Materials Chemistry and Physics 147 (2014) 1204e1209

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Hydrophilic Cu2O nanostructured thin films prepared by facile spin

coating method: Investigation of surface energy and roughness
A. Eskandari, P. Sangpour*, M.R. Vaezi
Department of Nanotechnology and Advanced Materials, Materials and Energy Research Center, Karaj, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Hydrophilic Cu2O nanostructured

thin films synthesized by a facile
method.

By increasing the cycle of deposition,
finer particles obtained.

Surface energy and contact angle
strongly depend on the film forma-
tion mechanism.

Transformation of the thin films
growth mechanism was studied.

a r t i c l e i n f o a b s t r a c t

Article history: We demonstrate a facile, uniform and large scale chemical route to synthesize the cuprous oxide (Cu2O)
Received 23 June 2013 nanostructured thin film via spin coating technique. The samples were characterized by X-ray diffraction
Received in revised form (XRD), atomic force microscopy (AFM), simultaneous thermal analysis (STA) and UVevisible spectra.
28 May 2014
Based on the results, the transparent Cu2O thin films were formed at the low temperature (275  C) due to
Accepted 9 July 2014
Available online 22 July 2014
employed N2 atmosphere in annealing processes. The average roughness is decreased by increasing the
number of layers from 11 to 6.4 nm for 1 and 5 times of successive deposition of copper oxide,
respectively. Afterward, by increasing the cycle of deposition, the roughness increased (~87%) owning to
Keywords:
Thin films
the transformation of the growth mechanism of thin films from VolmereWeber to StranskieKrastanov
Solegel growth mode. Moreover, the prepared films were extremely hydrophilic with water contact angle about 45 and
Atomic force microscopy (AFM) surface energy 54.26 mJ m2 after 10-cycle coating. The smooth and low energy surface with this
Thermogravimetric analysis (TGA) technique could be tailored for photoelectrochemical applications such as water splitting.
Differential thermal analysis (DTA) © 2014 Elsevier B.V. All rights reserved.

1. Introduction promising working anode for photoelectrochemical cells or cath-

ode of electrochromism tools [2e4]. As a consequence of opto-
Transparent conduction oxide (TCO) thin films have recently electronic and electrochemical criteria of Cu2O nanostructures, the
received broad attention due to high optical absorption efficiency great potential for negative electrode in Li-ion. Based batteries is
and low cost materials which make them as alternatives of silicon also considered [5]. There are different route to synthesize the
devices [1]. As an excellence family of p-type semiconductors, cuprous oxide thin films such as reactive magnetron sputtering
cuprous oxide (Cu2O) has found spectacular applications because of [6,7], molecular beam epitaxy [8], electrodeposition [9e11] and
narrow direct band gap (~2.1 eV) and band edge, which lead to thermal oxidation [12]. The main problems, however, are high
temperature, expensive equipments and special condition in
aforementioned procedures.
* Corresponding author.
E-mail address: sangpour@merc.ac.ir (P. Sangpour).

http://dx.doi.org/10.1016/j.matchemphys.2014.07.008
0254-0584/© 2014 Elsevier B.V. All rights reserved.
 A. Eskandari et al. / Materials Chemistry and Physics 147 (2014) 1204e1209 1205

According to the better tailoring and fabrication of thin films by

chemical routes, the solegel process has advantages over other
processes because of its simplicity, low cost of materials and lower
crystallization temperature [13]. In addition, to the best of author's
knowledge, there are not any reports about the spin coating of
cuprous oxide via solegel technique and investigation related
surface energy of the thin films.
In this paper, we report the facile preparation of Cu2O thin films
via sol gel spin-coating approach. The effects of number of layers on
microstructure, morphology, optical properties and surface energy
of thin solid films have been also investigated.

2. Experimental
Fig. 1. Differential thermal analysis and thermogravimetric analysis of Cu sol.

Copper (II) acetate, (Cu(C2H3O2)2, 99.999% purity) was used as

starting material for the synthesis of cuprous oxide thin films. The
details of preparation of Cu2O thin film was published elsewhere during initial heat treating procedure [14]. In this case, the first
[14]. Briefly, we prepared 0.05 M copper acetate solution endothermic peak is observed which can be attributed to the CuO
[Cu(C2H3O2)2] by using C2H5OH as solvents. Soda-lime glasses was formation as main phase confirmed by X-ray pattern (Fig. 2). At
employed as a substrate, which cut into a proper dimension for 271  C, a sharp increment can be detected which is related to the
spinning. Before using, the substrates were cleaned by ethanol and Cu2O formation [15]. In this regard, the exothermic peak can be
acetone in an ultrasonic bath. Then, the sol was introduced on the featured to Cu2O formation and the second step (endothermic) can
substrates 1 to 10 times. The spinning had two steps. The first one be related to the precursor decomposition. From the point view of
was accompanied by 1500 rpm for 15 s and then, the rate was weight loss, the changing slope in TG curve can be divided to the
increased up to 3000 rpm and the duration was about 30 s. The two parts as a result of metastable phase formation and decom-
layers were calcined in air at 150  C to evaporate the solvent be- position of residual organics materials. After 360  C, the further
tween each deposition stage. After the final stage, the layers were reduction was occurred. In fact, Cu2O phase was gradually trans-
heat treated in the tube furnace with inert gas (N2) atmosphere for formed to the Cu particles.
2 h at different temperatures ranged from 275 to 500  C. Pike et al. [16] claimed that depending on the reduction con-
The phase composition and the microstructure of thin films dition, Cu2O as intermediate phase, can be formed in 5% CO/He
were analyzed by X-ray diffractometer (XRD, Philips, X'Pert). The atmosphere at 400  C entirely. By raising the temperature in a
morphology of the film was observed using atomic force micro- reduction atmosphere they found that the nanocrystalline CuO was
scope (AFM Park scientific Instruments Auto Probe CP) with contact reduced in a two-step reduction process: Firstly, it completely
mode. Optical properties were measured using ultravioletevisible transformed to Cu2O and finally, it reduced to Cu phase. In contrast
(UVevis) spectroscopy model Perkin Elmer Lambda 900 in the to bulk scale in which CuO directly reduced to the copper, the
range 300e850 nm. Differential thermal analysis (DTA) and ther- monoclinic CuO nanoparticles can be reduced to the cubic cuprous
mogravimetric analysis (TGA) were employed using a PL-STA-1640 oxide and then face centered cubic Copper. Armelao and co-
to verify the decomposition of organic material during the heat workers [14] reported that the copper sol was transformed to
treatment of Copper oxide powder. CuO at 500  C for 1 h and reduced to Cu2O at 900  C for 5 h. Ac-
Water contact angles were measured using a homemade contact cording to sol preparation and limitation of thin films heat treat-
angle apparatus, 3 yL water droplets were used to minimize any ment due to diffusion of elements from the substrate to the films in
gravitational effects. The water droplet images were analyzed using this research, the temperature was decline from 900 to 500  C. At
a circular fitting method to obtain the contact angles on the surface. the highest heat treatment temperature (500  C), the metallic
The surfaces were tested from a range of areas over the substrate copper was produced due to completely reduction of sol [17]. It is,
plate. Water slip angles were also measured by noting the angle to therefore, necessary to decrease the time/temperature to make the
the horizontal at which a water droplet of known volume moved on cuprous oxide phase. Interestingly, we decrease the reduction
the surface. Spots from many positions were measured from each temperature form 900 [14] to 275  C in the present work. The
surface. Moreover, the samples were tested by polar (water) and crystallites size which were calculated by Scherrer equation were
nonpolar (Hexadecane) to calculate the surface energy of thin films. 11, 24, 38 and 45 nm for 250, 275, 300 and 500  C respectively.

3. Results and discussion

Annealing temperature and atmosphere have a great influence

on the phase formation of copper oxides. To have a better insight
for heat treating the prepared sol, Differential Thermal Analysis and
thermogravimetric analysis was employed. Fig. 1 shows the ther-
mal behavior of sol containing copper heated up to 500  C. As can
be seen, with increasing the annealing temperature from 250 to
500  C, the different phases are formed. From this figure, one can be
observed that the sharp decreasing (~60%) in weight is occurred
because of evaporation of solvent and acetate compound before
240  C. After that, two endothermic peaks can be also seen at 370  C
and 413  C, respectively. To understand the phase transformation/
formation of Cu oxides, the X-ray pattern at selective temperatures Fig. 2. X-ray diffractograms of Cu Sol at different temperature in N2 atmosphere at
was investigated (see Fig. 2). It is reported that the CuO was formed different annealing temperatures.
1206 A. Eskandari et al. / Materials Chemistry and Physics 147 (2014) 1204e1209

Fig. 3. AFM images and water droplet CA; of Cu2O thin films surface of (aea00 ) 1, (beb00 ) 5 and (cec00 ) 10 cycle spin-coating.

Fig. 3 reveals the atomic force microscopy images of cuprous It is definitely known that the higher surface area absorbs much
thin films annealed at 275  C with different number of coating. As more photons and hence yields an increase in photocurrent for
can be seen, the smooth surface (roughness 11 nm) was deposited photoelectrochemical applications [9].
by one cycle spin coating. In addition, the Cu2O films after one cycle Wet ability of the spin-coated Cu2O thin films have been
processing (Fig. 3(a)) demonstrated less uniformity than the other evaluated by the method of water contact angle (CA) measure-
coated films. In other words, after the annealing process, the copper ment. The investigation will be helpful for one to utilize such metal
oxide particles self-accumulated on the surface of the films [2]. oxide films in aqueous electrolyte for photoelectrochemical ap-
Further deposition (5-layer) resulted in decreasing the average plications such as dye-sensitized solar cells and water splitting
roughness (6.4 nm) which exhibited the fact that filling the po- devices. To obtain the surface energy of Cu2O films, the contact
rosities was occurring and the inter space particles on the surface angle for sessile oil were also measured. According to the Fowkes'
are also decreased, as well. In addition, more coated layers, finer theory, it is assumed that the surfaces forces are additive by
crystals obtained. This can be attributed to the increasing the different forces such as dispersion, polar, hydrogen, etc [18].
nucleation sites after each coating process which increase the Furthermore, the surface energy is calculated by OwenseWendt
surface area. equation as below [19,20]:
 A. Eskandari et al. / Materials Chemistry and Physics 147 (2014) 1204e1209 1207

Table 1 tension of substrate is the main factor which should be concerned.

Surface energy (E), Contact angel (q) and average roughness (R) of Cu2O thin films for Therefore, (q) of the first layer is the angle which mainly reflects the
different number layers.
intrinsic aspect of soda lam with small Cu2O particles. Contribution
Number of layers ɤd(mJ m2) ɤp(mJ m2) q E(mJ m2) R(nm) of layers density in contact angle and surface tension measurement
1 25.64 40.74 24 66.4 11 are increased by increasing the deposition process. Form Fig. 3 it
5 26.3 41.9 20 68.2 6.4 could be easily seen that the uniform thin layer films with average
10 27.06 28.2 45 54.26 12 particle size 200 nm are prepared via facile spin coating route. The
uniformity of layers results in decreasing the (q) and (R) which
rffiffiffiffiffiffiffiffiffiffiffiffi
 ffi ffi!
rffiffiffiffiffiffiffiffiffiffiffiffi
 shows increasing effect of layers with respect to the substrate. In
1 þ ɤl cos q ¼ 2 ɤds ɤdl þ
p p
ɤs ɤl (1) other words, the fraction role of substrate in total surface tension
and contact angle of layers decreases drastically. Further deposi-
tion, however, results in formation of finer particles (~100 nm) and
where ɤps and ɤds are respective polar and dispersion terms of solid increasing the roughness (~87%) which enhance the contact angle
p
surface tension (ɤs ). ɤdl and ɤl are the dispersion and polar terms of (~125%). This phenomenon could be attributed to the effect of layer
liquid surface tension (ɤl ) respectively. In this study, the hex- density, crystallite size, pores distribution and distance between
adecane and water were used as non-polar and polar liquid with adjacent particles. In contrast to general idea which is assumed that
specific surface tension. with decreasing the grain or crystallite size, the surface roughness
A typical photograph of the shape of a water sessile drop is would be decreased [21], the roughness of prepared thin films is
shown in Fig. 3 (C, C0 , C00 ). Accordingly, the tendency to adhere to increased surprisingly. This could be attributed to the thin film
the surface sticky is in good agreement to the Wenzel regime for 1 growth mechanism. During the deposition process, different
cycle coating. Further deposition process resulted in turning the mechanisms are observed. At the first steps of deposition, the is-
regime to the combined (Wenzel and Cassie-Baxter) mode due to land growth could be detected which related to the VolmereWeber
increasing the contact angel which could be attributed to the growth mode [27]. In this case adatomeadatom more strongly
presence of air in small interspaced grains and nano pores on the bounded to each other than to the substrate, leading to the for-
thin film structure [21e23]. Based on CA of these figures and uti- mation of three-dimensional adatom clusters or islands. Further
lizing the OwenseWendt equation and Fowkes model [24,25], the deposition resulted in changing the mechanism from Vol-
surface energy (E) is calculated and is shown in Table 1. mereWeber to StranskieKrastanov mode [28]. In StranskieKras-
In this table, it is clear that by increasing the cycle of depositions, tanov mode of film growth, 2D growth of a few monolayer followed
the surface energy and contact angle changed. In fact, the contact by 3D island formation, therefore, the roughness of the film is
angle and surface energy behaved inversely. The contact angle and increased up to 12 nm. In all cases, the hydrophilic behavior of Cu2O
the surface energy at the first layer deposition were ~24 and thin films is detected.
66.4 mJ m2, respectively. Further deposition resulted in increasing To have a better insight of microstructure of copper oxide thin
the surface energy to 68.2 mJ m2 (for 5 layer) and consequently film, scanning electron microscopic analysis was utilized and rep-
decreasing to the 54.26 mJ m2 (10 layered films) corresponding to resented in Fig. 4. Accordingly, the density of the layers is clearly
the fluctuating of contact angle. These changes could be interpreted increased by increasing the cycle of deposition. In addition, island
by Eq. (1) in which by increasing the q, the term of Cos(q) decreases, growth mechanism could be traced due to presence of accumulated
therefore, the surface tension of solid will be decreased. Not to be nanoparticles on thin surfaces. These images had a good agreement
neglected that the reason of changing the contact angel is strongly with AFM data. The 1 layer thin film containing coarse particles
depends on surface roughness which affected by density of layers, exhibits the rougher surfaces, therefore, having the higher contact
method of thin films preparation and geometrical factors [26]. angle is. More interesting, the smaller crystallite size is observable
Based on the AFM results (Fig. 3), at the first cycle of deposition, in the final step of layer deposition. Baumgartner et al. [29] claimed
the small cubic islands (~700 nm) are clearly observable. According that in chemical synthesis route of nanoparticles, there are IV
to the point that the many small separated clusters were formed, it nucleation-growth scenarios in which atoms/molecules trans-
could be concluded that the contact angle measurement of thin formed to the primary particles, amorphous or crystalline phases.
films was highly affected by substrate. In fact, the role of surface The atoms/molecules grow to form the primary particles which are

Fig. 4. SEM images of Cu2O coated layer after 1 (a), 5(b) and 10 (c) times deposition.
1208 A. Eskandari et al. / Materials Chemistry and Physics 147 (2014) 1204e1209

Fig. 5. Schematic of Cu2O nanostructure films preparation (a): 1 cycle deposition; separated primary particles (islands) formed on the substrate which could be grown in all
directions. (b) 5 cycle deposition; The Islands sticks to each other's. Note that growth directions are confined. (c) 10 cycle deposition; smaller particles were formed on large particles
and growth mechanism of thin films is changed from VolmereWeber to StranskieKrastanov mode.

not the crystalline. Consequently, the primary particles trans- boundaries play a confinement role to suppress the grain growth
formed to the bulk amorphous phase or crystalline matter directly. and coarsening (see Fig. 5)
Based on our results (Fig. 2) the partially crystalline materials could To investigate the optical properties of Cu2O thin films, the
be detected which transformed to the crystalline phases. The transmittance spectra of samples are considered in Fig. 6 and
presence of metastable primary particles in the nucleation pathway consequently, the optical absorption coefficient and band gap were
leads to a lowering of the thermodynamic barriers due to a release obtained. The films deposited at 275  C were transparent and
of energy by the consumption of the primary particles [29]. appeared yellow/brown in reflected light.
Moreover, the confinement of particle growth directions in the For transparent thin films, the optical density, defined as a
initial step of spin coating which resulted in island formation product of the absorption coefficient and the thickness of the films,
should be considered. The authors proposed the schematic primary can be evaluated as follows:
particle growth in as follows:  
Accordingly, the primary particles which formed island on the 1 1
a¼ ln (2)
substrate can grow in several directions by tendency of agglomer- d T
ation [30], particle coalescence or Ostwald ripening process, how-
ever, the growth direction of primary particle decreased by where a, d and T are absorption coefficient, thickness and trans-
increasing the layer deposition which means that the grain mission data value. Moreover, the optical band gap can be esti-
mated easily by following relation:
 h
ahy ¼ A hy  Eg (3)

where A is a constant and h is another constant that depends on the

nature of the transition and t is film thickness. Owning to direct
transition of copper oxide, h ¼ 0.5 resulted in a linear relationship
indicating a direct allowed optical transition in Cu2O thin films. By
intercepting the (athy)2 versus the hy, the band gap could be
measured. Fig. 6(a) shows the transmittance spectra of Cu2O thin
films annealed at 275  C in N2 environment for different coating
cycles. Interestingly, the transmittance value of 5 layers samples are
higher than 1 layer suggesting that more roughness of surface,
more scattering occurred resulted in decreasing light transmission
which effect on the absorption light [31]. The other literature
investigated the key role of surface roughness on the light scat-
tering/absorbing of the metal oxide surfaces as well [32]. Moreover,
the pure semiconductor compounds exhibit a sharp transmission
edge at a photon energy which attributed to the forbidden energy
band gap [31,33]. Based on Fig. 6(a), the 10- layer deposited films
have an inhomogeneous crystalline structure and stoichiometric
composition which could be as a result of the uncompleted re-
ductions of copper oxide and residual CuO at under-layers. The
calculated optical band gap (Fig. 6(b)) shows an apparent blue shift
from 2.17 eV for 1- time deposited layer to 2.2 for 5- time deposited
layer and finally 2.27 for 10 layers of Cu2O nanostructured thin films
which could be related to the crystals size variation.

4. Conclusion

We were able to prepare thin, polycrystalline solid films of p-

Cu2O by heat treating in N2 atmosphere at relatively low temper-
Fig. 6. (a) Optical transmittance spectra of Cu2O films annealed at 275  C in an N2
ature. The film surfaces and morphologies were characterized and
atmosphere with varying cycle of deposition and (b) plot of (athy)2 curve vs. photon the correlation between surface roughness, optical properties and
energy hy for Cu2O thin films. surface energy is discussed. Consequently, the surface energy is
 A. Eskandari et al. / Materials Chemistry and Physics 147 (2014) 1204e1209 1209

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