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Spectrally Selective Inorganic-Based Multilayer Emitter for Daytime

Radiative Cooling
Dongwoo Chae, Mingeon Kim, Pil-Hoon Jung, Soomin Son, Junyong Seo, Yuting Liu, Bong Jae Lee,*
and Heon Lee*
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ABSTRACT: Daytime radiative coolers are used to pump excess heat from a
target object into a cold exterior space without energy consumption.
Radiative coolers have become attractive cooling options. In this study, a
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daytime radiative cooler was designed to have a selective emissive property of

electromagnetic waves in the atmospheric transparency window of 8−13 μm
and preserve low solar absorption for enhancing radiative cooling
performance. The proposed daytime radiative cooler has a simple multilayer
structure of inorganic materials, namely, Al2O3, Si3N4, and SiO2, and exhibits
high emission in the 8−13 μm region. Through a particle swarm optimization
method, which is based on an evolutionary algorithm, the stacking sequence
and thickness of each layer were optimized to maximize emissions in the 8−
13 μm region and minimize the cooling temperature. The average value of
emissivity of the fabricated inorganic radiative cooler in the 8−13 μm range was 87%, and its average absorptivity in the solar spectral
region (0.3−2.5 μm) was 5.2%. The fabricated inorganic radiative cooler was experimentally applied for daytime radiative cooling.
The inorganic radiative cooler can reduce the temperature by up to 8.2 °C compared to the inner ambient temperature during the
daytime under direct sunlight.
KEYWORDS: daytime radiative cooling, atmospheric transparency window, particle swarm optimization,
one dimensional matrix formulation, inorganic radiative cooler, outdoor subambient cooling

1. INTRODUCTION alternating layers of SiO2 and HfO2 with a Ag solar reflector on

Based on the continuing increase in energy consumption,
global warming has become a prominent issue, and the
demand for energy-saving technologies is increasing at a
corresponding rate. Among the various aspects of energy
consumption, the usage of electrical energy for space cooling is
dramatically increasing every year.
Daytime radiative cooling has significant potential to
alleviate thermal control issues of buildings and the human
body.1−12 Daytime radiative cooling systems are designed to
provide wavelength-selective reflectivity and emissivity, which
means that they can passively be cooled by reflecting most of
the incident solar energy during the daytime and emitting
infrared (IR) energy in the atmospheric transparency window
(8−13 μm) to an exterior space with a 3 K cryogenic
temperature that can serve as an ultimate heat sink for radiative
cooling.13
For high-performance daytime radiative cooling, a daytime
radiative cooler must have high emissivity in the atmospheric
transparency window and high reflectivity in the solar spectral
region (0.3−2.5 μm) simultaneously. In previous studies,
elaborately engineered multilayer films, photonic crystals, and
metamaterials have been actively studied for radiative cooling
systems.14−23 A daytime radiative cooling system with seven
a silicon substrate was reported by Raman et al.15 This
multilayer radiative cooling system experimentally provided a
4.9 °C cooling temperature and 40.1 W m−2 of cooling power
under 850 W m−2 of solar irradiance. Although multilayer
systems have relatively low emissivity in the atmospheric
transparency window, the study played a major role in
attracting interest in daytime radiative cooling. In a study on
photonic crystal-structured daytime radiative cooling systems,
an optimized stacked structure consisting of Ag, TiO2, MgF2,
SiC, and α quartz exhibited more than 100 W m−2 of cooling
power at room temperature.16 Al and Ge pyramid-patterned
metamaterials that maximize emissivity in the atmospheric
transparency window through optimization of pattern size have
also been reported.14 Most studies on radiative cooling have
largely focused on emissivity in the atmospheric transparency
window and ignored reflectance in the solar spectrum.
Additionally, the fabrication of radiative cooling systems
Received: September 16, 2019
Accepted: January 28, 2020
Published: January 28, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.9b16742

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Figure 1. Refractive indices and extinction coefficients of (a) Al2O3, (b) Si3N4, and (c) SiO2 thin films used for the PSO method.
described above is very difficult because of their complex and
expensive structures. Therefore, daytime radiative cooling
systems for real-world applications were limited until the
introduction of microparticle-embedded metamaterial-based
radiative cooling systems.24 These hybrid metamaterials
contain randomly dispersed SiO2 microparticles in a polymer
matrix and exhibit superior performance for daytime radiative
cooling compared to previous daytime radiative coolers by
providing high emissivity in the atmospheric transparency
window and low absorptivity in the solar spectrum region. The
hybrid metamaterial-based daytime radiative cooling systems
are advantageous in that they can be easily fabricated at low
costs to cover large areas using a roll-based process. Since then,
various types of similar daytime radiative cooling systems, such
as particle-embedded polymers or nanoparticles, have been
studied and excellent radiative cooling performances have been
reported.9,11−13,25−31 However, only a few daytime radiative
cooling systems consisting purely of inorganic layers have been
studied.32−35 For real-world applications of daytime radiative
cooling, excellent radiative cooling performance and semi-
permanent lifespans are equally important. Polymer-based
radiative cooling systems have limited lifespans because of
oxidation, degradation, and peeling issues. Additionally,
polymers acting as IR-emissive layers can undergo yellowing
when exposed to exterior elements for long periods. In this
regard, radiative cooling systems composed of all-inorganic
materials should provide advantages in terms of system
lifespans.
In this study, a multilayer structured radiative cooler
consisting of all-inorganic materials was developed. Using a
one-dimensional matrix formulation for multilayer structures
and particle swarm optimization (PSO), material selection,
stacking sequence, and thickness optimization were performed
to maximize the radiative cooling performance. The proposed
inorganic radiative cooler comprises four inorganic layers. The
first three layers, namely, Al2O3, Si3N4, and SiO2, provide
strong IR emission in the atmospheric transparency window.
Metallic Ag mirror layers are used to reflect the incoming solar
energy. With only three layers consisting of all-inorganic
materials, high emission values in the atmospheric trans-
parency window can be achieved while maintaining very low
absorption in the solar spectral region. Because Al2O3, Si3N4,
and SiO2 are stable and chemically inert materials that are
typically used as passivation layers in semiconductor
fabrication processes, the inorganic radiative cooler proposed
in this study inherently exhibits superior mechanical robustness
and retainability, thus guaranteeing a long lifespan in exterior
environments.36,37 Most previously reported radiative coolers
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composed of all-inorganic materials have many alternatively
stacked layers or patterned surfaces that are not easy to
fabricate.14−17,22,23,32−35 However, our proposed structure
covers most of the atmospheric transparency window with
only three IR-emissive layers, which intrinsically have high
emissivity. Fabrication of the proposed inorganic radiative
cooler was carried out using a vacuum deposition process. The
fabricated radiative cooler consisting of four layers of inorganic
materials exhibited an average absorption of 5.2% in the solar
spectral region and an average emission of 87% in the
atmospheric transparency window. Low absorption in the solar
spectral region and high emission in the atmospheric
transparency window are necessary traits for good performance
of daytime radiative cooling. External cooling experiments
using the fabricated inorganic radiative cooler were conducted
in South Korea, which has a high relative humidity in the
night-time. The inorganic radiative cooler can reduce the
temperature to up to 8.2 °C compared to the inner ambient
temperature in daytime. The cooling performance of the
designed and fabricated inorganic radiative cooler was
calculated based on absorptivity and emissivity spectra.
2. DESIGN
To enhance the performance of inorganic radiative coolers, it is
necessary to have high emissivity in the infrared region (8−13
μm) and low solar absorptance in the solar spectrum (0.3−2.5
μm). Among the many available materials, Al2O3, Si3N4, and
SiO2 have large imaginary parts of the refractive index
(extinction coefficient) in the IR region and were used to
achieve a high and broad emission spectrum in the 8−13 μm
region.
Figure 1 presents the refractive index and extinction
coefficient values of Al2O3, Si3N4, and SiO2 thin films.36−38
The Al2O3, Si3N4, and SiO2 layers each have unique peak
extinction coefficient values in the atmospheric transparency
window. The peak extinction coefficient values of the SiO2,
Si3N4, and Al2O3 layers are 9, 11, and 15 μm, respectively. A
high extinction coefficient means that the electromagnetic
wave is rapidly decayed as the wave passes through the
medium. Because the reduced electromagnetic wave is
absorbed by the medium, a high extinction coefficient means
that high absorption occurs. According to Kirchhoff’s law of
thermal radiation, in a thermodynamic equilibrium state, the
absorption is equal to the emission at every wavelength.
Therefore, by combining these three layers, broadband
emission in the entire atmospheric transparency window can
be achieved. In addition, the highly reflective Ag layer was
added to minimize absorption in the solar spectrum. We
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∞
designed a multilayer-structured radiative cooler that is simple
in structure and easy to manufacture. To determine the
Psun = ∫0 IAM1.5(λ)ε(λ , θ )dλ
(4)
dimensions of the structure with the best cooling performance,
the design of the structure proceeded in three steps, as shown is the power that is heated due to the absorption of sunlight.
in Scheme 1. First, for the calculation of cooling performance, Pnonrad = hc(Tatm − T ) (5)

Scheme 1. Flow Diagram of Optimizing the Inorganic is the cooling power loss of the inorganic radiative cooler
Radiative Cooler caused by conduction and convection.
Here, equations of IBB = (2hc2/λ5)/[ehc/λkBT − 1] for
blackbody radiation and εatm(λ, θ) = 1 − t(λ)1/ cos (θ) for
angular atmospheric emissivity were used. h, c, kB, and hc
indicate the Planck’s constant, speed of light, Boltzmann
constant, and heat transfer coefficient, respectively. ε(λ, θ) is
the emissivity of the film. The cooling temperature (ΔTcool = T
− Tatm) was calculated by extraction of the cooling
temperature in the condition of Pnet(T) = 0. For calculating
the cooling temperature, the heat transfer coefficient hc was
fixed at 6 W m−2 K−1.
As a final step, the PSO method was used to obtain
structures with optimal cooling performance. PSO is one of the
evolutionary algorithms based on swarm intelligence, which is
fast and effective in optimizing multidimensional variable
problems.42 In PSO, particles represent each potential solution,
and the solutions are evaluated according to the objective
function. At each generation, two optimal points are evaluated:
one is the global optimal point found so far, and the other is
the local optimal point around the particle position. By
comparing the local optimal and global optimal found so far,
the position and velocity vectors were iteratively adjusted.43
For the optimization of the multilayered film structure for
radiative cooling using PSO, we used the PSO toolbox
provided by MATLAB. The thickness of each layer was set as a
design parameter, and the minimum cooling temperature was
set as an objective function. The boundary of parameters was
the spectral emissivity should be calculated. Because the set to 0 to 2000 nm, which is the fabrication limit for each
structure proposed in this study is a multilayered film, the depositing layer. The iteration was repeated 86 times until the
spectral emissivity was obtained using the one-dimensional optimal point was found, and we created 30 particles/iteration.
matrix formulation for analyzing field distribution and wave A total of 2580 particles were calculated to decide the
propagation in the one-dimensional multilayered film thickness of each layer for optimal radiative cooling perform-
structure. Four layers were set in the order of Ag, Al2O3, ance.
Si3N4, and SiO2 from the bottom, and the boundary conditions
were set in vacuum at the top and bottom of the multilayered 3. RESULTS AND DISCUSSION
film. The angle of incident light was set to be vertical, and The designed multilayer structure with the optimized cooling
calculations were performed in the 0.3 to 15 μm wavelength performance by the PSO method is shown in Figure 2a. The
range with intervals of 0.01 μm. substrate of the inorganic radiative cooler is silicon with a
The second step is to obtain the cooling temperature. The thickness of 500 μm and does not influence the optical
cooling performance can be investigated as follows according properties of the upper structure. A thin silver layer with a
to the law of conservation of energy.39−41 thickness of 200 nm is chosen as the solar reflective layer. The
thicknesses of the Al2O3, Si3N4, and SiO2 IR-emissive layers are
Pnet(T ) = Prad(T ) − Patm(Tatm) − Psun − Pnonrad (1) set to 1312, 312, and 276 nm respectively. Figure 2b shows a
where photograph of the fabricated inorganic radiative cooler with
2π π /2 ∞ dimensions of 5 × 5 cm2. One can clearly see that the film has
Prad(T ) = ∫0 ∫0 ∫0 IBB(T , λ)ε(λ , θ )cos θ sin θ a mirror-like silver color because all the IR-emissive layers
(Al2O3, Si3N4, and SiO2) over the Ag mirror layer are
dλ dθ dφ (2) transparent to visible light. A cross-sectional micrograph of the
inorganic radiative cooler is presented in Figure 2b. We used a
is the spectral radiation power emitted from the surface of the field-emission scanning electron microscope (S-4800, Hitachi,
inorganic radiative cooler. Japan) to capture this image. The interfaces between each layer
2π π /2 ∞ can be clearly observed, which confirms that the deposition of
Patm(Tatm) = ∫0 ∫0 ∫0 IBB(Tatm , λ)ε(λ , θ )εatm(λ , θ )
the multilayer was successful. The thicknesses of each layer
were obtained using SEM images, as shown in Figure 2b. The
cos θ sin θ dλdθ dφ (3)
thicknesses of the Ag, Al2O3, Si3N4, and SiO2 layers were 192,
is the power absorbed from the radiation of the atmosphere. 1402, 344, and 277 nm, respectively. The measured
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mirror. The average absorptivity in the solar spectrum is 5.6%

Figure 2. (a) Designed inorganic radiative cooler structure by the
PSO method. (b) Photograph of a fabricated mirror-like inorganic
radiative cooler with dimensions of 5 × 5 cm2, logo courtesy of
NMDL Korea University. (c) Cross-sectional scanning electron
microscopy image of the inorganic radiative cooler.
thicknesses of the layers were slightly different than the
designed thicknesses shown in Figure 2a.
Figure 3a presents the absorptivity/emissivity spectra of the
inorganic radiative cooler obtained via a one-dimensional
matrix formulation using the designed layer thicknesses in
Figure 2a and the actual measured data for the fabricated
inorganic radiative cooler in Figure 2c. The graph shows the
spectrally selective optical properties of the inorganic radiative
cooler clearly in terms of daytime radiative cooling. High
emissivity in the atmospheric transparency window can be
achieved by combining Al2O3, Si3N4, and SiO2 layers while
maintaining low absorption in the solar spectrum using the Ag
for the simulated results and 5.2% for the measured results.
The average emissivity in the atmospheric transparency
window is 91% for the simulated results and 87% for the
measured results. The layer-by-layer emissivity spectra of the
measured data can be seen in Figure S2, which correspond to
the extinction coefficient values in Figure 1. A strong emission
peak in the absorptivity/emissivity spectrum of the designed
inorganic radiative cooler is observed at wavelengths of 8.7,
10.5, and 13.7 μm. The peaks at wavelengths of 8.7 and 10.5
μm can be attributed to the intrinsic absorption properties of
SiO2 and Si3N4, respectively. Furthermore, the peak at the
wavelength of 13.7 μm is mainly caused by Si3N4. Slight
differences in the peak wavelengths between the simulated and
measured results can be observed because the refractive indices
and extinction coefficient values of Al2O3, Si3N4, and SiO2 used
in the PSO method may differ from those of the deposited
Al2O3, Si3N4, and SiO2 layers. Additionally, the deposited
thicknesses of the layers are slightly different from the designed
thicknesses. The peak in the measured data spectrum in the
wavelength range of approximately 3−4 μm is a result of
carbon dioxide and water vapor in the measurement chamber
of the Fourier-transform infrared spectroscopy (FT-IR)
instrument. Regardless of the slight differences in absorptiv-
ity/emissivity spectra between the simulated and measured
results, the average absorptivity/emissivity values closely match
each other. The average values of absorptivity in the solar
spectrum and emissivity in the atmospheric transparency
window, denoted as αmean and εmean, respectively, are
summarized in Table 1. With the optimized multilayered
film structure, high broadband emission in the atmospheric
transparency window in the 8−13 μm range is achieved. The
proposed multilayered film structure exhibits better perform-

Figure 3. (a) Absorptivity/emissivity spectra of the designed and fabricated inorganic radiative cooler at an incident angle of 5°. Yellow- and cyan-
colored spectra indicate an AM 1.5 direct + circumsolar solar power density (Figure S3a) and atmospheric transmittance of AM 1.5 atm in the
atmospheric transparency window (Figure S4a), respectively. (b) Contour color map of the emissivity values vs the incident angle and the
wavelength for the designed inorganic radiative cooler. (c) Mean emissivity of the designed and fabricated inorganic radiative coolers in the
atmospheric transparency window (8−13 μm) plotted as a function of the incident angle.

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Table 1. Averaged Absorptivity/Emissivity Values of the
Simulated Result and Measured Result
parameter simulated result measured result
αmean (0.3−2.5 μm) 0.056 0.052
εmean (8−13 μm) 0.91 0.87
ance than that of the structures studied previously. Figure 3b
shows the contour color map of emissivity of the designed
inorganic radiative cooler with an incident angle varying
between 0° and 85°. The three unique emissivity peaks are
maintained until the incident angle of 60° is reached. The
mean emissivity of the simulated and measured data in the
atmospheric transparency window with different incident
angles is shown in Figure 3c. The measured result has a low
mean emissivity, similar to the trend in Figure 3a. However,
the emissivity of the measured result is over 0.6 at an angle of
60°, showing good emissive properties for radiative cooling.
Figure 4 presents an illustration and photographs of the
custom radiative cooling measurement system used in outdoor
experiments. The measurement chamber was constructed
using a wooden frame with a transparent acrylic plate (200
mm wide, 100 mm high, and 0.3 mm thick), which was
covered with aluminum tape to avoid solar heating. White
polystyrene, which acted as a thermal insulator, was used as a
cradle for the sample. A slight step on the edge of the
polystyrene minimized the surface area where the sample and
polystyrene come into contact, thus minimizing heat exchange.
A band-format adhesive K-type thermocouple (ST-50, RKC
Instrument, Japan) was used to measure the temperature of the
backside of the sample, which was regarded as the sample
temperature. An IR-transmissive, low-density polyethylene
(LDPE) film (0.03 mm in thickness) was used to cover the
measurement chamber to prevent convection from the exterior
environment. The transmittance of the LDPE film is shown in
Figure S3b. Because the measurement chamber was isolated
from the outside by covering with an LDPE film, it can create a
greenhouse effect, causing a temperature difference between
the inside and outside of the measurement chamber.
Therefore, an additional copper wire-format K-type thermo-
couple for measuring the inner ambient temperature for
comparison with the sample temperature was installed inside
the chamber with the same height as the band-format K-type
thermocouple. The sample temperature and inner ambient
temperature were logged at intervals of 30 s by a data logger
(OM-CP-OCTTEMP-A, OMEGA engineering, U.S.A.). In
addition, the solar irradiance, relative humidity, outside
temperature, and wind speed at every 30 s were logged by a
Figure 4. (a) Illustration of the outdoor temperature measurement chamber. The wooden frame is covered with aluminum foil to reflect solar
energy. (b) Photographs of the outdoor cooling temperature measurement system when measuring. The side view (inset) shows that the chamber
is tilted at an angle of 30° and installed facing south.
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weather station (HD52.3D, Delta OHM, Italy) located around
the measurement sample. Figure 4b presents a photograph of
the customized radiative cooling measurement system installed
at an angle of 30° and facing south in the rooftop of a building
in the campus of Korea University.
Figure 5 presents the outdoor temperature measurement
data for the inorganic radiative cooler over 72 h between May
9 and May 11, which are denoted as day 1, day 2, and day 3,
respectively. During the measurement period, the relative
humidity was much higher in the night-time than in the
daytime. The inner ambient temperature, sample temperature,
outside temperature, and solar irradiance are presented in
Figure 5a. The relative humidity and wind speed are shown in
Figure 5b,c. The zoomed-in temperature graph of day 2 in
daytime from 11:00 to 16:00 is shown in Figure 5d. The
increase patterns of the inner ambient temperature and the
sample temperature matched the solar irradiance pattern well,
which means that the temperature increase was caused by solar
heating. In the whole measured time, the sample temperature
was kept lower than the inner ambient temperature, which
means that the inorganic radiative cooler had cooled down.
Because the measurement chamber was isolated using an
LDPE film, creating a slight greenhouse effect, the measure-
ment chamber exhibited a much higher temperature (up to
17.2 °C) during the daytime and a slightly lower temperature
(up to −3.6 °C) at night compared with the outdoor
temperature. Moreover, high wind speed in the daytime
shown in Figure 5c enlarges the difference between the inner
ambient temperature and outside temperature. The result of
the sample temperature being higher than the outside
temperature was also observed in a previous study, which
was conducted in Asia.34,47,48 During the daytime of day 1
between 11:00 and 16:00, the average inner ambient
temperature, sample temperature, and outside temperature
were 36.4, 30.7, and 22.9 °C, showing temperature drops of 5.7
°C for the inorganic radiative cooler compared with the inner
ambient temperature with an average solar irradiance of 813 W
m−2. The peak temperature drop in the daytime was 7.6 °C
observed at 13:25 with a solar irradiance of 901 W m−2. In the
night-time of day 1 from 00:00 to 04:00, the inorganic
radiative cooler showed an average temperature of 10.6 °C,
which is lower than the inner ambient temperature and outside
temperature by 1.3 and 3.7 °C, respectively. Although the
night-time has no sunlight, the severe humidity over 60%
negatively affects the cooling performance of the radiative
cooler by lowering the atmospheric transmittance.39,44−47
During the daytime of day 2 between 11:00 and 16:00, the
sky was clearer than on day 1 except from 14:30 to 16:00
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Figure 5. (a) Measured solar irradiance (orange), inner ambient temperature (black), sample temperature (red), and outside temperature (blue) vs
time graphs of over 72 h from May 9 to May 11. (b) Measured relative humidity graph and (c) wind speed graph measured by a pyrometer for 72
h. (d) Zoomed-in temperature graph of day 2 in the daytime between 11:00 and 16:00.

Figure 6. Calculated (a) net cooling power and (b) cooling temperature graphs vs ambient temperature based on the absorptivity/emissivity
spectra with heat transfer coefficients of 0, 4, 6, and 8 W m−2 K−1 for simulated and fabricated results.

because of the shade by clouds, as shown in Figure 5d. The
sample temperature showed an average drop of 6.2 °C
compared to the inner ambient temperature with an average
solar irradiation of 770 W m−2, and the maximum temperature
drop was 8.2 °C when the solar radiation was 872 W m−2. Both
the temperature drops were 0.5 °C higher than those measured
on day 1, which was caused by the lower solar irradiance on
day 2. On day 3, the inorganic radiative cooler reduced the
temperature by 1.5 and 2.8 °C compared with the inner
ambient temperature and outside temperature, respectively, in
the night-time between 00:00 and 04:00 and exhibited average
temperature drops of 6.2 °C compared to the inner ambient
temperature in the daytime between 11:00 and 16:00.
Figure 6 presents the calculated net cooling power and
cooling temperature as a function of temperature based on the
absorptivity/emissivity spectra of the simulated and measured
results in Figure 3a. The solar irradiance and atmospheric
8078
transmittance shown in Figures S3a and S4a are used. The
cooling power and cooling temperature were extracted with the
same method in the second step of the optimization process.
Because the ambient temperature can be regarded as the
effective sky temperature, we used Tamb instead of Tatm.39,49−53
In Figure 6a, the net cooling power of the simulated results
shows a higher net cooling power than that of the measured
results, which matches the averaged optical properties
presented in Figure 3a. At an ambient temperature of 27 °C
(300 K), the calculated net cooling powers of the simulated
and measured results were 73.8 and 66.4 W m−2, respectively.
It is noteworthy that even a simple multilayer structure using
only inorganic materials can provide more than 60 W m−2 of
net cooling power under direct sunlight illumination, which
has a power density of 888 W m−2. Figure 6b presents the
cooling temperatures of the simulated and measured results
with four different values of heat transfer coefficients. The
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cooling temperatures of the measured data are lower than

Table 2. Summary of the Radiative Cooler Structure, Optical Properties, and Radiative Cooling Performance of Daytime Radiative Coolers Purely Composed of Inorganic

vacuum with a ZnSe IR-trans-

missive window and alumi-
those of the simulated data, and the trend is similar to the one

measurement condition

nonvacuum and aluminum

in Figure 6a. Our designed inorganic radiative cooler can cool
the temperature by 29.2 °C at an ambient temperature of 27

num solar shade

°C in a vacuum, which can be deemed as hc = 0 W m−2 K−1 but

solar shade
still affected by the presence of atmospheric transmittance. The

nonvacuum

nonvacuum
fabricated inorganic radiative cooler can cool the temperature
by 28.3 °C under the same conditions mentioned above. With

NA

NA
NA
increasing the heat transfer coefficient between 0 and 8 W m−2
K−1, the cooling temperature significantly changed from −29.2

measurement

Seoul, South
Hong Kong
location
to −10.9 °C (hc = 4 W m−2 K−1), −8.4 °C (hc = 6 W m−2

California,

California,
U.S.A.

U.S.A.

Korea
K−1), and −6.8 °C (hc = 8 W m−2 K−1). The cooling power

NA

NA
NA
and cooling temperature with different atmospheric trans-
mittance values and heat transfer coefficients are presented in

perature (°C)
cooling tem-
measured
Figure S5, which shows that the atmospheric transmittance has

NA

NA
NA
4.9

7.2

6.2
a significant effect on the performance of radiative cooling.

42
We summarize the previous study for the daytime radiative
cooler composed of all-inorganic materials in Table 2. The

net cooling
cooling power and measured cooling temperature can differ

(W m−2)
power

40.1

85.5

96.4

66.0
105
because of dissimilar conditions. With the cooling perform-

NA
54
ance-optimized multilayered inorganic radiative cooler, high
broadband emission in the atmospheric transparency window

(8−13 μm)
in the 8−13 μm range is achieved, proving that a few layered,

emissivity
average

0.68

0.85

0.84

0.84

0.87
NA

NA
stacked, simple multilayered structures can be used for daytime
radiative cooling.

4. CONCLUSIONS

sorptivity
solar ab-
average

0.035

0.008
0.03

0.16

0.06

0.05
NA
In the summary, we proposed a multilayered daytime radiative
cooler purely composed of inorganic materials. The 1D matrix
formulation and PSO method were used for a cooling simulation and

simulation and

simulation and

simulation and
field measure-
field meas-

field meas-

field meas-
fabrication
performance-optimized daytime radiative cooler with a simple
method

simulation

simulation
urement

urement

urement
multilayer structure. With only three IR-emissive layers, the

ment
fabricated inorganic radiative cooler showed an average
emissivity of 87% in the atmospheric transparency window

eight alternating layers of four sets of bilayers each with 500 nm of SiO2 and 500 nm of TiO2 on
seven alternating layers of 230 nm of SiO2, 485 nm of HfO2, 688 nm of SiO2, 13 nm of HfO2, 73
nm of SiO2, 34 nm of HfO2, and 54 nm of SiO2 on 200 nm of a Ag solar reflector and Ti of 20

AZO metasurface of 1350 nm in width, 250 nm of a gap, and 100 nm in thickness on 1200 nm of
and exhibited an absorptivity of 5.2% in the solar spectral

276 nm of SiO2, 312 nm of Si3N4, and 1312 nm of Al2O3 on 200 nm of Ag and 30 nm of Cr

region, showing highly spectrally selective properties for eight alternating layers of 200 nm of TiO2, 200 nm of SiO2 with four pairs on 200 nm of Ag
2.5 μm-thick α quartz and 8 μm-thick SiC with 6 μm of periodicity and 5.4 μm-wide mesh

daytime radiative cooling. The use of inorganic materials

assures a stable operation in exterior environments with a long
70 nm of Si3N4 and 700 nm of Si on 150 nm of Al deposited on a silicon substrate

lifespan. In outdoor temperature measurement, the fabricated

inorganic radiative cooler could reduce the temperature by up
to 8.2 °C in the daytime compared with the inner ambient
temperature.
SiO2 and 80 nm of Al deposited on a SiO2-coated silicon substrate

200 nm of Ag and 20 nm of Ti deposited on a silicon substrate

5. EXPERIMENTAL SECTION
radiative cooler structure

5.1. Fabrication of an Inorganic Radiative Cooler. A p-type

(100) Si wafer was used as a substrate for the multilayered film. An E-
patterns on 3 sets of 5 bilayers with TiO2 and MgF2

beam evaporator (ULVAC, el-5k) was used for the deposition of Ag

and Al2O3 layers. As a solar reflector, Ag was carefully deposited on
the Si substrate with a deposition rate of 0.03 nm/s. As an adhesion
layer, 30 nm-thick Cr was deposited prior to Ag deposition. Next, in
nm deposited on a silicon substrate

situ deposition of the Al2O3 layer onto the Ag layer was performed.
The Si3N4 and SiO2 layers were consecutively deposited via plasma-
enhanced chemical vapor deposition (PECVD) using an Oxford
deposited on a Si substrate

Plasma Lab 800 Plus device. The PECVD deposition process was
performed at a temperature of 120 °C to avoid any damage to the
underlying Ag layer. Si3N4 was deposited at a deposition rate of 0.5
nm/s followed by in situ deposition of the SiO2 layer at the same
deposition rate.
5.2. Measurement of Optical Properties. Because the under-
lying Ag layer has no transparency over the entire wavelength region
from 0.3 to 15 μm, the transmittance value can be regarded as zero.
Materials

Therefore, the absorptivity/emissivity value was obtained using the

equation of 1 − R (reflectivity). In the wavelength of the solar spectral
reference

work

region, an ultraviolet−visible−near-IR (UV−vis−NIR) spectrometer

this
15

16

21

22
32

34

(Solid Spec-3700, Shimadzu, Japan) equipped with an integrating

8079 https://dx.doi.org/10.1021/acsami.9b16742
ACS Appl. Mater. Interfaces 2020, 12, 8073−8081
ACS Applied Materials & Interfaces
sphere was used for measuring the reflectivity of the inorganic
radiative cooler. A protected silver mirror (ME2S-P01, Thorlabs,
U.S.A.) was used as a baseline reference. The measured reflectivity
captured by the UV−vis−NIR spectrometer was transformed into
absolute values through multiplication by the absolute reflectivity
value of the protected silver mirror. The reflectivity spectrum of the
inorganic radiative cooler in the wavelength range of 2.5−15 μm was
measured using FT-IR spectroscopy. The FT-IR spectroscopy
measurement system contained a Nicolet IS-50 system (Thermofisher
Scientific, U.S.A.), MID-IR INTEGRATIR accessory (Pike Tech-
nologies, U.S.A.) for measuring reflectivity at an incident angle of 5°,
and VeeMAX III (Pike Technologies, U.S.A.) for measuring
reflectivity with varying incident angles (30°−80°) for measuring
the reflectivity of the inorganic radiative cooler with varying incident
angles. A gold reference was used for FT-IR measurements.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.9b16742.
Cooling performance and absorptivity/emissivity spectra
of inorganic multilayer structures using the PSO
method, solar irradiance and three different atmospheric
transparency windows for the calculation of cooling
performance and transmittance of the LDPE film used in
outdoor temperature measurement, and calculated net
cooling power and cooling temperature versus ambient
temperature graphs with varying heat transfer coef-
ficients (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Bong Jae Lee − Department of Mechanical Engineering, Korea
Advanced Institute of Science and Technology, Daejeon 34141,
Republic of Korea; Email: bongjae.lee@kaist.ac.kr
Heon Lee − Department of Materials Science and Engineering,
Korea University, Seoul 136-713, Republic of Korea;
orcid.org/0000-0001-6635-1880; Email: heonlee@
korea.ac.kr
Authors
Dongwoo Chae − Department of Materials Science and
Engineering, Korea University, Seoul 136-713, Republic of
Korea
Mingeon Kim − Department of Mechanical Engineering, Korea
Advanced Institute of Science and Technology, Daejeon 34141,
Republic of Korea
Pil-Hoon Jung − Department of Materials Science and
Engineering, Korea University, Seoul 136-713, Republic of
Korea
Soomin Son − Department of Materials Science and
Engineering, Korea University, Seoul 136-713, Republic of
Korea
Junyong Seo − Department of Mechanical Engineering, Korea
Advanced Institute of Science and Technology, Daejeon 34141,
Republic of Korea
Yuting Liu − Department of Materials Science and Engineering,
Korea University, Seoul 136-713, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.9b16742
Author Contributions
D.C. and M.K. contributed equally.
8080
www.acsami.org Research Article
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Creative Materials Discovery
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Science and ICT (NRF-
2018M3D1A1058972). This work was also supported by
Global Ph.D Fellowship Program conducted by NRF (Na-
tional Research Foundation of Korea) grant funded by the
Korean Government (NRF-2019H1A2A1076622) and the
Technology Innovation Program (N0002310) funded by the
Ministry of Trade, Industry and Energy (MOTIE, Korea).
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