Electrochromic NiO thin films prepared by spin coating

F. Özütok, S. Demiri, and E. Özbek

Citation: AIP Conference Proceedings 1815, 050011 (2017); doi: 10.1063/1.4976389

View online: http://dx.doi.org/10.1063/1.4976389
View Table of Contents: http://aip.scitation.org/toc/apc/1815/1
Published by the American Institute of Physics
 Electrochromic NiO Thin Films Prepared by Spin Coating
F.Özütok1, a), S.Demiri2,b) and E. Özbek3)
1
Department Of Physics, Science Faculty, ÇOMU, Çanakkale, Turkey
2,3
Materials Science and Engineering, Faculty of Engineering, ÇOMU, Çanakkale, Turkey
a)
Corresponding author: fatmaozutok@comu.edu.tr
b)
sanidemiri@gmail.com

Abstract. Recently, smart windows are very important because they are often being used in smart buildings and car
glasses (windows). At this point, producing effective electrochromic materials is so necessary. In this study, we produced
NiO thin films by using spin coating technique on In-doped SnO2 (ITO) substrate. Nickel proportions of these nickel
oxide (NiO) films are 3, 5 and 7 %. Nickel acetate tetrahydrate is the initial solution and solvents are ethylene gl ycol and
n-hexzane. Structural properties and surface images are investigated by using x-ray diffactometer (XRD) and scanning
electron microscope (SEM) device, respectively. In addition, electrochemical behavior is investigated by cyclic
voltammetry. A correlation between surface morphology and electrochromic performance was observed as well.

INTRODUCTION
Electrochromic materials are defined as changing optical transmittance and they are dependent on a changing
reversible color of materials under low DC voltage or current. The main mechanism is based on electron mobility
and double injection/extraction of ions between different layers in electrochromic materials. Their usage areas are
very extensive such as smart mirrors [1], rearview mirrors [2], energy storage batteries [3] and displays [4]. NiO
structure is very proper as an inorganic electrochromic material, characterized by a porous surface, high chemical
stability and good cyclic reversibility. But it has low coloration efficiency and charge capacity when compared to
WO3 which is traditionally preferred. NiO thin films are synthesized by different chemical methods such as
chemical bath deposition (CBD) [5], atomic layer deposition (ALD) [6] and spin coating [7]. Among them, spin
coating is the most effective method given it has a low cost and it obtains homogenous surfaces and high quality
films. In order to gain efficiency from these films, precursor has been solved in different solvents rather than
aqueous solution. [8]. In the presented study, nanocrystalline NiO thin films (3,5 and 7 % Ni including) are
synthesized on the ITO substrate at room temperature using the spin coating. NiO thin films were studied for
structural, morphological and optical properties as well as electrochromic properties.

EXPERIMENTAL DETAILS

Synthesis of NiO Thin Films

Firstly, ITO substrates were cleaned by ultrasonication in diluted ethanol, then in pure water and finally dried at
100 °C. All the chemicals were of analytical reagent(AR) grade and are used without further purification. Nickel
acetate tetra-hydrate [Ni(OCOCH3)2·4H2O] dissolved in n-hexzane, ethylene glycol (C6H12:C2H6O2 ). The volume
ratio of these solvents is (1:1) when used with magnetic stirrer at room temperature. After the obtained homogenous
solution, 3, 5 and 7 % Ni including NiO films were prepared by spin coating with 800 rpm and the procedure was
repeated for three times. Finally, after the spin coating procedure, NiO films were sintered at 150 °C for a duration
of 2 hours.

Turkish Physical Society 32nd International Physics Congress (TPS32)

AIP Conf. Proc. 1815, 050011-1–050011-4; doi: 10.1063/1.4976389
Published by AIP Publishing. 978-0-7354-1483-9/$30.00

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 Characterization of NiO Thin Films
The structural composition of these samples is characterized by X-ray powder diffraction in the 2θ range from
20° to 80°. (XRD; Rigaku SmartLab XRay Diffractometer, CuKα). The structural morphologies of the samples are
carried out through scanning of electron microscopy (SEM; JEOL JSM-7100 F). Optical properties were
investigated by Uv-Vis spectrometer in a range between 300 and 800 nm. (Uv; Shimadzu UV-2450
spectrophotometer). The measurements of the electrochromic processes were obtained by cyclic voltammetry (CV;
Instrument Model: CHI617E). Reference electrolyte type and scan rate was chosen 0.1 M LiClO4/CH3CN and 0.1
V/s, respectively.

RESULTS AND DISCUSSION

SEM Images of NiO Thin Films

The surface morphology image of NiO thin films under 20000 magnification rate are shown in Figure 1. All
films were distributed homogenously on the ITO surface. It was observed that while 3 % and 5 % Ni including NiO
films have pebble stone image, 7 % Ni including NiO film has worm image. It was seen that 7 % Ni including NiO
film are more porous than other samples. It is known that the porous structure is very important which is beneficial
for electrolyte penetration into the film structure thus electrochromic performance is enhanced [9].

(a) (b) (c) (d)

FIGURE 1. SEM images of NiO thin films [a) 3%, b) 5% and c) 7% Ni including NiO thin films (˟20000) magnificaiton rate d)
7% Ni including NiO thin films (˟4000) magnification rate, respectively]

XRD Patterns of NiO Thin Films

As given by Figure 2, the peaks at 37.1º and 43.1º can be assigned to the (111) and (200) diffraction peaks of
NiO, respectively, which corresponds to cubic NiO (JCPDS No: 71-1179) structre for all films. (200) diffraction
peak is preferential orientation for all samples. Other apparent peaks correspond to ITO substrate. There weren’t any
diffraction peaks related to impurities such as NiOOH or Ni(HCO3) detected. As FWHMs of diffraction peaks have
sharp and measurable which indicate polycrystalline structure. Calculated by Debye-Scheer equation, average
crystallite size of 3%, 5% and 7% Ni including films is 100, 150 and 70 nm, respectively.

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 FIGURE 2. XRD patterns of NiO thin films

Optical Properties of NiO Thin Films

Figure 3 shows the dependence transmittance on the wavelength λ in the range between 300–800 nm for NiO
thin films. It was observed that absorption edge is nearly 320 nm for all of the samples that originated from inter-
band π–π* electronic transition [9]. It can be clearly seen that the transmittance decreases as the nickel concentration
increases; and bleached state transmittance values higher than colored state transmittance values in three types of
films. The occurring case is actually expected [10,11].

FIGURE 3. Tranmittance spectrum of NiO thin films between 300-800 nm. range in the Uv-Vis area

Electrochemical Properties of NiO Thin Films

The cathodic/ anodic behavior of electrochromic NiO thin films was determined by cyclic voltammetry (CV)
measurements as seen in Figure 4 and it was done through a potential sweep between -3 V and +3 V and repeated
for 2 cycles. The color of the NiO films changes from brown into colored state and to transparent into bleached state
as seen in the literature [12]. It was explained by electrochromism for NiO thin films that according to the charge
transfer process reduction from Ni3+ to Ni2+ (anodic scan) and oxidation from Ni2+ to Ni3+ (cathodic scan) occurs.
Electrochemical reaction given by Equation 1 and 2:

NiO+ y Li+ y e- → LiyNiO (1)

LiyNiO +x Li+ +x e- → Li(x+y) NiO (2)
(colored) (bleached)

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 As seen in Figure 4, all films showed electrochromic behavior but the most proper films for electrochromic
applications 7% are Ni including NiO film. This due to its high current values under similar potential range of other
samples. This might be explained by the fact it has porous surface and there are much more grain boundaries among
them [13].

FIGURE 4. Cyclic voltammograms of NiO thin films from -3V V to +3 V at a scan rate of 10 mV/s, in a 0.1 M electrolyte,
after 2 cycles

CONCLUSION
In this study, nanocrystalline NiO thin films ( 3,5 and 7 % Ni including) were synthetized on the ITO substrate
using the spin coating. Etylene glycol and n-hexane are suitable solvents for synthesizing NiO thin films by spin
coating technique. SEM images showed that homogeneous particles are distributed and porous surface was
determined in 7%-Ni including NiO thin films. NiO films are highly transparent in UV-Vis region (> 50%) and
absorption edge is at ̴ 320 nm. This is in full congruence with literature. NiO films exhibited electrochromic
material. To sum up, the most electrochemical behavior was observed in 7 % Ni including NiO thin films.

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