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Hierarchical WO3−x Ultrabroadband Absorbers and Photothermal

Converters Grown from Femtosecond Laser-Induced Periodic
Surface Structures
Dongshi Zhang,* Ruijie Liu, Sihan Ji, Yunyu Cai, Changhao Liang, and Zhuguo Li*

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ABSTRACT: Oxygen-vacancy-rich WO3−x absorbers are gaining increasing attention because

of their extensive absorbance-based applications in near-infrared shielding, photocatalysis,
Downloaded via TSINGHUA UNIV on May 8, 2023 at 06:11:35 (UTC).

sterilization, interfacial evaporator and electrochromic, photochromic, and photothermal fields.

Thermal treatment in an oxygen-deficient atmosphere enables us to prepare WO3−x but lacks
the capacity for finely manipulating the grown structures. In this work, we present that laser-
induced periodic surface structure (LIPSS) obtained by femtosecond laser ablation is a good
template to grow various hierarchical WO3−x ultrabroadband absorbers and photothermal
converters by thermal oxidation annealing in air. Increasing annealing temperature from 600 to
1000 °C allows the manipulation of WO3−x crystal sizes from ∼70 nm to ∼4 μm, accompanied
by a color transition from brown to dark blue and finally to yellow. Benefiting from annealing-
induced surface cracks and phase transition into WO3−x (containing both WO3 and W18O49) at
600 °C, excellent UV−vis−NIR−MIR ultrabroadband absorbers were produced: >90% UV−
NIR absorbance (0.3−2.5 μm) and 50−90% MIR absorbance (2.5−16 μm), much better than
most W-based metamaterial absorbers. The higher the annealing temperature (1000 > 800 >
600 °C), the better the photothermal performances (sample temperature as the indicator) of annealed interfaces due to the
increased oxidation rates and resultant thicker oxide layers (6, 150, and 507 μm), a trend which is more apparent upon the
irradiation of high-density (3160 mW/cm2) and ultrabroadband (200−2500 nm) light but much less apparent for shorter-band
(200−800, 420−800, 800−2500 nm, etc.) and less-intensity (1694, 1540, 1460 mW/cm2, etc.) light irradiation. This phenomenon
indicates that (1) higher-performance ultrabroadband absorbers possess a higher photothermal conversion capacity; (2) thicker-
WO3−x oxide layer converters are more effective in preserving photothermal heat; and (3) both the W-LIPSS and metal tungsten
substrate can quickly dissipate the photothermal heat to inhibit heat accumulation in the oxide photothermal converters. It is also
proved that ablation-induced high-pressure shockwaves can produce deformation layers in the subsurfaces to release annealing-
induced stresses, beneficial for the formation of less-cracked non-stoichiometric WO3−x interfaces upon annealing. High-pressure
shockwaves are also capable of inducing grain refinement of LIPSS, which facilitates a homogeneous growth of small non-
stoichiometric metal-oxide crystals upon annealing. Our results indicate that femtosecond laser ablation is a convenient upstream
template-fabrication technique compatible with the thermal oxidation annealing method to develop advanced functional oxygen-
vacancy metal-oxide interfaces.
KEYWORDS: ultrabroadband absorber, femtosecond laser ablation, thermal annealing, photothermal, LIPSS,
oxygen-vacancy tungsten oxide

1. INTRODUCTION (RIE), in combination with repeated chemical vapor deposition

Broadband light absorbers in the manners of metal−dielectric processes.7 Instinct localized surface plasmon resonance
multilayer metamaterials,1 plasmonic,2 and oxygen-deficient (LSPR) characteristics make plasmonic metal structures
metal oxide absorbers3 are an ever-green topic because of their excellent light absorbers,8 but the high cost and ease to become
extensive applications such as solar energy harvesting, water
evaporation, thermal emitters, and imaging devices.4−6 From the
manufacturing perspective, some problems are still lying ahead Received: March 13, 2022
to inhibit their widespread applications in practice. For example, Accepted: April 19, 2022
metal−dielectric absorbers composed of alternating subwave- Published: April 29, 2022
length metal and dielectric layers must be fabricated by low-
throughput but high-cost equipment such as focused ion beam
or electron (E-beam) lithography milling or reactive ion etching

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c04523

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Figure 1. (a) Schematic illustration of fs-LA of a W plate (3 cm × 3 cm × 1 mm) in air at laser powers of 5 and 15 W, a pulse duration of 400 fs, a
repetition rate of 400 kHz, and a wavelength of 1030 nm using the line-by-line scanning method at a scanning speed of 200 mm/s. The scan line interval
is 15 μm. (b) Schematic illustration of the thermal annealing of pure W, fs-5W-W, and fs-15W-W samples in an oven at temperatures of 600, 800, and
1000 °C for 2 h. (c) Optical images of fs-5W-W and annealed samples obtained at temperatures of 600, 800, and 1000 °C. (d,f), (e,g), and (h,i) SEM,
AFM images, and depth profiles of the LIPSS for fs-5W-W and fs-15W-W samples, respectively. It is seen that few nanoparticles (NPs) deposit on the
fs-5W-W sample, whereas enormous NPs deposit on the fs-15W-W sample. (j) SEM image of the subsurface structure of the fs-5W-W sample
indicating the deformation and crack caused by fs-LA-induced shock waves.

aggregated strongly limit their widespread applications. Oxygen-
deficient metal-oxide materials such as WO3−x are gaining
increasing attention because of their merits of low cost and
LSPR-enhanced visible and near-infrared (NIR) light absorb-
ance.9 Compared with other excellent photothermal materials
such as carbon foam10 and carbonized wood,11 the significance
of further exploring oxygen-deficient metal-oxide materials lies
in their absorbance-based multi-functions including near-
infrared shielding, electromagnetic wave absorption, photo-
catalysis, sterilization, and electrochromic, photochromic,
photothermal, and thermal-to-electricity transition.12,13 Besides
these applications, oxygen-deficient metal-oxide materials can
also be used as sensing materials to detect trace chemical
contaminants and toxic and flammable gases such as volatile
organic compounds (methanol, ethanol, isopropanol, acetone,
etc.), NH3, SO2, H2S, and NO2.13 In long-term “closed”
environments such as a spacecraft and space station, these
substances can be generated from respiration systems, life
support subsystems, and intestines of human beings.14 Low-cost,
highly sensitive, and compatible WO3−x structures can help
build an alarm system to secure astronauts’ safety in space.
Electrochromic devices composed of WO3−x15 are also
potentially to be applied as thermal-emissivity modulation
“skin” devices for spacecraft thermal control.
Considering the extensively applicational scenarios, besides
WO3−x nanomaterials, hierarchical WO3−x interfaces with large
specific surface areas are highly demanded. Current synthesis
techniques (including the mechanochemical method, chemical
vapor transport, solid-phase reaction, inductively coupled
thermal plasma and hydrothermal and solvothermal methods13)
are merely good at producing WO3−x powders and nanoma-
terials, but it is difficult to construct hierarchical WO3−x crystal
structures, which can efficiently trap broadband light for
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absorbance-based applications.16 Thermal annealing of pure
metals17 offers the possibility to prepare oxygen-vacancy-
abundant metal-oxide crystals, and various annealing temper-
atures allow the manipulation of crystal morphologies.18
However, it is still challenging to construct hierarchical WO3−x
interfaces by thermal annealing unless with the aid of growth
templates. Hence, searching good templates to grow WO3−x
crystals in a hierarchical manner is highly demanded.
Femtosecond laser structuring offers a multi-scale (nanoscale,
microscale, and micro/nanoscale) structure19−24 and nanoma-
terial25,26 reservoir for selection to achieve this mission. They
have been proven to be good precursors to grow metal oxides
upon thermal oxidation annealing,27 hydrothermal treatment,
and electrochemical anodization.28 Among all achievable
structures by laser structuring,21,24,29−33 laser-induced periodic
surface structure (LIPSS) is the unique structure from
femtosecond laser structuring, which can be easily produced
on metals, polymers, semiconductors, and dielectrics.23,34−37
The absorbance of LIPSS structures, normally indirectly
measured by surface reflectance, has been investigated for a
long time. However, endowment of LIPSS on metals is merely
capable of increasing absorbance in the ultraviolet (UV: 200−
400 nm) and visible (vis: 300−750 nm) bands but incapable of
increasing the absorbance in the near-infrared (NIR, wave-
length: 800−2500 nm) band.38 If succeeded in transforming
metal LIPSS into oxygen-deficient metal oxides via thermal
oxidation annealing, a new route for developing ultrabroadband
interfacial absorbers will be verified and developed.
In this work, we present that by means of the thermal
oxidation annealing method, LIPSS is indeed a good template to
grow hierarchical WO3−x structures with excellent ultrabroad-
band absorbance and photothermal capacities. LIPSS is
generated by femtosecond laser ablation (fs-LA) of tungsten
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Figure 2. (a−c,d−f) Raman and XRD spectra of 600/800/1000 °C-annealed pure W, fs-5W-W, and fs-15W-W samples, respectively. (g,h) EDS
atomic percentages of W, O, and C elements of unannealed and annealed fs-5W-W and fs-15W-W samples and corresponding O/W atomic ratios.
Considering the existence of a large number of deposited particles on the LIPSS for the fs-15W-W sample, LIPSS and NPs are separately characterized
for comparison.

(W) in air at laser powers of 5 and 15 W while keeping other
parameters constant (a pulse duration of 400 fs, a wavelength of
1030 nm, and a repetition rate of 400 kHz). Two laser powers
are used to change the densities of deposited particles on the W-
LIPSS, similar to the method of changing the scan interval for
this purpose.39 To compare the impact of growth templates on
the annealing-induced structures and corresponding optical
properties, thermal annealing of unablated W metal plates is also
implemented. The structural morphologies are characterized by
scanning electron microscopy (SEM) and atomic force
microscopy (AFM). The compositions of resultant interfaces
are identified by Raman spectroscopy, X-ray powder diffraction
(XRD), and energy dispersive X-ray spectroscopy (EDS).
Ultrabroadband reflectance of different samples is characterized
by ultraviolet−visible (UV−vis) spectroscopy and Fourier
transform infrared (FTIR) spectroscopy. For bulky targets,
absorbance is equal to 1reflectance, so it is deduced based on
reflectance measurements. Photothermal capacities of unan-
nealed and annealed fs-5W-W samples are evaluated by light
irradiation at different wavelength bands (UV−vis, vis, NIR, and
UV−NIR) and different densities. The sample’s temperature
after 1 min irradiation is recorded by a thermal infrared camera
(FLIR, E60) to be used as photothermal conversion indicator.
The cross-section morphologies of annealed samples are
analyzed to correlate temperature-dependent oxidation rates
with photothermal variations.
2. EXPERIMENTAL SECTION
An fs laser system equipped with a galvanometer scanner was used for
laser ablation of W (dimensions: 30 × 30 × 1 mm) in air, as
schematically illustrated in Figure 1a. The pulse duration, wavelength,
and repetition rate of the laser system are 400 fs, 1030 nm, and 400 kHz,
respectively. Two laser powers of 5 and 15 W were adopted. The laser
spot size was 25 μm. The scan speed was set constant at 200 mm/s. The
line-by-line scanning method with the scan interval between adjacent
lines of 15 μm was used for fs-LA (Figure 1a). Thermal annealing of W
samples was performed in an oven at temperatures of 600 °C, 800 °C,
and 1000 °C for 2 h (Figure 1b). To simplify the description of samples,
they are termed by the fs−power−material−temperature criterion such
as fs-5W-W-600 °C, corresponding to the 600 °C-annealed W sample
which was obtained by fs laser ablation at a laser power of 5 W.

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The morphologies of surface structures and their elemental
distributions were characterized by SEM (NOVA NanoSEM 230,
FEI) equipped with an EDS module of 125 eV (Mn Kα). Reflectance
ranging from UV to near-infrared (NIR) and in the mid-infrared (MIR)
band was measured by UV−vis (Lambda 950, PerkinElmer, Inc.) and
FTIR spectroscopy (Nicolet 6700, Thermo Fisher), respectively. The
depth and cross-section profiles of nanostructures were measured by
AFM (Nanonavi E-Sweep, NSK Ltd., Tokyo, Japan). The compositions
of surface structures were analyzed by Raman spectroscopy (Senterra
R200-L, Bruker Optics) and XRD [Philips X’Pert X-ray diffractometer
with Cu Kα radiation (λ = 0.15419 nm)]. Photothermal transition
capacities were evaluated by irradiating each sample on a ceramic plate
using a light irradiator. Different bands of light were changed by using
light filters. The temperature was recorded every minute by using a
thermal infrared camera (FLIR, E60, USA), and three times of
photothermal tests were repeated for every sample under the same
irradiation condition.
3. RESULTS AND DISCUSSION
Thermal annealing induces an obvious color change of the
treated samples. To prevent a repetitive demonstration, the
optical images of the fs-5W-W sample and its corresponding
600/800/1000 °C-annealed samples are displayed in Figure 1c
as representatives. The LIPSS on the fs-5W-W sample originally
displays a brown color. After 2 h annealing in air at temperatures
of 600, 800, and 1000 °C, surface color transforms into dark blue
and yellow. Figure 1d−i displays SEM and AFM images and
cross-section profiles of LIPSS morphologies of fs-5W-W and fs-
15W-W samples. The periods of the LIPSS are ∼800 nm, close
to the wavelength of 1030 nm, indicating the formation of a low-
spatial frequency LIPSS (LSFL).40 The heights of the LIPSS on
the fs-5W-W and fs-15W-W samples are both around 300 nm
(Figure 1h,i), respectively. Because laser ablation is a subtractive
manufacturing technique, the subtractive materials turn out in
the manner of nanomaterials, which can spontaneously deposit
on the LIPSS as extra light absorbers and surface plasmon
polariton sources.26 Choosing laser powers of 5 W and 15 W for
LIPSS structuring is aimed to investigate how different densities
of deposited particles will induce the change of optical
properties before and after thermal annealing. At a lase power
of 5 W, only a small amount of NPs deposit on the LIPSS
(Figure 1d,e), while many NPs deposit on the LIPSS using 15W
laser power (Figure 1f,g). Analysis of the subsurface structure of
fs-5W-W (Figure 1j) shows that fs-LA can induce deformation
and cracks in the subsurface of ablated W metal plates because of
the generation of high-pressure shockwaves29 and plasticity of W
metal.36,41
To identify the compositions of annealed samples, Raman
measurement was performed with results shown in Figure 2a−c.
Five Raman peaks at 134, 272, 326, 715, and 805 cm−1 are
identifiable, being attributable to the formation of α-WO3.42 It is
noteworthy that the Raman peak intensities of 600/800/1000
°C-annealed fs-15W-W samples are much lower than those of
annealed W and fs-5W-W samples due to the existence of
deposited NPs and their light trapping effect. Upon annealing,
the deposited particles can easily transit into thermodynamically
stable stoichiometric orthorhombic α-WO3 crystals, so the
Raman peaks mainly come from α-WO3 rather than its
underlying structures. Raman peak intensities of 800/1000
°C-annealed W and fs-5W-W samples are significantly enlarged
than those of the 600 °C-annealed sample, which allow us to
identify more tungsten oxide phases besides α-WO3 Raman
peaks, including 243, 612, and 185/219/377/640 cm −1
originating from tri-WO3, WO2, and o-WO3, respectively.43
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The peaks at 400, 418, and 446 cm−1 belong to other phases of
WO3.44 The flattened bands in the range of 703−727 and 794−
827 cm−1 are attributed to the formation of tungsten oxide
crystals in multiple polymorphous states such as the γ-
monoclinic phase of WO3,45 tri-WO3, WO2, and o-WO3.43
The broadened band at 635 cm−1 is discovered from all samples,
indicating the formation of WO3−x.46 Oxygen vacancies can
render LSPR property to the tungsten oxide structures, which, in
turn, enhance the Raman signals.
The deposited particles make it difficult to characterize the
underlying structures of annealed fs-15W-W samples, so XRD
measurement was carried out for both fs-5W-W and fs-15W-W
samples. Figure 2d−f indicates that the compositions of crystals
formed at annealing temperatures of 600, 800, and 1000 °C are
almost the same for both fs-5W-W and fs-15W-W samples, so
their compositions have a high similarity. The discovery of the
broadened 635 cm−1 peak in all Raman spectra makes it
reasonable to conclude that all samples are WO3−x even though
α-WO3 is the main phase of 800/1000 °C-annealed samples. To
confirm this speculation, EDS analysis of the samples is further
implemented with the atomic percentages of C, W, and O shown
in Figure 2g and the O/W ratio shown in Figure 2h. It is found
that the LIPSS and NPs have different oxidation rates (Figure
2g,h). The LIPSS becomes more oxidized than the deposited
NPs (oxygen percentage ratios: 25.56% vs 17.69%, Figure 2g,h),
which can be explained by the following reasons: (1) NPs are
generated from the spallation/ejection of materials from the
molten layers or Coulomb/phase explosions during ablation of
each fs laser pulse.26 This process is often accompanied by the
oxidation of outermost surfaces of NPs because of the
decomposition of oxygen gas molecules in air.39 (2) In light of
a high repetition rate of 400 kHz being used for experiments, the
LIPSS must be subjected to multi-pulses’ ablation; successive
oxidations occur to the LIPSS, so its oxidation rate is much
higher than that of NPs. Besides W and O elements, a 25−27%
atomic percentage of carbon is also detected from both the
LIPSS and NPs, which should originate from CO2 decom-
position during fs laser ablation in air.39 Annealing significantly
increases the oxygen percentage to the range of 60−65% but
greatly decreases the carbon percentage to ∼10% (Figure 2g).
The O/W ratios of the LIPSS for the fs-5W-W and fs-15W-W
samples are 0.42 and 0.52, respectively, which indicates that fs-
LA at a higher laser power can cause a higher oxidation rate of
the ablated surfaces (Figure 2g).
After thermal oxidation annealing at temperatures of 600, 800,
and 1000 °C, O/W atomic ratios increase to the range of 2.2−
2.7. Cifuentes et al. once performed the thermal oxidation of
pure tungsten plates in air and confirmed the formation of WO3,
W18O49, and WO2.92,17 showing a possibility to induce the
formation of both non-stoichiometric and stoichiometric
tungsten oxide crystals. Through analysis of XRD patterns,
they speculated that WO3−x crystals should locate in the
innermost part of the oxide layers.17 Liang et al. reported that
besides stoichiometric WO3 crystals, yellow-color tungsten
oxide crystals can also be associated with WO3−x crystals
possessing a certain amount of oxygen vacancies.47 Hence, there
can also exist many oxygen vacancies in the 800/1000 °C-
annealed samples despite their yellow color (Figure 1c), in
accordance with the conclusion from the Raman analysis
(Figure 2a−c).
Air rather than an oxygen-deficient environment like vacuum
adopted for producing WO3−x crystals is due to the following
reason. Non-stoichiometric WO3−x48,49 reported for broadband
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ACS Applied Materials & Interfaces
Figure 3. (a−h) W4f and O 1s XPS spectra of fs-5W-W and 600/800/1000 °C-annealed samples.
absorbance applications are mainly W18O49 and WO2.92 crystals
with sufficient oxidation rates. Nevertheless, the main
composition of LIPSSs is tungsten metal (Figure 2g). Hence,
to increase the oxidation rates of LIPSSs, air was adopted as the
annealing environment. In addition, we have performed thermal
oxidation annealing of pure W in air at 400 °C for 2 h and found
that no obvious change occurs to the annealed W sample, so 600
°C was chosen as the starting annealing temperature for
comparison.
To identify the WO3−x phase and to check how surface bonds
and oxygen-vacancy percentages change upon annealing, the
ablated (fs-5W-W) sample and corresponding 600/800/1000
°C-annealed samples are chosen for XPS analysis. Figure 3
displays the W 4f and O 1s spectra of fs-5W-W and 600/800/
1000 °C-annealed samples and correspondingly deconvoluted
peaks. For the fs-5W-W sample, metallic W (W0) peaks at 31.3
and 33.4 eV,50 stoichiometric WO3 (W6+) peaks at 35.8 and 38.0
eV,51 and nonstoichiometric WO3−x (W5+) peaks at 34.4 and
36.7 eV52 are identifiable (Figure 3a). The loss feature peak
located at ∼41.7 eV53 is also found. After annealing at 600/800/
1000 °C, metallic metal W0 featured peaks disappear. Instead,
only oxide peaks are found. Despite the domination of WO3, the
nonstoichiometric metal oxide of WO3−x (W5+) can still be
identified (Figure 3b,c,e), which is ascribed to the formation of
W18O49.54 Deconvoluted O 1s XPS spectra (Figure 3d−f,h)
show that the percentage of W−O bonds gradually increases
from 11.0% for the fs-5W-W sample to 50.4, 60.6, and 73.0% for
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600/800/1000 °C-annealed samples, respectively, with oxygen-
vacancy percentages of 18.0, 20.5, 34.2, and 21.0%, respectively.
Specifically, O 1s peaks at 530.4, 531.0/531.1, 532.2−532.7, and
533.6 eV (Figure 3d,e) are assigned to the W−O bonds of
tungsten oxides, oxygen vacancies, adsorbed oxygen (−OH),
and adsorbed water molecules, respectively.55,56 Hence,
deduced from Raman, XRD, and XPS analysis, it can be
concluded that WO3−x containing W18O49 crystals are formed
on all ablated and annealed samples.
Figure 4 displays the surface morphologies of annealed W, fs-
5W-W, and fs-15W-W samples. Annealing causes the formation
of microcracks on all three kinds of samples at temperatures of
600 and 800 °C. The cracking rates are sample-specific. Large
network crack islands are generated on the W-600 °C sample
(Figure 4a). The inset image of Figure 4a displays an enlarged
crack island with an irregular shape, showing that the crack
island is more than 100 μm2. In contrast, zigzag cracks with
lengths of tens of micrometers are formed on the annealed
LIPSS surfaces (Figure 4d,g). The horizontal crack is in line with
the orientation of the LIPSS, and the crack islands are no longer
generated for annealed LIPSS samples. Cracking normally takes
place due to the volume-change-induced compression stresses
during oxide formation and cooling-induced thermal stresses.17
The crack densities of fs-5W-W-600 °C and fs-15W-W-600 °C
samples are much less than that of the W-600 °C sample, which
indicates that fs laser structuring is helpful to release the stresses
generated during thermal annealing and subsequent cooling due
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Figure 4. SEM images of W (a−c), fs-5W-W (d−f), and fs-15W-W (g−i) samples after thermal annealing of unablated and ablated samples in air at
temperatures of 600, 800, and 1000 °C for 2 h. Inset images shown in (a,d,g) indicate the crack states of each sample.
to the existence of deformation structures in the subsurface
(Figure 1j). The higher the laser power used for LIPSS
production, the less the cracks take place after 600 °C annealing.
Crack becomes more distinct at 800 °C because of the higher
stresses induced during crystallization, as featured by the
formation of deeper and larger cracks, crack propagation, and
appearance of structure protrusions at the boundary of cracks
(Figure 4b,e,h). The maximal crack length is more than 100 μm
(Figure 4e,h). At 1000 °C, no crack can be found (Figure 4c,f,i).
Instead, hierarchically macroporous structures are found. Our
findings are in accordance with previous reports which showed
that cracking events are very limited at 600 °C, whereas an
intense crack takes place at 800 °C, which allows the attainment
of a denser tungsten oxide layer;17 further increasing the
temperature up to 1000 °C enables a continuous growth of
tungsten oxide crystals.57
Figure 5a−d displays the higher-magnification images of
annealed micro/nanoscale structures. Many crystal clusters are
located among crack islands of the W-600 °C sample due to
heterogeneous nucleation and growth of metal oxide crystals.58
Careful examination of the clusters allows us to identify the
particle size in a broad range of 63−1100 nm (Figure 5a,b).
Increasing the annealing temperature to 800 and 1000 °C
(Figure 5c,d) gives birth to NPs and microparticles with sizes in
the range of 200−600 nm and 0.7−5.3 μm, respectively. Figure
5a−d indicates that crystals grown from a pure W plate are
inhomogeneous with a broad size distribution, especially at the
annealing temperatures of 600 and 1000 °C.
Benefiting from the surface cracks induced by 600 °C
annealing, LIPSS′ trenches become deeper (Figure 5e,i). The
annealed LIPSS is fully decorated by small particles of ∼70 nm in
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diameter (Figure 5f). With respect to the particle-deposited
LIPSS of the fs-15W-W-600 °C sample, the annealed surface is
still characterized by loosely deposited particles (Figure 5j) and
compactly grown WO3−x LIPSS structures, on top of which
intense nanoparticles of ∼140 nm in diameter are identifiable
(Figure 5m), twice that of WO3−x particles formed on the fs-5W-
W-600 °C sample (Figure 5f). Due to the compactness of grown
LIPSS structures and newly formed crystals, the height of the
resultant fs-15W-W-600 °C surface structure is only within the
range of 200 nm (Figure 5n,o), much less than that of the LIPSS
(Figure 1g,i). The reason why the structure morphologies of fs-
5W-W-600 °C and fs-15W-W-600 °C are a little different is
unknown, which may be aroused by different crystal growth
behaviors of LIPSSs obtained under different ablation
conditions. Increasing the annealing temperature to 800 °C
increases the size of crystals to ∼270 nm for both fs-5W-W-800
°C and fs-15W-W-800 °C samples. The enlarged crystals
overlap with each other, making it difficult to identify the
original LIPSSs.
With respect to the fs-15W-W sample, the deposited NPs
cannot be found after 800 °C annealing, which indicates that
deposited NPs have been merged with the underlying LIPSS
structure to serve as seeds for WO3−x crystal growth at higher
temperatures no less than 800 °C. At 1000 °C, not only larger
macroporous structures with macropore sizes of 1∼4 μm are
formed (Figure 5l, right part, corresponding to the upper side
region of Figure 4i), while small crystals of ∼1 μm in diameter
are tightly packed in the regions of nonporous surfaces (Figure
5l, left part, corresponding to the lower side region of Figure 4i).
In contrast, the crystals on the fs-5W-W-1000 °C sample have
very limited macropores due to the lack of deposited particles
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Figure 5. (a−d), (e−h), and (i−l) SEM images of the pure W, fs-5W-W, and fs-15W-W samples annealed at 600, 800, and 1000 °C, respectively. (m-o)
AFM height profiles (top and side view) and the cross-sectional profile of the fs-15W-W-600 °C sample.

Figure 6. Schematic illustration of structural morphology evolution upon annealing of pure W, fs-5W-W, and fs-15W-W samples in air at temperatures
of 600, 800, and 1000 °C for 2 h.

(Figure 4f), whereas the crystals on the W-1000 °C sample are
macroporous (Figure 4c) owing to the annealing-induced dense
cracks and surfaces’ warpage.
Figure 6 summarizes both the microscale and nanoscale
growth routes for flat W, LIPSS, and LIPSS-NP interfaces at
annealing temperatures of 600, 800, and 1000 °C. For the flat W
surface, large and deep cracks form with many clusters filling the
inside of the deep trenches at 600 °C. Further increasing the
annealing temperature to 800 °C exacerbates surface cracks,
which results in the formation of much deeper cracks and
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production of more crystal clusters. These crystal clusters
loosely fill the crack trenches, and many of them are well above
the horizontal level of the interfaces. These protruded clusters
will act as the growth seeds at the temperature of 1000 °C to
induce macropores. Due to the randomly located crystal
clusters, some regions grow tightly to form densely small
crystals, while some regions grow loosely to form larger crystal
macroporous structures. The similar scenario occurs for the
deposited NPs on the fs-15W-W sample. The difference is the
shallow depth of cracks originating from the LIPSS and the
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Figure 7. (a−c) UV−vis and (d−f) MIR absorbance of pure W, fs-W-5W (c,d), and fs-W-15W samples and corresponding 600/800/1000 °C-
annealed samples. The absorbance spectra (obtained by 1-reflectance) of pure W and fs-W-5W are adapted from ref 39, Copyright 2021, Elsevier. (g)
Schematic illustration of the experimental setup for photothermal measurements. (h) Photothermal-induced temperatures of different samples after 1
min light irradiation at different wavelength bands (200−800, 420−800, 800−2500, and 200−2500 nm) with light densities of 1694, 1540, 1460, and
3160 mW/cm2. Different wavelength bands of light were adjusted by using light filters. Photothermal temperatures of each sample were measured
three times. The room temperature was 19 °C as the starting temperature. (i) IR thermal images of fs-5W-W-600/800/1000 °C samples after 1 min’s
light irradiation, which indicates that the higher the annealing temperature, the better the photothermal effect. The highest temperature of the
irradiated sample surface from the IR image is used as the photothermal indicator for analysis.

growth seeds generated by fs-LA. Fs-LA can greatly refine the
grains in the substrate into nanoscale structures,59 so the grown
crystals become highly uniform after annealing at 600 °C for 2 h.
Due to the lack of deposited NPs to create a large region of
macropores, the density of macropores grown from the fs-5W-W
sample is very limited, and only separated macropores can be
found. Overall, it can be concluded that the LIPSS provides a
better template for the nucleation and growth of smaller and
more homogeneous particles than pure W plates and facilitates
the formation of hierarchical nanostructures at 600/800 °C and
hierarchical macroporous structures at 1000 °C while deposited
by a high density of NPs.
We evaluated the absorbance of non-annealed and annealed
samples in both UV−NIR and MIR ranges with the results
shown in Figure 7. The pure W plate has a low absorbance
because of the absence of surface structures (Figure 7a).39
Specifically, the metallic W surface has the highest absorbance in
the UV band and then gradually decreases to 24% with
increasing the wavelength to 2500 nm. Endowment of the LIPSS
on flat W surfaces via 5W-fs-LA can significantly increase the
absorbance in the UV−vis range but cannot significantly
increase absorbance in the whole NIR range, as featured by a
dramatic decrease in the absorbance within the 1500−2500 nm
24053
wavelength band (Figure 7b),39 which is ascribed to the low NIR
absorption capacity of the metallic LIPSS.38 This trend is also
applicable to the absorbance in the MIR range shown in Figure
7d,e which indicates that fs laser structuring of the LIPSS is only
capable of slightly increasing MIR absorbance. Deposition of a
large amount of WO3−x particles on the LIPSS via high-power
15W fs-LA can slightly further enhance the absorbance in the
whole UV−MIR broadband (Figure 7c,f) due to the intrinsic
broadband absorbance of WO3−x particles60 and the light
trapping effect of assembly particle aggregates.39 Nevertheless,
the efficacy of partial coverage of the LIPSS by WO3−x particles
in enhancing absorbance is very limited. In our previous report,
we demonstrated that only in the case of the whole coverage of
the LIPSS via self-assembly of macroporous WO3−x particle
aggregates, an excellent UV-to-MIR ultrabroadband absorber
can be acheived.39 However, these assembly WO3−x particles are
loosely deposited, which can be easily washed away to cause a
significant decrease in UV-to-MIR absorbance.
Annealed samples display different absorbance capacities in
the UV−NIR and MIR bands (Figure 7a−f). After endowment
of WO3−x crystals and construction of hierarchical nanostruc-
tures induced by 600 °C annealing (Figure 3e), NIR band
absorbance is dramatically enhanced (Figure 7a−c) due to the
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ACS Applied Materials & Interfaces
Figure 8. (a−c) Cross-sectional images of fs-5W-W-600 °C, fs-5W-W-800 °C, and fs-5W-W-1000 °C samples, respectively. (d−f) EDS analysis of the
cross-sectional structures of the fs-5W-W-600 °C sample.
oxygen-vacancy-enhanced absorbance and light trapping effect.
In consequence, all 600 °C-annealed samples have the highest
absorbance in the UV−NIR broadband. Increasing the
annealing temperature to 800 °C and 1000 °C leads to the
increase in the size of WO3−x crystals (Figures 4 and 5) and
meanwhile alters the density of oxygen vacancies (Figure 3f). In
consequence, the intrinsic absorbance of WO3−x crystals
becomes much more apparent, which causes a significant
decrease in vis−NIR absorbance (Figure 7a−c).
Absorbance valleys originating from the intrinsic absorption
of tungsten oxide crystals in the UV−vis bands61 are also
identifiable for W-600 °C and fs-15W-W-600 °C samples
(Figure 7a,c) but indistinguishable for the fs-5W-W-600 °C
sample, making it the best ultrabroadband absorber (Figure 7b)
with >90% absorbance in the UV−vis−NIR ultrabroadband
(200−2500 nm) and >80 and >50% within light bands of 2.5−9
and 9−16 μm, respectively. The structural light trapping effect is
deemed to cause the indistinguishability of intrinsic absorption
of tungsten oxide crystals for the fs-5W-W-600 °C sample, which
can also be deduced from W-1000 °C and fs-15W-W-1000 °C
samples, which has a higher absorbance in the band of 500−
1500 nm than 800 °C-annealed counterpart samples due to the
formation of macroporous structures (Figure 7a,c).
There is no big difference of absorbance in the 2.5−10 μm
MIR range for all annealed samples. A little difference in the
longer 10−16 μm MIR range is observed due to structural and
compositional variations with 1000 °C-annealed samples
possessing the highest MIR absorbance (Figure 7d−f).
Developing such broadband absorbers is very important for
broadband sensors,62,63 such as noncontact IR thermometers
and non-dispersive infrared gas sensors which require excellent
absorbance in the wavelength bands of 8−14 and 3−5 μm,
respectively, with great potentials to be used for biomedical tests,
epidemic and environmental risk prevention/control applica-
tions.
To extend the application scope of LIPSS-grown WO3−x
interfaces, we measured the photothermal properties of the
LIPSS fs-5W-W sample and correspondingly annealed samples
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using the setup shown in Figure 7g. Figure 7h displays the
temperatures detected after 1 min irradiation using different
bands of light (200−800, 420−800, 800−2500, and 200−2500
nm) with light densities of 1694, 1540, 1460, and 3160 mW/
cm2. Light bands and densities were adjusted by using light
filters.
For each annealed sample, photothermal-induced temper-
atures gained after visible (420−800 nm) and NIR (800−2500
nm) light irradiation are almost the same. The higher the
annealed temperature (1000 > 800 > 600 °C), the better the
photothermal performance, which can even offset their low
absorbance capacities. This phenomenon is attributable to the
increased oxidation of annealed samples, as indicated in Figure
8. As measured from the cross-sectional SEM images (Figure
8a−c), the thicknesses of oxidation layers for fs-5W-W-600 °C,
fs-5W-W-800 °C, and fs-5W-W-1000 °C samples are around 6,
150, and 507 μm, respectively. EDS analysis shown in Figure
8d,e indicates that the upper structural layer is an oxide layer
with a 52.64% atomic percentage of oxygen, while the bottom
layer is the metal substrate with merely a 4.03% atomic
percentage of oxygen. The line-scanning EDS analysis shown in
Figure 8f further confirms that there exists an interface between
metal and metal-oxide layers. Annealing LIPSSs at 600 °C not
only induces the growth of tungsten oxide crystals from the
substrate but also induces the formation of macropores
hundreds of nm long underneath the upmost surface, as
indicated by the white arrows in Figure 8a, which is attributed to
the horizontal growth and bending of WO3−x-grown crystals.
These macropores correspond to the regions of LIPSS trenches,
which can well explain the periodicity of macropores. The depth
of the fs-5W-W-600 °C LIPSS is about 500 nm, a little higher
than the depth of the LIPSS shown in Figure 1e,f, indicating that
annealing treatment indeed deepens the LIPSS height via crystal
growth.
The average photothermal-induced temperatures from UV−
vis light (200−800 nm) irradiation are 56, 60, and 69 °C for fs-
5W-W-600/800/1000 °C samples, respectively. Despite the fs-
5W-W-600 °C sample being much thinner (6 μm) compared
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ACS Applied Materials & Interfaces
Figure 9. Schematic illustration of the sample states upon irradiation by light at bands of 200−800, 420−800, 800−2500, and 200−2500 nm with
corresponding light intensities of 1694, 1540, 1460, and 3160 mW/cm2 and summary of the photothermal conversion capacity and heat preservation
capacity for fs-5W-W and fs-5W-W-600/800/1000 °C samples.
with (150 and 507 μm) fs-5W-W-800/1000 °C samples, the
accessible photothermal temperature is only a little lower. This
finding is indicative of a better UV−vis photothermal conversion
capacity of the fs-5W-W-600 °C sample under the same
irradiation conditions (Figure 9), a trend which is also applicable
to the vis (420−800 nm) and NIR (800−2500 nm) bands light
irradiation, as shown in Figure 7h. Special attention should be
paid to temperature differences of 15/9/7 °C aroused by
irradiation of 200−800 and 420−800 nm wavelength band light
for fs-5W-W-600/800/1000 °C samples, respectively. It
indicates that the fs-5W-W-600 °C sample has the highest
photothermal conversion capacity for light within the wave-
length band of 200−420 nm, attributable to its highest UV
absorbance with indistinguishably intrinsic absorption of
tungsten oxide crystals (Figure 7b). Deduced from the above-
mentioned findings, the fs-5W-W-600 °C sample with a WO3−x
layer with the uppermost hierarchical LIPSS nanostructures
should be superior to 800/1000 °C-annealed WO3−x layers, if at
the same crystal thickness, for photothermal applications due to
its better ultrabroadband absorbance.
Photothermal-induced temperatures greatly differ upon
broadband (200−800 and 200−2500 nm) light irradiation
with average temperatures of 56/60/69 °C and 60/80/109 °C
for fs-5W-W-600/800/1000 °C samples (Figure 7h), respec-
tively. That is, for the fs-5W-W-600 °C sample, using higher-
density and broader-band light (200−2500 nm) only leads to a
temperature rise of 4 °C but 20/40 °C for fs-5W-W-800/1000
°C samples. This phenomenon indicates that thermally
conductive tungsten underneath a very thin oxide layer of the
fs-5W-W-600 °C sample can efficiently transfer photothermal-
induced heat to the substrate very quickly (Figure 9). This
deduction is in accordance with the photothermal conversion
behavior of the fs-5W-W sample where the highest detectable
temperature appears on the supportive substrate rather than on
the LIPSS (Figure 7i). In contrast, photothermal heat can be
well preserved in the thicker tungsten oxide layers of fs-5W-W-
800/1000 °C samples (Figure 7i). This means that other than
the thickness of tungsten oxide photothermal converters, the
supportive substrate is another critical factor to be considered
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for developing high-performance photothermal converters
(Figure 9).
Table 1 lists the best absorber of this work and tungsten-based
absorbers produced using other techniques. Regarding tungsten
oxide absorbers, reports are mainly about their UV−NIR
absorbance in the colloid state64 and transmittance in the film
state.65 It can be seen that absorbance of the fs-5W-W-600 °C
sample in the ultrabroadband of 200−2500 nm is much better
than that of metal−dielectric−metal (e.g., W/SiO2/W)
metamaterial66 and W-coated anodic aluminum oxide (AAO)
nanowires.67 Although the UV−NIR absorbance capacity of the
fs-5W-W-600 °C sample is lower than that of Al2O3/W/Al2O3/
W/Si metal−insulator−metal (MIM) resonators,68 hierarchical
LIPSS/NPs structures of the fs-5W-W-600 °C sample presented
in this work excel at high absorbance in a much broader light
band. One of the best W-based ultrabroad absorbers is tungsten-
coated Si nanopillars with >95% absorbance in the 220−2600
nm range,69 which were produced by five procedures including
spin coating, polystyrene sphere (PS) lithography, magnetron
sputtering, metal-assisted chemical etching (MACE), and
atomic layer deposition (ALD). Compared with this work, the
absorbers prepared by fs laser ablation and thermal oxidation
annealing are much simpler, based on which the diversity of
WO3−x interfacial structures can be enriched.
4. CONCLUSIONS
This work demonstrates that the combination of fs laser
structuring and thermal oxidation annealing is a facile method to
prepare ultrabroadband tungsten oxide absorbers using LIPSS as
crystal growth templates. The best template is the LIPSS with
low-density deposited particles. After annealing in air at 600 °C
for 2 h, the LIPSS transforms into a hierarchically nano-
structured WO3−x (containing W18O49 crystals as confirmed by
XRD and XPS) absorber, possessing more than 90%, 80%, and
50% absorbance (calculated by 1- reflectance) in the light bands
of 200−2500 nm, 2.5−9 μm, and 9−16 μm, respectively. For the
tungsten oxide absorbers grown by 600 °C annealing of a pure W
plate and high-density WO3−x-NP-deposited LIPSS obtained by
fs laser ablation at a higher laser power, an obvious absorbance
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ACS Applied Materials & Interfaces www.acsami.org Research Article

valley corresponding to the intrinsic absorption of tungsten

work
Ref
Table 1. Comparison of Preparation Methods and Absorbance Performances for Fs-5W-W-600 °C Absorber (This Work) and Tungsten-Based Ultrabroadband Absorbers

>90% in the 200−2500 nm range, >80% within this

oxide crystals turns out in the UV−vis band, thus diminishing

>90% in the 200−2500 nm range, >80% in the 39

66

67

68

70

69
their broadband absorbance. Increasing the annealing temper-

below 40% and 90% in the vis and NIR ranges

>95% in the 650−1750 nm range, but drops to
≈90% in the 250−2500 nm range but strongly
ature from 600 to 800 and 1000 °C changes the surface color

>90% absorbance in the 400−1700 nm range

>95% absorbance in the 220−2600 nm range

UV−NIR and MIR absorbance capacity

from brown to dark blue and finally to yellow, gradually increases

2.7−5 μm, 50−80% within 5−14 μm crystal size from ∼70 nm to ∼4 μm, and alters intrinsic
2.5−9 μm, >50% within 9−16 μm

>90% in the 275−1000 nm range absorbance of WO3−x crystals. Formation of increasingly thicker
metal-oxide layers (6, 150, and 507 μm thickness for 600/800/
fluctuates in the NIR range 1000 °C-annealed samples, respectively) gradually enhances the
absorber’s photothermal conversion capacity upon high-density
(3160 mW/cm2) and ultrabroadband (200−2500 nm) light
irradiation but is much less effective upon lower-density (1694,
1540, and 1460 mW/cm2) and shorter-band (200−800, 420−
800, and 800−2500 nm) light irradiation. This finding allows us
to deduce that the conductive metal substrate can quickly
dissipate photothermal heat, while the tungsten oxide layer can
hexagonal prism arrays: prism base edge: 100 nm, prism height: 50 nm, unit

100 nm top protection layer of Al2O3, a semitransparent layer consisting of

well preserve heat. If taking into account oxide layer thickness,

the best ultrabroadband absorber of LIPSS-grown hierarchical
nanostructure (fs-5W-W-600 °C sample) is more effective and
AAO: 6 μm thick, distance between adjacent bundles was 1−4 μm

efficient for photothermal conversion. In addition, it is also

12 nm W, a 100 nm Al2O3 spacer, 100 nm bottom W layer,

found that the deformation layer formed in the ablated W

subsurface is helpful to release the thermal pressure for the
formation of less-density cracked surfaces.

■
structure properties
LIPSS decorated by ∼170 nm WO3 crystals

AUTHOR INFORMATION
Corresponding Authors
hierarchical WOx particle aggregates

period: 290 nm, 40 nm thick SiO2

Dongshi Zhang − Shanghai Key Laboratory of Materials Laser

20−60 nm W and 20 nm Al2O3

Processing and Modification, School of Materials Science and

Engineering, Shanghai Jiao Tong University, Shanghai
35−55 nm W thickness

200240, China; orcid.org/0000-0003-4425-2704;

Email: zhangdongshi@sjtu.edu.cn
Zhuguo Li − Shanghai Key Laboratory of Materials Laser
Processing and Modification, School of Materials Science and
Engineering and The State Key Lab of Metal Matrix
Composites, School of Materials Science and Engineering,
Shanghai Jiao Tong University, Shanghai 200240, China;
Email: lizg@sjtu.edu.cn
Al2O3/W/Al2O3/W/Si MIM resonators

Authors
composition and layout

Al2O3/W/Si, tungsten-coated Si

Ruijie Liu − Shanghai Key Laboratory of Materials Laser

metallic tungsten nanocones

Processing and Modification, School of Materials Science and

W-coated AAO nanowires

Engineering, Shanghai Jiao Tong University, Shanghai

200240, China
Sihan Ji − Key Laboratory of Materials Physics and Anhui Key
Laboratory of Nanomaterials and Nanotechnology, Institute of
W + WO3−x

W + WO3−x

nanopillars
W/SiO2/W

Solid State Physics, Hefei Institutes of Physical Science, Chinese

Academy of Sciences, Hefei 230031, China
Yunyu Cai − Key Laboratory of Materials Physics and Anhui
Key Laboratory of Nanomaterials and Nanotechnology,
PS sphere lithography + magnetron sputtering
anodic oxidation + metal coating + annealing

spin-coating + (PS) spheres self-assembly +

Institute of Solid State Physics, Hefei Institutes of Physical

E-beam deposition + direct current (DC)

oxygen RIE electron-beam evaporator

Science, Chinese Academy of Sciences, Hefei 230031, China

600 °C-thermal anneal + fs structuring

metal−dielectric−metal metamaterial

Changhao Liang − Key Laboratory of Materials Physics and

Fs structuring + particle deposition

Anhui Key Laboratory of Nanomaterials and Nanotechnology,

Institute of Solid State Physics, Hefei Institutes of Physical
methods

Science, Chinese Academy of Sciences, Hefei 230031, China;

orcid.org/0000-0003-0202-0438
+ MACE + ALD

Complete contact information is available at:

https://pubs.acs.org/10.1021/acsami.2c04523
sputtering

Notes
The authors declare no competing financial interest.
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ACS Applied Materials & Interfaces
■
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■
NOTE ADDED AFTER ASAP PUBLICATION
Originally published ASAP April 29, 2022; Figure 5 graphic and
associated text updated May 13, 2022.
https://doi.org/10.1021/acsami.2c04523
ACS Appl. Mater. Interfaces 2022, 14, 24046−24058