0.23 μm, average: 61.5 nm 2001)
13 TiO2 Composite Particle size: 280 nm Polyethylene Emissivity: 0.87 (8–13 µm) Diurnal 10 °C – (Qi et al., 2017)
14 TiO2 Composite Nanoparticle Acrylic Reflection: 91% Diurnal – – (Peoples et al.,
d = 104 ± 37 nm 2019)
15 TiO2, SiO2, and SiC Nanolayers SiO2 particle size: 1 μm Al Reflectivity: 90.7%;Emissivity: 90.11% Diurnal 17 °C at night; 5 °C 150 W/m2 (Bao et al., 2017)
(8–13 µm) during daytime
16 TiO2 and carbon black Nanolayers Particle size: 0.2 μm Acrylic resin Reflectivity > 90%Emissivity > 0.9 Diurnal – 100 W/m2 (Huang and
particles (8–13 µm) Ruan, 2017)
17 Al2O3, TiO2, SiO2, Nanolayers 200 nm thick for each layer Ag Emissivity: 71% (8–13 µm) Diurnal – 103 W/m2 (Kecebas et al.,
2017)
18 Al/SiO2/ SiNx/SiO2/ Nanolayers Thicknesses: 157 nm (SiNx), Al Reflectivity: 88% Diurnal 7.4 °C (Nocturnal), 43 W/m2 (Cunha et al.,
TiO2/SiO2 1.6 µm (SiO2 rutile) and 83 nm 2.5 °C (Diurnal) 2020)
(TiO2)
19 Metal-dielectirc Pillars Pillar size: 30 nm height, Al Emissivity: 0.9 (8–13 µm). Diurnal 58 °C 116.6 W/m2 (Hossain et al.,
20 nm width 2015)
20 Nanodiamond powder, MF nanocoating Particle size: 20 nm Al – – 7 °C (0% or pure AC), – (Suryawanshi
multiwall carbon 9 °C (0.4%), 14 °C and Lin, 2009)
nanotube & carbon black (0.7%), and 17 °C
(1%)
(continued on next page)
Solar Energy 207 (2020) 247–269
of multiwall CNT contributes to a 17 °C temperature reduction. With
(Kim and Lenert,
(Xu et al., 2018)

more active phonons in molecular fan coating, the increase of CNT
(Mandal et al.,
loading will reduce the panel’s equilibrium temperature.
Reference
2018b)
2018)
3.1.3. Other metallic oxides
Materials with reliable absorption in the atmospheric window can
be added to achieve better emissivity performance. For example, Al2O3
Maximum cooling
rate: ~120 W/m2
shows non-absorption in the near-infrared and visible spectrum, and it

Cooling power
96 W/m2 shows higher absorption rates beyond 10 µm spectrum compared to

SiO2 and TiO2 (Kecebas et al., 2017). As shown in Fig. 8(a), Kecebas
et al. (2017) enhanced the RC performance by combining an Al2O3 film
with conventional coating structures (with identical overall thickness).
–
The Al2O3 design dramatically increases the emission, improving the

lower than the TiO2
temperature under
average emissivity from 55% to 71% in the 8–13 µm spectrum (Fig. 8b).
coating is 2–4 °C
Indium tin oxide (ITO), a transparent conductive oxide, is one of the

Temperature
and CaCO3
promising plasmonic material for selectively emitting in the infrared

The space
reduction
wavelength. Dao et al. (2019) proposed tri-layer plasmonic absorbers of

35 °C
6 °C
ITO-Al2O3-ITO tri-layers with hexagonal ITO disks on top. The structure

gave perfect absorptivity of 0.99 (simulated) and 0.92 (fabricated).
Nocturnal
The nocturnal RC only plastic foils with non-absorbing pigments can

Diurnal/
Diurnal
Diurnal
be used for water condensing, food refrigerating and buildings, etc.

These foils can efficiently reflect the solar radiation through the at-
–
mospheric window at night, so it can reduce the underlying material

Reflectivity: 88.04% (0.2–2.5 μm)Emissivity:
temperature during the night while work as selective covers to prevent

direct sunlight during daytime. For example, the optimal ZnS pig-
mented polyethylene foils prepared by Nilsson et al. (1992) solar re-
flectance could be 0.825, which was predicted to provide a 12 K am-
Solar reflectivity & emissivity
bient temperature reduction and a 52 W/m2 cooling load at night. For

polyethylene foil pigmented with TiO2, ZnSe, ZnS, ZnO and ZrO2, only
ZnS was able to cool a blackbody inside the insulated housing during
> 0.9 (2.5–25 μm)
¯LWIR = 0.97 ± 0.02
noontime, where heating power was estimated to be 7.2 W/m2 (Nilsson

and Niklasson, 1995).
3.2. Reflection material

–
3.2.1. Titanium dioxide (TiO2)

As a typical reflection material, TiO2 has a wide bandgap, stable
metal, plastics,
substrates like
None. diverse
chemical properties, high refractive index and being transparent to

Broadband
and wood
Substrate
most infrared radiation (Mastai et al., 2001). The submicron anatase

emitter
and rutile TiO2 particles could be solar reflector to scatter sunlight ef-
Al
ficiently (Bao et al., 2017; Vargas, 2000). Mastai et al. (2001) pig-
mented polyethylene foils with nanocrystalline TiO2. The TiO2 (rutile,
Nanoparticle size: 50–300 nm
centered at ~0.2 (nanopores)

Particle width: 1 μm; length:
and ~5.5 mm (micropores)

Bimodally distributed pore
~60 nm) colloidal suspension was spread between two polyethylene

sizes, broad distributions
sheets by hot pressing. The homogeneous shields gave high solar re-
flectance and high IR transmittance. Such simple and economical fab-
rication of nanocrystalline TiO2 films have the potential to be wide-
Morphology
spread due to their excellent optical characteristics.

By utilizing a wide spectral range of solar radiation, Peoples et al.
10 μm
(2019) used hierarchical particle sizes in a TiO2 nanoparticle-acrylic

system to increase solar reflection. A thin coating of nanoparticles (~2
nm) was fabricated to decrease charging effects. The designed hier-
archical combinations of particle sizes ranging between 50 and 800 nm
Nanoporous cover
Radiative cooling
achieved a ~91% of solar reflectivity, which was higher than the single-
Nanolayers
sized 100 nm (~78%) and 400 nm (~88%) particles. Compared to any

structure
Coating
single-sized particles, the hierarchical-sized particles can efficiently

scatter over a broad spectrum, which also can save the manufacturing
cost due to less need on precise particle size control. Additionally, for
co-hexafluoropropene) [P
Poly(vinylidene fluoride-
the homogeneous rutile or anatase pigmented polymer structure, the

solar reflectance could be optimized by adjusting pigment size, which
Mg11(HPO3)8(OH)6
will influence the effective scattering coefficients per unit length. It

BaF2, ZnS, and
(VdF-HFP)HP]
Table 1 (continued)
shows that the utile (anatase) pigmented coatings with a 10% particle
Nanomaterial
polyethylene
volume fraction can give solar reflectance values of 75% (65%) (Vargas,
2000).
Qi et al. (2017) compared the cooling performances of four types of
TiO2 combined with poly(acrylonitrile-styrene-acrylate) (ASA) resin.
No.
21
22
23
All the hybrid materials show high thermal emissivity of over 0.86. The
254
Fig. 7. (a) Scanning electron microscope image and (b) Rooftop performance measurement of the photonic radiative cooler (Raman et al., 2014).
Fig. 8. Comparisons of (a) Scheme of the design structures and (b) Emission curves for structures with/without including Al2O3 (Kecebas et al., 2017).
addition of TiO2 particles can significantly improve solar and NIR re- et al., 2014). However, the use of HfO2 is not necessary, and it can be
flectance, decreasing the temperature of ASA resin by up to 10 °C under replaced with less expensive material, TiO2. HfO2 also shows non-zero
the natural condition and 34 °C in the indoor temperature test. Among emission and absorption through the atmospheric window (8–13 mm
different TiO2, rutile TiO2 particles have a higher refractive index and wavelength) (Bright et al., 2012).
showing better NIR and solar reflectance than the anatase ones. Spe-
cifically, the hybrid material of hydrophobic rutile TiO2 particles (5 wt 3.2.3. Other crystal
%) and ASA has a thermal emissivity of 0.87 in the region of 8–13 µm, Some crystals show their cooling potential in RC applications. Xu
whose excellent characteristics of water resistance making it satisfy the et al. (2018) hydrothermally synthesized a new crystal
strict requirements in the outdoor environment. Mg11(HPO3)8(OH)6 (Fig. 9a). The crystal could efficiently dissipate heat
to outer space owing to 87.57% emissivity occurring between 2.5 and
3.2.2. Hafnium dioxide (HfO2) 25 µm region and reflect most of the solar light radiation up to 88.04%
HfO2 has low ultraviolet absorption and serves as a high-index between 0.2 and 2.5 µm range. In a cooling test under direct sunlight,
material, which can be used to optimize the solar reflectance, while the Mg11(HPO3)8(OH)6 coating can be 6 to 8°Celsius smaller than the
optically transparent SiO2 can serve as the low-index layer (Raman Al-foil, and 2 to 4°Celsius lower than solar reflective products consisting
Fig. 9. (a) SEM of Mg11(HPO3)8(OH)6 particles (×5 & ×80 K); (b) Comparison of the measured cooling effect of different coatings, specifically: Mg11(HPO3)8(OH)6,
TiO2, CaCO3 and Al-foil (Xu et al., 2018).
255
of CaCO3 as well as TiO2 (Fig. 9b). radiation than the one in the dense membrane and a traditional textile
(Fig. 11). Thus, the proposed membrane could be 0.4–1.7 °C cooler than
3.3. Back-reflector (mirror layer) the commercial clothing garments and 1.0–2.5 °C cooler than the sur-
rounding air temperature under an isolated thermal convection and
Various substrates have significant influences on the spectral conduction condition, showing thermal-moisture comfortability and
emissivity of cooling coatings. The emissivity of an RC structure gra- sufficient air permeability because of its interconnect micropores and
dually increases with the declining substrate reflection (Cheng et al., nanopores.
2019). Different from the reflective material layer, the back-reflector is Compared to the microstructure-based coating, the simple poly-
more commonly existing in the RC structures. Highly reflective metal, merization could be less expensive; therefore, it can be used as a matrix
such as aluminium (Al) (Suryawanshi and Lin, 2009), silver (Ag) (Liu material for massive applications. Poly (acrylonitrile-styrene-acrylate)
et al., 2019c) and copper (Cu) (Cunha et al., 2020) are typical back- (ASA) resin was selected due to its excellent weather resistance (Qi
reflectors. Al has a higher average reflectivity than Ag, showing an et al., 2017). For micro SiO2 spheres randomly distributed structure,
increased absorption in the ultraviolet (Wang et al., 2015). The Ag layer polymethyl pentene (TPX) is used as the matrix material due to the
could be more efficient and achieve higher reflection at the visible lightweight and easy to laminate on curved surfaces, showing a negli-
spectrum when combined with high index-low index periodic layers gible impact on the overall performance (Zhai et al., 2017). Carbon-
(Kecebas et al., 2017). based materials are also dispersed in acrylate emulsion as composite
Bao et al. (2017) propose a scalable double-layer coating with SiO2, materials (Suryawanshi and Lin, 2009). Fan et al. (2019) introduced a
TiO2, and SiC nanoparticles to achieve selective radiative properties. double-layer structure composing of a SiO2 microballs embedded
The cooling performances of the double-layer layer on different sub- within silver coating (FPI@SiO2/Ag) and transparent fluorinated
strates, Al thin sheet covered with/without dark paint, were compared polyimide. The FPI@SiO2/Ag foil was doped with 3 wt% and possessed
(Fig. 10). The double-layer coatings can reduce the dark surface tem- high emissivity (0.94 ± 0.03 at 8–13 μm wavelengths) and ultralow
perature by 30 °C or more during daytime and cool down the alumi- solar absorptivity (0.07 ± 0.02), achieving a temperature reduction of
nium sheet by 5 °C at nighttime and 8 °C at daytime. Meanwhile, 4.6 °C under direct solar radiation. Being prepared through a simple
TiO2 + SiC and TiO2 + SiO2 can cool the aluminium substrate by a process of in situ polymerization, the foil is cheaper than microstructure
couple of degrees heated directly by solar radiation and be 5°below air coatings.
temperature during nighttime. Similarly, the hierarchically porous poly(vinylidene fluoride-co-
hexafluoropropene) [P(VdF-HFP)HP] coatings show ideal intrinsic
3.4. Matrix material electromagnetic properties for RC applications (Mandal et al., 2018b).
As shown in Fig. 12(a), the hierarchical structure consists of ~2–10 mm
For the large-area applications, nanoparticle mixture materials and micropores divided by a nanoporous phase, where the ~5 mm micro-
polymer materials are the first choices because of the low cost and pores scatter efficiently all-wavelength radiations while those with sizes
mature manufacture technology (Fan et al., 2019; Liu et al., 2019c). of ~50–500 nm strongly scatter visible, shorter wavelengths. The paint-
Lallich et al. (2009) modelled the radiative transfer in nanoporous silica like applicable coating shows a high longwave IR emittance of 0.97 and
matrices. Xiao et al. (2019) utilized a nanofiber membrane (NFM) to a substrate-independent hemispherical solar reflectivity of around 0.96.
enhance the infrared radiation for the efficient RC of the human body. Thus, it can efficiently radiate heat in the atmospheric window, redu-
Such textile has proper selective thermal radiation and infrared re- cing ~6 °C of the sub-ambient temperature (Fig. 12b) and ~96 W/m2 of
sonance absorption to enable radiating from the human body to outer the cooling powers.
space. The RC device randomly distributes SiO2 submicron spheres in An accessible and inexpensive black acryl paint was used as a sub-
the polyamide 6 (PA6) nanofiber membrane, and it has higher IR strate coating in a hybrid photothermal as well as RC collector (Hu
Fig. 10. Schematic of a double-layer coating design and the measured emissive spectra of different nanoparticles coated on Al foil and black substrates (Bao et al.,
2017).
256
Fig. 11. (a) SEM, (b) Schematic and (c) Ultraviolet–visible-near-IR spectrophotometry and Fourier transform IR transmittance of the polyamide 6/SiO2 nanofiber
membrane (in blue) compared with fabric (in the dark) and PA6/SiO2 dense membrane (in red) (Xiao et al., 2019).
et al., 2019). Its thermal efficiency could be 63.0% at zero-reduced compared. Among them, BaF2 showed the best RC performance with a
temperature and 58.3% at zero-dimensionless temperature difference max cooling rate up to ~120 W/m2 and a saturation temperature below
under bright sky condition. Zhao et al. (2019a) fabricated a radiative 270 K. In contrast, a slightly higher temperature reduction rate could be
cooler with a polydimethylsiloxane film and a reflective metal sub- found in ZnS at higher (near ambient) temperatures.
strate. The field test results show that such structure can reduce the Kou et al. (2017) introduced a mirror-like polymer with silica for
ambient temperature by 3.2 °C, indicating its potential to achieve passive RC, where from top to bottom layers are polydimethylsiloxane
daytime sub-ambient RC. layer, a silver back-reflector layer and a fused silica wafer layer. Be-
cause of the absorption of PDMS and silica, an almost unity emissivity
3.5. Insulation material could be found in IR wavelengths greater than 4.5 μm (Fig. 13). The RC
structure showed almost perfect reflection within the solar spectral
Besides the surface-based designs with selective emission, selective range as a near-perfect blackbody within mid-IR range, it could de-
radiation can be achieved by particular transmission through the increase the surrounding temperature by 8.2 °C under solar radiation
sulating cover. Kim and Lenert (2018) investigated various designs of directly and by 8.4 °C at night. This cooling ability exceeds that of the
IR-transparent thermal insulation for RC used below ambient tem- vacuum-deposited nano-layered structures by nearly 3 °C. The cooling
peratures. An excellent RC performance with a 35 K temperature re- power during daytime was estimated to be ~127 W/m2.
duction was achieved by combining selectively high transparency and The low-density polyethylene film is widely used in RC devices due
low thermal conductivity in the atmospheric window. Then the per- to its high transmittance in the vast majority of spectral-region, which
formances of structures with BaF2, ZnS, and polyethylene (PE) were allows the solar irradiance and infrared thermal emission to penetrate
Fig. 12. (a) Micrographs and (b) Temperature data measured of P(VdF-HFP)HP (Mandal et al., 2018b).
257
Fig. 13. Measured emissivity of the polymer-silica-mirror (black solid) and silica-mirror (red solid) from ultraviolet to far-infrared. Ideal scenarios where unity
emissivity beyond 4.5 μm (green dashed) and only in the main atmospheric transparency window (blue dashed) (Kou et al., 2017). (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
(Cunha et al., 2020; Hu et al., 2020a). For example, the combined (Ono et al., 2018), the system performs RC with a higher temperature
photothermic and RC module includes a 6 μm-thick film as the wind- above the transition temperature of VO2, and automatically shut down
screen and a 2.8 mm-thick ultra-white glazing cover to protect the when the temperature drops below the transition point. Using the
emitter (Hu et al., 2020a). thermally switchable Fabry-Perot-like resonance mode for the atmo-
Leroy et al. (2019) integrated the existing emitters with a poly- spheric window, Wu et al. (2018) introduced a structure with a VO2/
ethylene aerogel (PEA) material. Due to the highly porous structure SiO2/VO2 cavity, which could thermally switch the RC power of pro-
(Fig. 14a), PEA has a thermal conductivity as low as the air one and posed metasurface up to four-fold theoretically. Taylor et al. (2017)
strongly scatter at shorter wavelengths (0.3–2.5 mm), bringing a high proposed an asymmetric Fabry-Perot emitter with an opaque alumi-
reflectance of 0.922 and a 79.9% transmittance (8–13 mm). The nium substrate and VO2 thin films. When vanadium dioxide is dielectric
structure can achieve a passive cooling by up to 13 °C lower than am- below 68 °C, the film has less thermal radiation loss and high reflection
bient temperature (Fig. 14b) and a daytime 96 W/m2 cooling power. (Fig. 15a). When the temperature rises to above 72 °C, the metallic VO2
have a Fabry-Perot resonance cavity, which provides wideband emis-
3.6. Dynamic switch sivity occurring 10 mm wavelength and therefore, the RC effect
(Fig. 15b). As shown in Fig. 15(c) and (d), with phase transition of
Adaptive control of broadband light is essential for light modulation vanadium dioxide, the emission power of the structure could be im-
and building energy management, and it can be achieved by the phase proved by 6.5 times for extra-terrestrial spacecraft systems and 7.3
change materials including thermochromic materials (Ji et al., 2018; times for buildings. Therefore, the dynamic radiative cooling applica-
Ono et al., 2018; Taylor et al., 2017), electrochromic materials (Mandal tions could be a promising choice especially for a variable environment.
et al., 2018a) and materials achieving optical switching through wet- A similar function can be provided by the “visible to infrared wa-
ting (Mandal et al., 2019), etc. velengths” electrochromic materials. Li4Ti5O12 varies from a wide-
Thermochromic materials, i.e. vanadium dioxide (VO2), can be used bandgap semiconductor to a metal with Li+ intercalation, and it con-
to achieve a self-adaptive RC system (Ono et al., 2018; Taylor et al., tributes to a sub-ambient temperature up to 3.9 °C and a tunable tem-
2017). As a harmful differential thermal emissivity material, VO2 can perature range of 18 °C under sunlight (Mandal et al., 2018a).
change its structure from metal to insulator at 68 °C, actively mod- Besides the adaptive control achieved by temperature variation,
ulating infrared emissivity and reacting to the ambient temperature. It materials sensitive to the wetting can reflect the optical change. Mandal
is an adaptive camouflage material for both mid- and far-infrared re- et al. (2019) presented porous polymer coatings (Fig. 16a and c), whose
gions and can be applied with large or complex substrates (Ji et al., optical transmittance changes upon reversible wetting with common
2018). The metallic VO2 and V2O5 share the same emissivity, while liquids. The coatings change from reflective to transparent with the
significantly different ones in mid-infrared regions if heated up over the reduced optical scattering upon wetting changes under solar radiation
phase transition temperature (Ji et al., 2018). (Fig. 16b and e). The solar and visible transmittance changes of poly
By adopting the phase change materials, RC can automatically be (vinylidene fluoride-co-hexafluoropropene) coatings could be up to
turned on or off based on its temperature at no expense of extra energy 0.74 and 0.80, respectively (Fig. 16c). The infrared transparent poly-
input for switching. For a VO2 integrated spectrally selective filter in ethylene coating showed an “icehouse-to-greenhouse” transition
Fig. 14. (a) SEM Image of a PEA sample; (b) Stagnation temperature of radiative cooler with/without 12 mm-thick PEA over a 24-h period (Leroy et al., 2019).
258
Fig. 15. Schematic of the proposed structure and wave propagation when the VO2 top layer is a) metallic (T > 72 °C) and b) insulating (T < 68 °C); Comparisons of
(c) Total hemispherical emissivity and (d) Radiative power (Taylor et al., 2017).
(Fig. 16e) with the decreasing thermal infrared and increasing solar 4. “Continuous” “Discrete” structural configuration of radiative
transparencies caused by the wetting (Fig. 16f). The coating gave an cooling technology
above-ambient solar heating of 21.4 °C and a 3.2 °C switchable sub-
ambient radiative cooling, making it attractive for large-scale thermal Instead of material selection, the RC structures can be improved to
and optical managements. obtain better cooling performance. Their design optimization mainly
Fig. 16. (a) SEM, (b) Photo and (c) Spectral hemispherical transmittance of porous P(VdF-HFP) in dry and wet states; (c) SEM, (d) LWIR thermographs and (e)
Spectral hemispherical transmittance of porous polyethylene in dry and wet states (Mandal et al., 2019).
259
Table 2
Different RC structures.
No. Structure Schematic diagram References
1 Double layers structure (Bao et al., 2017)
2 Seven alternating layers structure (Raman et al., 2014)
3 Metallodielectric multilayer structure (Suichi et al., 2018)
4 Multilayer structure (Chae et al., 2020)
5 Metasurface structure (Zhai et al., 2017)
6 Metasurface structure (Huang and Ruan, 2017)
(continued on next page)
260
Table 2 (continued)
No. Structure Schematic diagram References
7 Metasurface, Al-doped ZnO (Sun et al., 2018)
8 Multilayer and metasurface structure with VO2/SiO2 cavity (Wu et al., 2018)
9 Multilayer and metasurface structure (Rephaeli et al., 2013)
10 Multilayer and metasurface structure (Zhao et al., 2018)
adopts the basic configuration of “continuous layered structure” and higher refractive index (Fig. 17a & b). The device gave high emittance
“discrete nanostructures” or both. Table 2 presents a selection of dif- and low reflectance in the sky window, and high hemispherical re-
ferent RC micro/nanostructures. flectivity. The experimental results show the device will reduce the
temperature by averagely 7.4 °C during nighttime and 2.5 °C during
4.1. Multi-layered composite structure design daytime in winter, corresponding to a net cooling performance up to
~43 W/m2 (Fig. 17c).
The multi-layer structure is widely adopted to enhance cooling ef- With large imaginary parts of the refractive index in the infrared
fects through (1) photonic structure optimization including using per- region, Al2O3, Si3N4 and SiO2 were selected and composed a simple
iodic layers; (2) multi-function layers. The supplement of materials (e.g. multilayer structure to achieve broad and high emission through the
insulation and reflection materials) can efficiently improve the RC atmospheric window (Chae et al., 2020). This inorganic cooler has an
performance without reselecting the emitting materials. For emitting averaged emissivity of 87% (8–13 μm) and absorptivity of 5.2%
materials, the super-lattice characteristic of multilayer design can en- (0.3–2.5 μm), and it can reduce the temperature to 8.2 °C lower than
hance the absorption ability in the relevant spectral range (Diatezua the ambient one under sunlight radiation. The stacking sequence and
et al., 1996; Eriksson et al., 1985) or cover the whole atmospheric thicknesses of these material layers are usually determined by the
window (8–13 μm) (Chae et al., 2020). For example, from single SiO structure design. Unlike most structure, the double-layer coatings pro-
film (Granqvist and Hjortsberg, 1981) to silicon oxynitride multilayers posed by Bao et al. (2017) has a reflective coating layer with high solar
(Diatezua et al., 1996), the broadened absorption peak within 8–13 μm reflectivity at the top, and a high emissivity layer with properly de-
contributed to a significant temperature drop and an increasing cooling signed SiO2, SiC and TiO2 nanoparticles on the bottom (Fig. 10).
power for the nighttime RC. Additionally, for materials with complementary optical character-
By integrating various macroscopically planar into a multilayer istics, a periodic layer design of them can yield high reflection and
structure though the photonic approach, the radiative coolers can col- emission around the desired wavelength (Kecebas et al., 2017; Raman
lectively achieve strong thermal emission and high solar reflectance et al., 2014). Most conventional techniques use high reflective metallic
within a wide wavelength range (Chae et al., 2020; Cunha et al., 2020; (silver) layers, while they could be less efficient because of the high
Raman et al., 2014). Cunha et al. (2020) produced a multilayer selec- absorption in the near-infrared and visible spectrums. To avoid such
tive RC coating with Al/SiO2/SiNx/SiO2/TiO2/SiO2 via direct current strong absorption, a structure of repetitive high-low index periodic
magnetron sputtering. Compared to amorphous SiO2 and SiNx layers, layers can be adopted (Fig. 18a) (Kecebas et al., 2017). In this practical
TiO2 layer with partial rutile polycrystalline lattice arrangement has a structure, TiO2 is a layer with a high refractive index and SiO2 a low
261
Fig. 17. (a) Schematic and (b) Crosssectional SEM image of the multilayer cooling device; (c) Surface temperature of the cooling device (Tdesign) was compared with
ambient temperature (Tambient) during the day and night times (Cunha et al., 2020).
refractive index. The structure can generate a desired high reflection A numerical study of an RC coating from Cheng et al. (2019) shows
zone with alternating high-low refractivity between its dielectric layers. that the characteristic spectral parameters decrease with the increasing
As shown in Fig. 18(b), the averaged reflections could be enhanced size of nanoparticles. The higher the particle volume fraction, the better
from 98.51% to 99.9% and the absorption percentages from 68.53% to the emissivity and spectral parameters. The spectral reflectance differ-
79.74% if the number of layers increased from 6 to 12. The increasing ence of coatings with/without uniform distributed particles cloud be up
high reflection and emission gave high-performance improvements in to 27.3%. Moreover, most significant effects of particle parameters and
the desired spectra, which increased the reflectance of the near-infrared substrate reflectance for the RC coating can be found in the 10–12 μm
and visible spectrums averagely by 3–4% with a minimum 35 W/m2 band, where the spectral emissivity rises with the increasing coating
cooling power. thickness. However, caused by the strong absorption of SiO2 particles,
The alternating multi-layer structure was also considered in the 7- there is less variation for coating with different particle parameters and
layer structure proposed by Raman et al. (2014), as shown in Fig. 7. The reflectance within regions of 8–10 μm and 12–13 μm wavelength
layer thicknesses were optimized by simulated annealing and quasi- (Cheng et al., 2019).
newton methods. With a substrate layer of Ag, HfO2 and SiO2 are al- Besides the size selection of the nanomaterials, their morphology
ternating inserted layers. The photonic RC device was coated via E- and nanostructures instead of the flat layer are optimized to improve
beam evaporation on the surface of the silicon substrate by LGA thin the RC performance. The light could easily pass through the smaller
films, then Ti adhesion layer, followed by silver and other seven al- (nano-scale) structures and further enhance the absorption and emis-
ternating dielectric layers of SiO2 as well as HfO2. sion of some wavelengths and suppress that of others. Li et al. (2019b)
Moreover, since various materials have different optical character- completely delignify and densify the wood to develop a cooling struc-
istics, their combination can provide additional functions to the structural material. Its cellulose nanofibers can backscatter sunlight and emit
ture, such as the functions of adaptive control obtained through ther- strongly through the atmospheric sky window with an average emis-
mochromic materials (Ji et al., 2018; Ono et al., 2018; Taylor et al., sivity of more than 0.9. Moreover, since both surface and atmospheric
2017), electrochromic materials (Mandal et al., 2018a) and materials emissivity rely on the radiation angle and usually the normal direction
achieving optical switching through wetting (Mandal et al., 2019), etc. receives the maximum radiation, it is ideal for RC surfaces to have less
variation in emissivity as the zenith angle ranging from 0 to 90°
(Granqvist and Hjortsberg, 1981). Besides adjusting the device, the
4.2. Discrete Nano/micro-structures design angle can be tuned at the material level (Zhao et al., 2019f). Therefore,
the morphology of the nanostructures should be optimized to improve
RC performance depends on the size (morphology) of their mate- the RC more efficiently.
rials. For the RC coating, the actual particles constitute a non-uniform To obtain ideal thermal emitter, Hossain et al. (2015) design and
distributed particle cloud, where the spectral reflectance of the actual demonstrate a microstructure consisting of a metamaterial that is fab-
substrate can significantly influence the cooling effect. The Reststrahlen ricated with small pillars shaped like micro-cones (Fig. 19a), the pillars
band of the material refers to the spectral regime of strong optical have alternating layers of germanium and aluminium. Every pillar has
phonon coupling. The Reststrahlen band of a bulk material shows a seven periods of metal-dielectric layers, and every dielectric and metal
strong reflection peak. In contrast, the nanoparticle-sized material can layer maintain the circular symmetry along the vertical axis, forming a
induce surface phonon polariton and show strong optical absorption conical shape structure. This structure can radiate through the
and emission (Bao et al., 2017).
Fig. 18. Schematic of the multi-structure and its (b) absorptions in 8–13 µm spectrum with 6, 8, 10 and 12 layers (Kecebas et al., 2017).
262
Fig. 19. (a) SEM images and (b) Calculated emissivity spectra of the CMM structures with different bottom pillar diameters (Hossain et al., 2015). (c) Normal-view
and (d) a side-view SEM images of the 2D silica photonic crystal structure (Zhu et al., 2015); (e) Measured emissivity/absorptivity of absorber structures with nothing
(black), planar silica layer (blue) and silica photonic crystal (red) (Zhu et al., 2015). (f) Schematic and (g) emissivity/absorptivity spectrum (black) of the modified
structure with quartz bar array on top of silicon nanowires (Zhu et al., 2013). (For interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
atmospheric window selectively and minimize the radiation absorption visible transparent with two phonon-polariton resonances at specific
outside the transparency window (Fig. 19b). Therefore, it shows a near- phonon wavelengths, α-Quartz was used to radioactively achieve RC of
unity absorption of unpolarized light, a 2 °C temperature reduction the structure with the same color preserved under direct sunlight (Zhu
compared to the ambient temperature and high cooling power of more et al., 2013). As shown in Fig. 19(f), on top of silicon nanowires or-
than 100 W/m2. thogonally lays a periodic array of quartz bars. Fig. 19(g) shows the
Zhu et al. (2015) fabricated a photonic crystal made of silica as a structure’s absorptivity over a 0.3–30 μm wavelength. The addition of
visibly transparent thermal blackbody. As shown in Fig. 19(c) and (d), quartz array can enhance the emissivity at thermal wavelengths, and
the 500 μm-thick 2D silica photonic crystal structure has a 6 μm peri- almost keep the same absorption visible spectrum with original color
odicity and 10-μm deep holes in the centre. Compared to the bare remained.
structure (black curve), the emissivity could be significantly improved The nanoscale structure is commonly integrated with the multi-
by fabricating a uniform silica planar layer on the top (blue curve), and layer structure design. For example, Hervé et al. (2018) proposed a
even provide a near-unity one with the photonic crystal made of silica structure by placing the gratings on top of the multi-layers (Boron Ni-
(red curve) (Fig. 19e). The blackbody can preserve or slightly enhance tride, SiC and SiO2) for the first time. The structure can improve the
the sunlight absorption, which can reduce the temperature of the ab- emissivity in the atmospheric window and provide an almost ideal re-
sorptive silicon layer beneath by up to 13 °C under sunlight. Being flectivity in the solar spectrum, therefore, an averaged value of 55 W/
263
m2 during daytime and a maximum RC power of 80 W/m2 at night. attractive energy saving while no energy input and limited maintenance
Rephaeli et al. (2013) proposed an optimized radiative cooler design needed (Testa and Krarti, 2017; Zhao et al., 2019f). For a sizeable cool
consisting of SiC and quartz to achieve RC in outdoor daytime condi- roof application in Sicily, the eco-friendly paint has a washable gloss
tions. As shown in Fig. 20, the metal-dielectric photonic structure emits emulsion coating and double-layer paint on primer, and it shows ex-
actively in the mid-infrared spectrum through the sky window and cellent solar reflectance (85.9%) and radiative emittance (0.88). Cool
behaves as a broadband mirror for sunlight. It gave a brilliant RC roofs could decrease the surface temperature by up to 20 °C, the op-
performance with a net cooling performance over 100 W/m2 at ambient erative temperature averagely 2.3 °C and 54% of the cooling energy
temperature. demand, which shows its potential under European climatic conditions
The micro/nanostructure should not limit to the utilization of op- (Romeo and Zinzi, 2013). Li et al. (2019b) introduced a cooling
tical metasurfaces; the structures themselves can show better perfor- structural material made from wood, with high emissivity and solar
mance with other physical effects. For example, metals usually serve as reflection, the highly efficient RC material would contribute to the
back-reflectors rather than thermal emitters due to their “close to zero” energy savings of 20–60% if applied to the exterior surfaces of build-
emissivity. Instead of the conventional nanostructure patterning to in- ings.
crease emissivity, Wang et al. (2015) proposed an alternative approach Most cool roofs have a thermal emittance of 0.90 (Testa and Krarti,
by using the tunneling effect in ultra-thin films. Thus, without sufficient 2017), and they usually can achieve net cooling powers of over 90 W/
charges to screen the oscillating current, the emission of the extremely m2 during daytime (Hossain et al., 2015; Huang and Ruan, 2017;
thin flat film was drastically improved at low cost. Rephaeli et al., 2013; Zhai et al., 2017) and over 120–180 W/m2 at
nighttime (Hossain et al., 2015; Huang and Ruan, 2017; Kim and
5. Radiative cooling technology for buildings Lenert, 2018) at the ambient temperature. Many existing references
have studied the cooling potential and indoor thermal comfort im-
Buildings can apply the RC technology in a passive way (e.g. cool provements brought by cool roofs (Bozonnet et al., 2011; Kolokotsa
roofs, painting, etc.) or an active way for PV and water cooling. et al., 2013; Romeo and Zinzi, 2013; Takebayashi et al., 2012; Xu et al.,
2012).
Cool roofs have superior advantages than the conventional roofs.
5.1. Cool roofs
Fang et al. (2019) developed a new cool roof with metamaterial film
called RadiCold. With an improved Roof Thermal Transfer Value
As a directly passive utilization, a cool roof can reflect more solar
model, RadiCold was estimated to dissipate more than 100 kWh/
radiation to the outer space and absorb less heat when compared to a
(m2·yr) of heat from the buildings to the outdoor environment for a
standard roof. With exterior RC surfaces or coatings, cool roofs can
year. In contrast, buildings with shingle and another cool roof material
maximize thermal emittance and minimize solar absorption, to reduce
called Thermoplastic Polyolefin absorbed heat. The cooling load re-
urban heat island (UHI) effect, air pollution and building cooling de-
duction would further save the cooling electricity by more than 88
mands (Kolokotsa et al., 2013; Santamouris et al., 2011; Xu et al.,
kWh/(m2·yr). Cool roofs can successfully reduce the internal ceiling
2012). The commercial cool roof products can be categorized as white
surface temperature averagely by up to 5.5 °C and cooling demand of
finished metal panels, liquid-applied coating and single-ply (ASHRAE,
190 kWh/m2/year, which can bring thermal comfort to low income
2011). The reflectance of white elastomeric coating ranges from 0.60 to
households in tropics (Kolokotroni et al., 2018). Zhao et al. (2019d)
0.85, and the single-ply one is usually more than 0.70; emittance of the
integrated the cool roof and radiative air-cooling system by utilizing RC
non-metallic surface is 0.80–0.90 while the low emittance of metal
technology to cool the attic temperature. The glass-polymer radiative
makes it as hot as the dark roof (Testa and Krarti, 2017).
cooler in Zhai et al. (2017) was constructed to be a 1.08 m2 radiative air
Applications of RC materials on cool roofs are appealing with
Fig. 20. (a) Scheme and (b) Emissivity

ε(λ,0) of the optimized daytime radiative
cooler at normal incidence (black) with the
scaled AM1.5 solar spectrum (yellow) and
atmospheric transmittance t(λ) (blue)
(Rephaeli et al., 2013). (For interpretation
of the references to color in this figure le-
gend, the reader is referred to the web ver-
sion of this article.)
264
cooler. For the experimental results, the ambient temperature was RC. Similarly, the multi-selection of power and heat collections were
measured to be reduced by 3–5 °C during noontime under direct sun produced in (Hu et al., 2020b). They combined the nocturnal RC and
heating and 5–8 °C at night. Therefore, with different attic insulations, diurnal solar heating technologies as a collector (Fig. 21b). This col-
the temperature of the attic could be reduced by 15.5–21.0 °C when lector can realize annual heat gains more than 2423.53 MJ/m2, and net
compared to a shingle roof in summer in a single-family house. yearly RC gains more than 741.63 MJ/m2 (Hu et al., 2018). Lu et al.
The thermal performance of cool roofs depends on their solar albedo (2017) proposed to use ultra-broadband versatile textures in the silicon
(a), thermal emissivity (E), and R-value (insulation). Through 18 si- solar cells, which shows an emissivity of over 0.96 (8–13 μm) and a
mulations for parameter analysis conducted by Gentle et al. (2011), conversion efficiency improvement of 3.13%. The cost-effective and
high albedo shows the predominance in RC, and its increase will long-term durable textures would be beneficial to the light and thermal
weaken the sensitivity of heat gains to R-value and emissivity. The management of PV.
traditional approach of thermal insulation (increasing R-value) brings The conventional PV module covered by glass has a hemispherical
relatively higher costs for roofs with high albedo; therefore, the roof emissivity of 0.84, contributing to an additional cooling of 1.5 °C
with high a and E but moderate R-value performs the best when con- (Gentle and Smith, 2016). The temperature reduction of the solar cell is
sidering the costs. With high albedo (> 0.96) and emissivity (> 0.97), only ~1 °C if the glass is replaced by a material with a unity emissivity
the super-cool rooftop was predicted to have a cooler temperature (Sato and Yamada, 2019), and the average efficiency improvement is
below the ambient one throughout the year and double the cooling about 1.0% (Nižetić et al., 2017). Considering the marginal cooling
energy saving when compared to the typical white roofs (Baniassadi performance and additional costs brought by the emissivity improve-
et al., 2019). ment, the typical glass is sufficient for the PV cooling, and more effi-
As for the payback periods and costs of cool roofs, the applications cient cooling methods are still in need.
of cool roofs (reflectance of 0.3–0.4) can save the energy cost ranging
from USD$0.16/m2 to $0.36/m2 per year under US climates (Testa and 5.3. Water cooling
Krarti, 2017). For tropical climate (e.g. in Singapore), the application of
cool roof paint is estimated to save annual cooling energy by USD$33/ Besides the passive approaches to apply RC technology to air, it can
m2 through life cycle analysis, and the payback periods are < 6 or also be used more efficiently and actively to cool the heat transfer fluid.
2 months for the roofs with or without ventilation (Zhang et al., 2016). The heat can be transferred from circulating water to the sky through
solar collector pipes, and the maximum dissipation power could be
5.2. PV cooling 100 W/m2 (Guerrero Delgado et al., 2020). Guerrero Delgado et al.
(2020) studied the dissipation powers of systems with water circulating
The photovoltaic (PV) cells used in buildings could be overheated to inside pipes or flowing down to the collector, and the mean values were
worsen the desired operating conditions due to their exposure to high- 1.3 kWh and 2.3 kWh, respectively.
temperature sources such as the sun. Thus, their efficiency would de- Zhao et al. (2019e) proposed a so-called RadiCold water-cooling
cline by about 0.45% with a 1 °C temperature rise for crystalline silicon module, as shown in Fig. 22. The central flat panel water container was
solar cells (Skoplaki and Palyvos, 2009). Meanwhile, the aging rate surrounded by polyisocyanurate board insulations and covered by a
doubles for every 10 °C increase under the operation condition (Sharma metamaterial thin film. The polymer-based low-cost RC metamaterial
and Chandel, 2013). The operating temperature of solar cells should be was proposed by Zhai et al. (2017) and manufactured through roll-to-
reduced while ensuring their solar absorbance. Therefore, unlike most roll (R2R) extrusion. This system can reduce the temperature of a large
traditional RC studies (Catalanotti et al., 1975; Nilsson and Niklasson, mass of water by up to 10.6 °C lower than the surrounding temperature
1995; Nilsson et al., 1992), solar cells should absorb sunlight during by under solar irradiation at noon. With a 13.5 m2 RC surface, the
daytime while achieving RC. The ideal RC materials used in PV cells system with can achieve a maximum of 1296 W cooling power during
should have high spectral absorptivity (emissivity) values to achieve a nighttime, and an averaged 607 W cooling power at noon. Integrated
high cooling power at nighttime while efficient heating during daytime. with HVAC and cold-water storage system, this system is predicted to
Fig. 21(a) presents the characteristics of ideal PV cells for both solar save up to 46% of the annual cooling electricity and achieve a payback
absorbing and RC. Hu et al. (2017) proposed a novel combined solar period of 4.8–8 years with maximum acceptable incremental costs of
photovoltaic PV with thermal radiative RC combination to collect heat $50.0–$78.9/m2 for a single-family house (Zhang et al., 2018). The RC
energy and electricity during the day through photothermal and PV cooling can also be combined with thermoelectric TE cooling to en-
conversions and achieve cooling performance during the night through hance the cooling performance by increasing the coefficient of
Fig. 21. (a) Spectral absorptivity (emissivity) of the ideal surface for both solar heating and radiative cooling; (b) Scheme of the solar heating and nocturnal radiative
cooling (SH-RC) collector (Hu et al., 2018).
265
Fig. 22. Schematic of (a) RadiCold Module and RadiCold Metafilm and (b) Bilayer RadiCold metafilm on top of the polycarbonate water container. (c) Photograph of
the roll-to-roll (R2R) produced RadiCold metafilm without (left) and with (right) silver layer (Zhao et al., 2019b).
performance (COP) of system. Theoretically, the RC subsystem could concentrating solar thermal power plants. These coolers can be added
provide to 55.0% and 45.0% of the yearly cooling power capacity (heat after the air cooler, and it can efficiently enhance the system efficiency
dissipation) for the diurnal and nocturnal cooling, respectively (Zhao by 5% and 7% for the simple and recompression supercritical carbon
et al., 2020). dioxide cycles, respectively (Zeyghami and Khalili, 2015).
5.4. Other applications 6. Recommendations and conclusions
The RC technology can also be applied on greenhouse (Liu et al., As a promising approach to prevent cities from overheating, radia-
2019a), windows (Tso et al., 2017; Wong et al., 2018), and integrated tive sky cooling has been proposed and investigated through recent
with solar power plants (Zeyghami and Khalili, 2015). Particularly, the decades. This review comprehensively summarizes the materials and
RC materials can be directly used in the greenhouse. Liu et al. (2019) nano/microstructures of the radiative cooling technology. The mate-
prepared plastic films with UV stabilizer and non-metal oxide particles. rials with high reflectivity in the solar spectrum and high emissivity in
The net cooling power of the RC film was 28 W/m2 higher than that of the transparent window are required for the daytime cooling. In con-
the conventional PE film, and RC film was 2.2 °C cooler than the contrast, the high emissive materials are needed for nighttime cooling.
ventional one. In this review, we have covered numerous works and summarised
Most of the radiative coolers perform better under hot and dry cli- the following recommendations in order to enhance the RC materials,
mates, while poor in a humid environment because of the effects of configuration design and highlighting limitations:
humidity and cloud coverage (Feng et al., 2020). To enhance cooling
power in high humidity climatic conditions, Wong et al. (2018) first (1) Continuous multilayer structures have one of the highest or best
integrated the system with an asymmetric electromagnetic transmission cooling performance. However, they are expensive and difficult to
(AEMT) window, the combined structure can allow greater outgoing fabricate due to the vacuum deposition technique (Raman et al.,
emittance and reflects incoming direct radiation belonging to identical 2014).
wavelengths. Theoretically, the AEMT window could save the cooling (2) Discrete nano/micro-particles have relatively worse cooling per-
performance of RC cooling by 57%. Tso et al. (2017) compared the formances versus continuous multilayer structures (Gentle and
diurnal and nocturnal performances of three designs including one Smith, 2010; Miyazaki et al., 2016; Xiao et al., 2019).
system with a single KCl IR-Pass window, non-vacuum and vacuum (3) Discrete nano/micro-particles on the polymer are mainstream, low-
with seven KCl IR-Pass windows under different clear, overcast and cost and affordable (Raman et al., 2014).
partially overcast climatic conditions. The RC cooler with seven KCl IR- (4) Better radiative cooling structure with economic and robust cooling
pass windows and the one without vacuum gave good temperature performance can be achieved through the combination of “multi-
reduction during the night with a 6–7 °C ambient temperature reduc- layer” and “nanostructure” from a materialistic perspective.
tion, while no cooling performance during the day under Hong Kong’s (5) Popular materials such as SiO2 nanoparticles are cheaper and
hot and humid climatic conditions. widely studied, while expensive toxic materials such as HfO2 and
The radiative coolers show the potential to integrate with air-cooled vacuum deposition are not recommended.
266
(6) The dynamic switch, including thermochromic materials, will in- Acknowledgement
crease the cost of materials and complexity of RC system. Popular
thermochromic phase change materials such as VO2 and organic This work has been supported by NUS-AGC Inc. project R-296-000-
pigments have been studied. 183-597 and Start-up Grant R-296-000-165-133. Acknowledgement is
(7) High humidity affects the performance of RC cooling (Feng et al., also given to Department of Building, National University of Singapore.
2020), especially the emitting performance. Therefore, novel ma-
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Solar Energy 207 (2020) 247–269

Contents lists available at ScienceDirect

A materials perspective on radiative cooling structures for buildings T

ARTICLE INFO ABSTRACT

1. Introduction wavelength ranging from 8 μm to 13 μm, without external energy input

Nomenclature PEA Polyethylene aerogel

Fig. 1. Overview of the review paper.

fundamental theory of RC technology and depicts the ideal materials; where d =2 0

to their functions; Section 4 highlights the design principles of these e 1

Fig. 3. The heat balance of building surfaces.

2.2. Ideal materials

3. Materials used in radiative cooling technology

These materials are summarised based on their primary functions:

3.1. Selective emitting material

Fig. 5. Schematic of radiative transfer for RC nanomaterials (Cheng et al., 2019).

Fig. 6. Design and optimization of the radiative cooling material structures.

of multiwall CNT contributes to a 17 °C temperature reduction. With

(Kim and Lenert,

(Xu et al., 2018)

shows non-absorption in the near-infrared and visible spectrum, and it

96 W/m2 shows higher absorption rates beyond 10 µm spectrum compared to

The Al2O3 design dramatically increases the emission, improving the

Indium tin oxide (ITO), a transparent conductive oxide, is one of the

promising plasmonic material for selectively emitting in the infrared

wavelength. Dao et al. (2019) proposed tri-layer plasmonic absorbers of

ITO-Al2O3-ITO tri-layers with hexagonal ITO disks on top. The structure

The nocturnal RC only plastic foils with non-absorbing pigments can

be used for water condensing, food refrigerating and buildings, etc.

mospheric window at night, so it can reduce the underlying material

temperature during the night while work as selective covers to prevent

bient temperature reduction and a 52 W/m2 cooling load at night. For

¯LWIR = 0.97 ± 0.02

noontime, where heating power was estimated to be 7.2 W/m2 (Nilsson

3.2. Reflection material

3.2.1. Titanium dioxide (TiO2)

chemical properties, high refractive index and being transparent to

most infrared radiation (Mastai et al., 2001). The submicron anatase

centered at ~0.2 (nanopores)

and ~5.5 mm (micropores)

~60 nm) colloidal suspension was spread between two polyethylene

spread due to their excellent optical characteristics.

(2019) used hierarchical particle sizes in a TiO2 nanoparticle-acrylic

sized 100 nm (~78%) and 400 nm (~88%) particles. Compared to any

single-sized particles, the hierarchical-sized particles can efficiently

the homogeneous rutile or anatase pigmented polymer structure, the

will influence the effective scattering coefficients per unit length. It

1 Double layers structure (Bao et al., 2017)

2 Seven alternating layers structure (Raman et al., 2014)

3 Metallodielectric multilayer structure (Suichi et al., 2018)

4 Multilayer structure (Chae et al., 2020)

5 Metasurface structure (Zhai et al., 2017)

6 Metasurface structure (Huang and Ruan, 2017)

(continued on next page)

No. Structure Schematic diagram References

7 Metasurface, Al-doped ZnO (Sun et al., 2018)

9 Multilayer and metasurface structure (Rephaeli et al., 2013)

10 Multilayer and metasurface structure (Zhao et al., 2018)

Fig. 20. (a) Scheme and (b) Emissivity

5.4. Other applications 6. Recommendations and conclusions