Accepted Manuscript

Growth of tungsten oxide nanostructures by chemical solution deposition

L.H. Jin, Y. Bai, C.S. Li, Y. Wang, J.Q. Feng, L. Lei, G.Y. Zhao, P.X. Zhang

PII: S0169-4332(18)30269-1
DOI: https://doi.org/10.1016/j.apsusc.2018.01.251
Reference: APSUSC 38390

To appear in: Applied Surface Science

Received Date: 16 November 2017

Please cite this article as: L.H. Jin, Y. Bai, C.S. Li, Y. Wang, J.Q. Feng, L. Lei, G.Y. Zhao, P.X. Zhang, Growth of
tungsten oxide nanostructures by chemical solution deposition, Applied Surface Science (2018), doi: https://doi.org/
10.1016/j.apsusc.2018.01.251

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Growth of tungsten oxide nanostructures by chemical solution deposition

L.H. Jin1,*, Y. Bai2, C.S. Li1, Y. Wang1, J.Q. Feng1 , L. Lei2, G.Y. Zhao2, P.X. Zhang1

1
Northwest Institute for Nonferrous Metal Research, Xi’an 710016, P. R. China
2
Department of Material Physics and Chemistry, School of Materials Science and

Engineering, Xi’an University of Technology, Xi’an 710048, P. R. China

Abstract: Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates

by a simple chemical solution deposition. The decomposition behavior and phase

formation of ammonium tungstate precursor were characterized by thermal analysis

and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures

were analyzed by scanning electron microscopy, atomic force microscopy and X-ray

photoelectron spectra. The effects of crystallization temperature on the formation of

nanodots and nanowires were investigated. The results indicated that the change of

nanostructures had close relationship with the crystallization temperature during the

chemical solution deposition process. Under higher crystallization temperature, the

square-like dots transformed into the dome-like nanodots and nanowires. Moreover

high density well-ordered nanodots could be obtained on the substrate with the further

increase of crystallization temperature. It also suggested that this simple chemical

solution process could be used to adjust the nanostructures of tungsten oxide

compounds on substrate.

Keywords: chemical solution deposition; nanostructure; tungsten oxide

* Corresponding author. Email: lhjin@c-nin.com.

1
1. Introduction

Engineering nanomaterials have been of great interest on the basis of their large

surface area and unique optical, electrical and catalytic properties [1]. Tungsten

oxides are important semiconductor materials and have been investigated as the

promising applications in smart window, semiconductor sensor, optical display, and

photocatalyst because of their outstanding properties [2-4]. For example, the

three-dimensional structured tungsten oxides contributed the improvement of

oxidation effect for methane [5].

Various fabrication processes of nanoparticals, nanorods and nanowires have been

intensively studied [6-8]. Hajime Wagata et al. have fabricated well-aligned

honeycomb-designed layers of potassium tungstate by spray deposition using

polystyrene colloidal crystals templates [9]. This potassium tungstate layer consists of

numerous one-dimensional nanowires grown on the honeycomb wall surfaces.

Tungsten oxide nanoparticles have been successfully synthesized by thermal

decomposition of ammonium tungstate loading on g-C3N4 [10]. Potassium tungsten

nanorods were synthesized by hydrothermal treatment. The size and shape of

nanorods could be controlled by stirring speeds and temperatures [11]. Moreover, a

high quality tungsten oxide thin film was efficiently fabricated using a freshly

electrochemical activated substrate as catalysts with a facile dipping process. This

tungsten oxide film exhibited a significantly improved electrochromic performance

due to the high proton diffusion coefficient and strong interface contact [12]. In

summary, tungsten oxides or thin films can be conventionally synthesized by

hydrothermal, thermal decompositions, vapor deposition methods. However, these

methods still have some disadvantages, such as a little complicated process and

uneasy adjustment of nanostructure. Further development of very simple ways to

2
control the self-assembled formation of tungsten oxide nanostructures is necessary.

Chemical solution deposition (CSD) has been widely used to prepare a broad range

of functional oxide films, such as Pb(Zr,Ti)O3 , (Ba,Sr)TiO3, LaSrMnO3, CeO2,

REBa2Cu3Oy, etc [1,13-17]. In comparison with chemical vapor deposition and

physical vapor deposition, CSD shows some merits such as low cost, simplicity,

adaptable and good stoichiometric control [1,13]. Recently CSD has been adopted for

the fabrication of other types of nanostructures, for example, self-assembled BaZrO3

nanodots [18] and Ce1-xGdxO2-y nanostructures [19]. Growth of nanostructures

requires the use of ultradiluted precursor solutions and precise adjustment of the

nucleation and growth processes [1,13]. However, there are no more reports about the

fabrication of tungsten oxide nanostructures with CSD. An understanding of the

growth behavior of tungsten oxide nanostructures is crucial to the improvement of

properties and application for functional materials.

In this work, tungsten oxide layers were deposition on LaAlO3 (LAO) (00l)

substrates by a simple chemical solution process. By tuning crystallization

temperature, tungsten oxide layers with different morphologies of square-like dots,

dome-like nanodots and nanowires can be acquired. The result is helpful for the

understanding of the nucleation and growth behaviors of tungsten oxide. It also

indicates that chemical solution deposition as a promising simple method may be

applied to many other functional nanostructures.

2. Experimental

Precursor solutions for tungsten oxide growth were prepared by dissolving

ammonium tungstate hydrate ((NH4)6W12O39·xH2O, Alfa Aesa) in the solvents of

N-methyl pyrrolidone (NMP) and ethanol. The mixture was continuously stirred at 40
o
C to get a stable solution. The volume ratio of N-methyl pyrrolidone and ethanol was

3
kept at 2:1. The final solution’s concentration was modified within the range of 0.005

- 0.05 mol/L.

Tungsten oxide nanostructures were prepared by spin-coating on LaAlO3 (LAO)

(00l) single crystal substrates. Prior to the spin coating process, LAO substrates were

cleaned with ethanol in an ultrasonic bath. The coating process was finished under dry

air and room temperature. The precursor solution was coated onto LAO substrates

with a spinning rate of 3000 rpm for 30 s [16]. The samples were crystallized in a

continuous flowing Ar+4%H2 gas atmosphere at 500 °C, 700 °C and 900 °C, which

named A, B, C, respectively. The heating rate was kept at ~100 oC/min during the

crystallization. The dwell time was controlled at 30 minutes. At the end of heat

treatment, the furnace cooling was adopted. The tungsten oxide nanostructures were

prepared with the low concentration solution (0.005 mol/L), and powders were

obtained with the high concentration precursor solution (0.05 mol/L) at the same

conditions.

Thermal gravimetric analysis and differential scanning calorimetry were performed

with a heating rate of 20 K/min in Ar atmosphere (TG-DSC Q1000DSC). The

morphology of nanostructure was characterized by scanning electron microscopy

(SEM JSM-6700) and atomic force microscopy (AFM SPM-9500J3). AFM images

with scanning areas of 20 µm × 20 µm were obtained in a tapping mode. The phase

composition was analyzed using X-ray diffraction with CuKα radiation

(λ=0.15418nm) of 40 kV and 50 mA (XRD, Bruker D8 Advance). The chemical

states of nanostructure were evaluated by X-ray photoelectron spectra analysis (XPS,

ESCALAB 250Xi).

3. Results and discussion

The decomposition information of the ammonium tungstate precursor was obtained

4
by TG-DSC analyses. Fig. 1 shows the TG-DSC curves of (NH4)6W12O39·xH2O

precursor. The endothermic and exothermic peaks along with obvious weight loss

suggest that the important decomposition reactions take place in the temperature

range of 50 oC - 500 oC. Two endothermic peaks (128 oC, 337 oC) and a strong

exothermic peak (440 oC) can be observed on the DSC curve in the whole temperature

range. Corresponding to the peaks in the DSC curve, the weight loss of ammonium

tungstate precursor can be divided into three temperature stages of 50 oC - 210 oC, 210
o
C - 400 oC and 400 oC - 500 oC. In the first stage, the endothermic peak at 128 oC can

be ascribed to dehydration of ammonium tungstate. The weight loss of ~ 2.8% may

indicate the loss of about four molecules of H2O for every one molecule of

(NH4)6W12O39·4H2O. In the second stage, the endothermic peak at 337 oC along with

weight loss of 4.5% can be assigned to the release of NH3 and water. When

(NH4)6W12O39 transforms to (NH4)2W12O37, the ratio of NH4 to WO3 will accordingly

change from 6:12 to 2:12 [20]. In the third stage, the last exothermic peak at 440 oC is

assigned to the decomposition of (NH4)2W12O37 and the formation of tungsten oxide.

The gaseous and final products of precursors are listed in Table 1. Three stages of

decomposition behaviors are close to that reported by French et al. [20] and Basu et al.

[21]. It is concluded that tungsten oxide can be acquired from the decomposition of

ammonium tungstate when the temperature is above 500 oC under Argon atmosphere.

The powders and nanostructures were prepared under the same heat treatment

process with high concentration solution and dilute precursor solution, respectively.

Fig. 2 gives the XRD patterns of the tungsten oxide powders crystallized under

Ar+4%H2 atmosphere with different crystallization temperatures. Samples show

different peaks, indicating the formation of different phases. When crystallization

temperature is at 500 oC, the diffraction peaks can be identified as WO2.92 phase

5
(JCPDS 30-1387). With further increasing crystallization temperature, the diffraction

peaks of WO2.72 appear. The sharp peak of WO2.72 indicates the loss of oxygen and

good crystalline of tungsten oxide (JCPDS 65-1291). When crystallization

temperature reaches 900 oC, the diffraction peaks of W appear (JCPDS 89-4900). The

results reveal that the formation of tungsten oxide with nonstoichiometry oxygen can

be easily realized by tuning crystallization temperature. It also suggests that the

oxygen-free atmosphere can promote the transformation from the tungsten oxide to

tungsten at high temperature.

The diluted precursor solution was used to prepare very thin film of tungsten oxide.

The nanostructures appear on the surface of LAO substrate under oxygen-free

atmosphere at different crystallization temperatures. Fig. 3 shows the SEM images of

tungsten oxide nanostructures deposited on LAO substrates with different

crystallization temperatures. The crystallization temperatures of samples A, B and C

are 500 oC, 700 oC and 900 oC, respectively. Thick and smooth film prepared at 900
o
C is listed as reference (sample D), shown in Fig. 3d. There are different

morphologies of other samples. Some large squares of tungsten oxide can be clearly

observed in sample A (Fig. 3a), which are accompanied by small nanodots. It may be

significantly noticed that both nanowires and nanodots of tungsten oxide appear on

the surface of sample B with the crystallization temperature of 700oC (as shown in Fig.

3b). At the case of 900 oC, highly ordered nanodots of tungsten can be seen in sample

C (Fig. 3c), in comparison with the smooth thick film. There may be different

nucleation and growth behaviors of these nanostructures. It also suggests that the

morphology of nanostructures strongly depends on the crystallization temperature.

Fig. 4 displays the AFM images and the corresponding height profiles of samples A,

B and C, respectively. The morphology of thick film D is also listed as reference (Fig.

6
4d). Thick film illuminates a smooth and homogeneous surface with a low root mean

square roughness (Rrms) value of ~2.9 nm. In comparison with thick film, three special

nanostructures are obviously different. As shown in the Fig. 4a (sample A), all

square-like WO2.92 dots show medium lateral size of ~1 μm and medium height of

~276 nm with an average density of ~0.1 dots/μm2. Moreover, some very small

nanodots are also observed in the background of square (Sample A). The mixture of

dome-like nanodots and nanowires are shown on the surface of sample B (Fig. 4b).

Some parts of wires grow up to nanowalls. The average height and lateral width of

nanodots are ~80 nm and ~0.4 µm, respectively. And the average height and length of

nanowires are ~80nm and ~2 µm, respectively. The densities of dots and wires are

~0.41 dots/μm2 and ~0.4 wire/μm2, respectively. It implies that a bimodal size

distribution exists on sample B at such heat treatment condition. Furthermore, only

dome-like tungsten nanodots exist on the surface of sample C without other

nanostructures (Fig. 4c). The average height and lateral size of tungsten nanodots are

~71 nm and ~0.14 µm, respectively. The density of nanodots is ~6 dots/μm2. With

increasing crystallization temperature, the nanostructures change from square-like

dots to the mixture of wires and dome-like dots. And then the wires disappear and

only pure dome-like dots exist on the substrate. Besides, the average size of nanodots

decreases and the density increases with the increase of crystallization temperature. It

suggests that the formation of nanostructures on the surface of substrate can be

controlled by tuning crystallization temperature under reducing atmosphere. This

microstructure may be associated with the nucleation and growth of tungsten oxide.

The thermal driven is eventually responsible for the formation of nanostructures.

XPS was employed to analyze the chemical state of the tungsten oxide

nanostructures. The 4f energy level of tungsten splits into two energy levels of 4f7/2

7
and 4f5/2 with energy splitting of 2.15 eV due to the spin-orbit coupling [22]. Fig. 5

shows the XPS peaks of W (4f) of samples A, B and C with different crystallization

temperatures. Two peaks of W 4f7/2 and W 4f5/2 energy levels are at ~35.77 eV and

~37.87 eV, as shown in sample A, which can be ascribed to the presence of WO2.92.

With the crystallization temperature of 700 oC, there are two peaks at binding energies

of ~35.27 eV and ~37.47 eV, which are corresponding to the chemical state of WO2.72.

The shift of peak position towards low binging energy indicates that there is chemical

state transformation of tungsten oxide [23]. With increasing crystallization

temperature, reduction of anoxic tungsten oxide happens and the high valence

tungsten oxide changes to low valence. At the temperature of 900 oC, the peaks at

~31.77 eV and ~33.97 eV can be assigned to binding energy levels of elemental W,

which implies the full reduction of tungsten oxide into tungsten. It is in agreement

with the results of XRD analysis. It indicates that the heat treatment under

oxygen-free atmosphere has important influence on the morphology and phase

formation of tungsten compound film.

Chemical solution process includes coating, decomposition, nucleation, and growth

steps. The nucleation and growth of nanostructure may be correlated with the

thermodynamic and kinetic mechanism, including atomic diffusion, surface energies

and nucleation barriers [24-27]. Gibert et al. reported the self-assemble of BaZrO3

nanodots from chemical solution under oxygen atmosphere [28]. There is obvious

coarsening effect and the size of BaZrO3 nanodots increases at high crystallization

temperature. However, the phenomenon in this study is different. The size of tungsten

oxide decreases under oxygen-free atmosphere at higher crystallization temperature.

In this work, tungsten oxide begins to nucleate and grow at the interface between the

amorphous film and substrate. The driving forces that govern the transformation from

8
the amorphous film into crystalline compounds can play a significant role in defining

the active nucleation events and film microstructure [29, 30]. Here, the nucleation and

growth of tungsten oxide still follow the Volmer-Weber mechanism. The exact

process of self-assemble nanostructure may be complex. When a Gibbs energy barrier

is overcome, large square dots are formed on the surface at 500 oC under the

oxygen-free atmosphere (Fig. 4a). Large dots may be ascribed to the coarsening effect

of tungsten oxide under the oxygen-free atmosphere. With increasing crystallization

temperature, both the driven force and the nucleation density increase correspondingly.

The shape of dot changes from square to dome and the wire appears at 700 oC (Fig.

4b). Meanwhile, the average size of dots decreases from ~1 µm to ~0.4 µm and the

dot density increases from ~0.1 dots/μm2 to ~0.41 dots/μm2. Moreover, the generation

of nanowires is controlled by the thermally activated diffusion process. It implies that

this crystallization condition may be beneficial for the atomic diffusion and

coarsening of nanowires. On the other hand, at the case of 900 oC, the dot density

increases significantly from ~0.41 dots/μm2 to ~6 dots/μm2, and the size of dot

decreases from ~0.4 µm to ~0.14 µm. It indicates that the nucleation barrier decreases,

leading to the remarkable increase of nucleation density. Besides, the transformation

from anoxic tungsten oxide to tungsten is governed by oxygen-free atmosphere. The

atomic diffusion may be inhibited by the oxygen-free atmosphere. Under this

condition, the well-ordered nanodots form on the surface of substrate. The results

support that crystallization temperature plays an important role on the formation of

tungsten oxide nanostructures prepared by chemical solution deposition. It is worth

mentioning that this simple method may be useful for the fabrication of precisely

controlled oxide nanostructures and the microelectronic applications.

4. Conclusions

9
 Tungsten oxide nanostructures, consisting of square-like dots, dome-like nanodots

and nanowires, have been successfully fabricated on LAO substrate by chemical

solution process. Thermal gravimetric analysis indicates that the precursor

decomposes before 500 oC to form anoxic tungsten oxide. XRD analysis reveals that

there is a phase transformation from anoxic tungsten oxide to tungsten under

oxygen-free atmosphere. The morphology of nanostructure is greatly dependent on

the crystallization temperature. With increasing crystallization temperature, the square

dots are changed to dome-like dots and the nanowires appear simultaneously. And

then the well-ordered nanodots without other morphologies are formed on the surface

of substrate with further increase of crystallization temperature. The formation of

nanowires may be related to the atomic diffusion and coarsening effect. The

increasing density of well-ordered nanodots may be ascribed to the higher nucleation

density derived from the driven force. The morphology of nanostructure can be

significantly adjusted by tuning crystallization temperature under oxygen-free

atmosphere. The results indicate that chemical solution deposition may be a promising

simple method for the fabrication of nanostructures.

Acknowledgements

This work was financially supported by the National Science Fund Program of

China (No.51777172), the Natural Science Basic Research Plan in Shaanxi Province

(No. 2017ZDJC-19), the Science & Technology Nova Program of Shaanxi Province

(No.2014KJXX-23 and 2017KJXX-08).

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 Tab. 1 List of products of Ammonium tungstate hydrate precursor

Decomposition region Weight Loss Gaseous product Final product

50 ~ 210 oC ~2.7 % H2O (NH4)6W12O39

210 ~ 400 oC ~4.5 % NH3, H2O (NH4)2W12O37, WO3-δ

400 ~ 500 oC ~1 % NH3, H2O WO3-δ

Figure Captions

Fig. 1 TG-DSC curves of the ammonium tungstate precursor.

Fig. 2 θ–2θ scans of tungsten oxide powders prepared with different crystallization

temperatures. (a) 500 oC, (b) 700 oC, (c) 900 oC.

Fig. 3 SEM images of tungsten oxide nanostructures deposited on the LAO substrates

with different crystallization temperatures. (a) 500 oC Sample A, (b) 700 oC Sample B,

(c) 900 oC Sample C, (d) thick film prepared at 900 oC as reference, Sample D.

Fig.4 AFM images and the corresponding height profiles of nanostructures deposited

on the LAO substrates. (a) 500 oC, (b) 700 oC, (c) 900 oC, (d) thick film prepared at

900 oC as reference .

Fig. 5 W4f scans of XPS spectra for nanostructures deposited on the LAO substrates.

(a) 500 oC, (b) 700 oC, (c) 900 oC.

13
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Graphical abstract

14
Highlights

The formation of nanostructures can be acquired by a simple chemical solution

deposition.

Square dot, dome nanodot and nanowire can be controlled by the adjustment of

crystallization temperature.

The pure well-ordered nanodots with high nucleation density are formed on the

substrate at high temperature.

15