Applied Surface Science 289 (2014) 430436

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Applied Surface Science

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Investigations on the role of alkali to obtain modulated defect concentrations for Cu2 O thin lms
Anirban Chowdhury a, , Pavan Kumar Bijalwan a , Ranjan Kumar Sahu b
a b

Research & Development, Tata Steel Limited, Jamshedpur, 831001, India MST Division, CSIR-National Metallurgical Laboratory, Jamshedpur, 831007, India

a r t i c l e

i n f o

a b s t r a c t
An economic successive ionic layer adsorption and reaction (SILAR) method has been investigated for depositing thin Cu2 O layers on steel. The mole ratios of the Cu+ ions to OH ions in the alkali bath were varied and the changes in the properties were characterised by X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and Ultravioletvisible spectroscopy techniques. The increase in the binding energy values of the Cu 2p peaks in XPS established that an optimum copper vacancy concentration can be obtained for a Cu+ /OH mole ratio between 1:10 and 1:15; SEM studies conrmed a dense, uniform microstructure for Cu2 O thin lms coated with these compositions. The strongest absolute peak intensity counts in PL for the peak at 580 nm along with low energy peaks (1.21.4 eV) due to Cu vacancy was found to be most prominent for thin lm made with Cu+ /OH mole ratio 1:15. The role of alkali concentration has been explained in relation to create a stable Cu2 O structure with optimum copper vacancy. This is an easy way to modulate surface reactivity of the Cu2 O thin layers and the concept can be utilised for large area device integrations for various electrical and mechanical applications. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.

Article history: Received 18 September 2013 Received in revised form 30 October 2013 Accepted 31 October 2013 Available online 8 November 2013 Keywords: X-ray photoelectron spectroscopy (XPS) Photoluminescence (PL) spectroscopy Successive ionic layer adsorption and reaction (SILAR) Cuprous oxide Vacancy Defect

1. Introduction The CuO system has two stable oxides: cupric oxide (CuO) and cuprous oxide (Cu2 O). Copper and copper oxide (metalsemiconductor) is one of the rst photovoltaic cells invented [1]. Cupric oxide (CuO) is a non-stoichiometric semiconductor having a monoclinic crystal structure and a band gap of 1.92.1 eV [2]. Cuprous oxide (Cu2 O) is an attractive semiconductor material that could be used as anode material in thin lm lithium batteries [3] as well as in solar cells [4]. Cu2 O is a reddish ptype semiconductor with a direct band gap of 2.17 eV [5]. For Cu2 O, it is known that the material usually includes considerable amounts of non-stoichiometry such as copper vacancies, VCu , and oxygen vacancies, VO [5]. The Cu2 O p-type conductivity is usually linked to the Cu vacancies (VCu ), however the existence of oxygen vacancies (VO ) has also been considered to explain the general behaviour of their physicochemical properties [5,6]. Cuprous oxide draws signicant interest because of its high optical absorption

Corresponding author at: Materials Science & Engineering, Indian Institute of Technology Patna, Patliputra Colony, Patna, BR 800013, India. Tel.: +91 612 2260232; fax: +91 612 2277383. E-mail address: anirban.chowdhury@gmail.com (A. Chowdhury).

coefcient in the visible range with reasonably good electrical properties [7]. Oxide layers on metal surface play a pivotal role by inuencing their properties for various technological applications owing to their nature, thickness and stoichiometry. Some of these cases include adhesion of elastomers to metal surfaces [811], sealing of electronic packaging [1216], lowering of friction during wet drawing [17,18], enhancing solar cell efciency [1921], and extent of biocompatibility of biomaterials [2224]. Cu2 O has been proven to be one such candidate that can improve metalrubber adhesion in pneumatic cycle-tire beads [8,9] and as an adhesion promoter in the area of electronic packaging [15,16]. Properties of bead wire have been investigated for past several decades since the introduction of coating on the bead wire, and adhesion is one of the big concerns for bead wire. Traditionally, it is assumed that adhesion is established by the chemical reaction between copper in the coating of a bead wire and active sulphur from rubber during vulcanisation. The properties of the oxide layer that forms on most of metals play a vital part in the formation of bonding during vulcanisation. In the case of copper, the ionic state could be either monovalent of copper Cu+ or divalent of copper, Cu2+ , due to its dual oxide phases; Cu2 O and CuO. It is therefore proposed that copper sulphide is formed by the reaction between active state of sulphur and the ionic state of copper, and this reaction requires electron transfer during the process. The particular

0169-4332/$ see front matter. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2013.10.183

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oxide, which is the key ingredient for higher pull out force or better adhesion, was found to be cuprous oxide [8]. Su et al. [9] has also described in situ, continuous monitoring system designed to detect the rate of adhesive bond formation between rubber and steel reinforcement during the vulcanisation process. Parameters such as oxide chemical structure and thickness were investigated to assess the rate of bond formation during vulcanisation and their effect on adhesion. The study also points towards the need of a method for obtaining a defect controlled oxide surface. In this work, we have shown a simple method for developing a Cu2 O coated surface with modulated defect concentrations which will nally change the surface reactivity. Cu2 O thin lms were characterised by X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and ultravioletvisible spectroscopy techniques. The changes in the structural properties of the thin Cu2 O coatings have been suitably characterised and a sound correlation was obtained with respect to the varying defect concentrations of the coatings. The concentration of defects is expected to play a pivotal role during any chemical reaction(s) thereafter, where, this oxide layer plays the role of an interface, e.g., between metalrubber interface during vulcanisation. Moreover, these Cu2 O coatings are made on steel by an economic chemical process which can be readily used for any large area applications and will also be suitable for any device integration. The same Cu2 O with modulated surface defects is also expected to play an important role in other electronic and optoelectronic applications, e.g., in solar cell and printed circuit boards for electronic packaging.

Fig. 1. Cu 2p core-level XPS spectra of samples AE; the inset gure (a) shows the extent of peak shifts (i.e. variation in binding energy) in all these samples.

2. Experimental We have used the parent recipe rst reported by Ristov et al. [25]. The recipe is based on a type of successive ionic layer absorption and reaction (SILAR) process which was primarily popularised for making sulphide thin lms [26]. The core idea of the recipe is to nd a stable Cu+ complex which the authors [25] had made by mixing sodium thiosulphate and copper(II) sulphate solutions. The process then leads to the successive deposition of the complex solution and in a hot sodium hydroxide solution at 7080 C. This reported recipe [25] used a particular molar ratio of Cu ion (as in the complex) to the hydroxide solution concentration. Later on, many other researchers [2731] have also followed the same recipe with the same molar ratio for different applications. However, there was no reason explained behind such a selection in any of these reports. We, therefore, have tried to vary this particular molar ratio to investigate the effects that it could bring in terms of the structural and other related properties of the lms. The mole ratios of the Cu+ ions to OH ions were varied in the following way: 1:4, 1:7, 1:10, 1:15 and 1:20. 1 M CuSO4 5H2 O solution was mixed with a freshly prepared 1 M Na2 S2 O3 5H2 O solution to obtain a nal colourless solution; only demineralized water was used for the whole synthesis process. 1 M hot solution of NaOH was made separately and was kept at 70 C. For all the coatings, the whole process was carried out for two times with ve different concentrations of NaOH bath. For each case, thin Cu2 O layers were deposited on steel and sometimes on cleaned glass substrates. For the ease of understanding, the respective samples will be designated as samples A (1:4), B (1:7), C (1:10), D (1:15) and E (1:20) throughout this paper. X-ray photoelectron spectroscopy (XPS) analyses were carried out with SPECS, Germany spectrometer using Mg K X-ray source (h = 1253.6 eV). The binding energy of each XPS peak was calibrated with the C 1s peak of energy 285.0 eV. Photoluminescence (PL) spectroscopy measurements were carried out at room temperature using HeCd laser operating at

325 nm. The PL signals were analysed using a TRIAX 320 monochromator and detected by a Hamamatsu R928 photomultiplier tube. The microstructure and surface morphology of the thin Cu2 O coated steel samples were observed by a scanning electron microscope (SEM, SUPRA 25, ZEISS FEG). The voltage used for analysis was 15 kV. Grain size measurements were carried out using an image analysis system and the mean linear intercept grain size was considered. Measurements were carried out for minimum 400 grains for the selected samples. Film thickness was measured by Olympus (LEXT OLS4000) confocal laser scanning microscope. A step was made by etching the lm with aqueous NH4 Cl solution. UVvisible diffuse reectance spectra of Cu2 O thin lms on steel were obtained using an UVvis spectrometer (Shimadzu UV-2550) by using BaSO4 as a reference and the optical band gap values were obtained using reection data by the KubelkaMunk method. 3. Results and discussion XPS is a powerful tool to determine the chemical states of Cu. Therefore, this would be an ideal instrument to know the type(s) of compositional phases formed in the coated lm. Furthermore, the binding energy of peaks depends on the chemical bonding of Cu atom with the neighbouring atoms. In fact, creation of vacancy or doping of any other elements around the Cu atom alters the electron density on it, which ultimately affects the binding energy. Therefore, the chemical shift of XPS would also provide information about the vacancy formed either by the Cu ion or oxygen. Figs. 12 show the Cu 2p and Auger XPS spectra of the samples AE prepared by varying Cu+ ions and alkali at the ratio of 1:4, 1:7, 1:10, 1:15 and 1:20. The Cu 2p exhibits a doublet peak (Fig. 1) due to the strong spinorbit coupling. The peaks at 932.37 and 952.19 eV of the sample A (1:4) are assigned to the Cu 2p3/2 and Cu 2p1/2 peak, respectively. According to the literature data [3238], the observed peak at 932.6 eV is due to the presence of Cu2 O. This also rules out the presence of impurity phase of CuO, which shows the main peak and satellite peak at 933.8 eV and between 940945 eV respectively [34,35]. However, due to the proximity between the binding energy values [3537] of Cu and Cu2 O, we decided to analyse the Cu LMM Auger peaks, Fig. 2. The individual energy values are illustrated in Table 1. In general, the Auger parameter depends on the dielectric and electronic properties of the photoexcited atom. Since the

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Fig. 2. Cu(LMM) Auger spectra for samples AE with varying mole ratios of the Cu+ ions to OH ions.

Table 1 XPS data table showing binding energy for the Cu 2p peak and the kinetic energy values for the Cu LMM Auger peaks for Cu2O. Cu(2p3/2 ) 932.37 (1:4) Cu LMM (KE) 917.02 (1:4) Reference Present work; the ratios mentioned in the bracket represent mole ratios of the Cu+ ions to OH ions as used for synthesis

Fig. 3. PL spectra for samples B, C, D and E with normalised intensity counts; the inset plot (a) showing the same with absolute intensity counts.

932.40 (1:7) 932.50 (1.10) 932.46 (1:15) 932.32 (1:20) 932.5 0.2 (FWHM = 1.2 eV) 932.4 932.5 0.3 932.5 932.4 932.8 (FWHM = 1.99 eV)

916.92 (1:7) 916.84 (1.10) 917.11 (1:15) 916.92 (1:20) [35] [37] [33] [32,38] [36] [34]

916.5 916.6

electronic structure of Cu2 O is different than Cu, the Auger peak of Cu2 O appears at 916.5 eV [36] while the Cu LMM appears at 918.4 eV [36]. We conclude from the binding energy of the Cu 2p peak in association with the Auger peak that our coated samples on steel predominantly contains Cu2 O phase. Besides, it is noted from the spectra that the binding energy values of the Cu 2p peak increases with the alkali ratio up to 1:10 (sample C) and then, it decreases. We have conrmed this trend in our repeated trials with different thickness values for the Cu2 O lms. Since it rules out the presence of impurity phase, the shifting of binding energy can be explained related to the vacancy concentrations in these Cu2 O lms. The copper or oxygen vacancy formation in Cu2 O could have happened either by missing of Cu atom or oxygen atom. It is known that the missing of Cu or oxygen atoms alters the electron density of its neighbouring atoms, which leads to chemical shift. Therefore, the analysis of chemical shift yields important information about the origin of defect. In a stochiometric copper oxide compound, chemical shift is dominated by electronegativity. Since O atom has more electronegativity value than the Cu atom, a partial positive charge develops on the Cu atom when the Cu atom is bonded with the O atom. Such electronegative effect on Cu atom does not exist in the case of the missing of its neighbouring O atom [3941]. As a result, based on the electron density on Cu atom, it is expected that the binding energy should decrease in the case of vacancy due to oxygen atom, whereas it should increase due to the Cu vacancy.

Therefore, the shifting of binding energy towards higher energy values indicates that the concentration of the Cu vacancies created in the lm also increases as the alkali (NaOH) ratio is increased up to the optimum ratio of 1:10. Due to closeness of the binding energy values between C (1:10) and D (1:15), it can be concluded from the XPS analyses that the changing of alkali ratio in the range between 1:10 and 1:15 optimises Cu vacancy concentrations in the lms. It should also be noteworthy that the evidence Cu(OH)2 is not observed in the XPS spectrum. Photoluminescence (PL) spectroscopy is an effective tool to study the defects and opto-electronic properties of the samples. Generally, the peaks relating to the different electronic transitions can be categorised into two main groups: the band-to-band transition (free exciton emissions) and the impurity transition (bound exciton emission from impurities). The excitation wavelength of 325 nm is used as the excitation source with photon energy of 3.8 eV, which was higher than the band gap of Cu2 O. PL spectra of the Cu2 O thin lms coated on steel substrates are shown in Fig. 3. Steel substrate will be PL inactive and hence we believe that all the signals are coming from the thin layers of Cu2 O. The absolute intensity PL plot (inset Fig. 3a) clearly depicts that the signal intensity is highest for sample D (1:15) for both 500700 nm and 9001050 nm regions. The PL plot has been shown separately for sample D (1:15) with peak tting, Fig. 4. For the ease of discussion, we have split the PL spectra in two wavelength regions: 9001050 nm and 500700 nm. The higher wavelength region of 9001050 nm is primarily due to different vacancy related defects. For sample D, the major peaks and/or shoulders are noticed at energies of 1.33 eV (933 nm), 1.31 eV (950 nm), 1.27 eV (980 nm) and 1.24 eV (1000 nm). The normalised spectra also clearly reveal that this region (9001050 nm) is most prominent and intense for sample D (1:15), hence we have selected sample D for designating the peaks for the energy transitions. The peaks at emitting energy around 1.27 eV (980 nm) and 1.31 eV (950 nm) are due to the emission from excitons bounded by copper vacancies [42,43]. The peak at 1.24 eV (1000 nm) is coming from transitions from the trap states created by the copper and oxygen vacancies [44]. Park et al. also have attributed the peaks below 2 eV to the defect peaks [45]. The next section is for direct band-to-band transition (free exciton emissions) in the wavelength range 500700 nm. The

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Fig. 5. Schematic energy band diagram (based on photoluminescence results) showing the defect levels in Cu2 O.

Fig. 4. PL spectra for sample D (1:15) showing peaks at 554 nm, 580 nm and 605 nm after Gaussian multipeak tting.

major peaks located here are as follows: 2.24 eV (554 nm), 2.14 eV (580 nm), 2.05 eV (605 nm) and 1.91 eV (650 nm). Quite a few small but sharp peaks appeared between 660 and 890 nm region are believed to be due to plasmonic resonance and hence not included for our discussion. The emission at 1.91 eV (650 nm) is due to the recombination of excitons bounded to oxygen vacancies (VO ) [43]. This peak has often been correlated with an intrinsic property of the crystal due to the formation of exciton-defect complexes; which are analogous to -centres in the alkali halides [44,46]. The highest intensity peak was noticed for 580 nm (2.14 eV) peak for transition from 3d shell; this is the strongest peak observed in all samples. Researchers have reported strongest intensity PL peak at 570 nm for Cu2 O nanostructures and have correlated this to quantum connement effect [4749]. Because the band gap of Cu2 O is about 2.17 eV, the emitting at 2.05 eV (605 nm) can be referred as near band emission. Also, the emission peak of 2.24 eV (554 nm) is attributed to the excitonic transitions from the different sublevels of conduction band to the Cu d-shells of the valence band [43]. Noteworthy is the change in the ratio of their relative intensities of the peaks at 554 nm and 580 nm as observed in the normalised intensity plot (Fig. 3). This I554 /I580 ratio is minimum (0.66) for sample E (1:20) and gradually increases to 0.69, 0.78 and 0.78 for samples B (1:7), C (1:10) and D (1:15), respectively. The peak intensity, in any PL experiment will be proportional to the number of photons released, which is again directly related to the density of carriers. Cu vacancy is the predominant carriers in all these cases and therefore, we conclude that this concentration of vacancy is highest for these samples (C and D). From XPS analyses also, we found that the binding energy for the Cu 2p is maximum and very close for samples C (1:10) and D (1:15). Although, it must be noted that, the absolute peak intensity counts for the peak at 580 nm was maximum for sample D and also the low energy peaks (9001050 nm) due to Cu vacancy was found to be most prominent for sample D (1:15). The proposed band diagram has been shown in Fig. 5 and our PL results obtained room temperature matches reasonably well with previous works [44,46]. The types of defects mostly discussed for Cu2 O lattice involve: (a) neutral or ionised copper and oxygen vacancies, (b) associations and/or correlations of multipolar characters formed by copper and oxygen vacancies. The concentrations

and the ionisation states of these defects vary upon annealing and cooling conditions [44]. Presumably, a lot of these defect associations are found at low temperatures as reported previously [44,46]. Our PL data at room temperature, however, mostly found transitions involving neutral copper and oxygen vacancies. The new addition is due to the peak at 2.24 eV (554 nm) which we correlated with the transitions from the higher sub-levels to the 3d state [43,45]. The lm morphology of sample A (1:4) is typical of a combination of different sized spheres accumulated on a surface with an average size of 130 40 nm, Fig. 6a. Presence of sharp ribbon-like structures was also noted in abundance. These structures are noted more at the interface of the coated and uncoated part of the steel substrate. We are unsure about their origin. Similar long ribbon-like nanostructures with sharp boundary has been previously reported for Cu(OH)2 [50]. Researchers have also reported these types of rod/needle shaped structures for Cu-oxide systems [5154] .This evidence has been correlated with the Raman data and discussed in supplementary Fig. s1. Presence of these ribbons is also noted also in B (1:7) but in small numbers, Fig. 6b. No ribbon-like akes was observed (Fig. 6cd) for samples C (1:10), D (1:15). Their grain sizes were also similar for samples B (70 20 nm), C (70 20 nm) and D (60 20 nm). Sample B (1:7) showed less topography compared to A (1:4) and the grain size distribution is more uniform here. In terms of lm continuity and density the lm samples B (1:7), C (1:10) and D (1:15) appears to be similar. The thickness of the lms for C (1:10) and D (1:15) appears to be similar as 70 15 nm. Unlike sample C and D, lm E (1:20) lacked the continuity and the thickness was around 85 30 nm. Fig. 7 represents the spectral variation of the (F(R)h )2 of sample B and C cuprous oxide thin lms deposited on steel substrates; reectance (R) versus wavelength graph of same samples is shown in inset. The diffuse reectance R can be used to dene a function F(R), KubelkaMunk function [55,56]. Cuprous oxide is a wellknown direct band gap semiconductor [20,57] and the energy gap (Eg ) can thus be estimated by assuming direct transition between conduction band and valance bands. The value of the direct band gap has been found to be 2.64 eV and 2.87 eV for B (1:7) and C (1:10) cuprous oxide lms respectively, Fig. 7. This value is slightly higher [31,58] than those reported for Cu2 O thin lms. We attribute these changes to lm thickness, grain size, annealing conditions and vacancy/defect concentrations. Nair et al. [31] reported an optical band gap of 2.4 eV for Cu2 O lm of

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Fig. 6. SEM micrographs of the selected Cu2 O thin lms coated on steel substrate for samples (a) A (1:4), (b) B (1:7), (c) C (1:10) and (d) D (1:15) respectively.

Fig. 7. Determination of band gap of selected Cu2 O coatings (samples B and C) on steel substrates by drawing a tangent line at[F(R)h ]2 = 0. The inset gure in (a) shows the diffuse reectance (%R) spectra of those Cu2 O coatings.

70 nm thickness to approximately 2.0 eV in the case of a lm of 150 nm thickness. Annealing of such lms further resulted in minor alteration of the band gap values. Cu2 O has often been termed as a self-compensating semiconductor [59] where the concentration of the copper and oxygen vacancies are competing each other. Even without any doping, a

small synthesis parameter alteration, e.g., pH [60], surfactant [61] changes its type of conductivity by changing the concentrations of the major carrier. It has been widely reported that p-type Cu2 O is formed in alkaline condition (pH 712) while strong acidic conditions (<pH 5) facilitate the growth of n-type Cu2 O [60,62]. Also, it has been previously reported that band gap shift has a direct connection with NaOH concentration for other oxide systems, e.g. ZnO [63,64] where the authors correlated the decrease of optical band gap of ZnO with the decrease of NaOH concentration during synthesis. In our case for the Cu2 O thin lms, we observe a similar trend in the band gap value for C (1:10) compared to B (1:7) as the NaOH concentration is decreased. Noteworthy is also the change in slope in the lower h region (2.492.67 eV). Researchers have correlated such denite changes in slope with different existing trap levels in other systems [65]. However, we believe that this needs a further in-depth analysis of the existing spectroscopy results and hence keep this open for a scope of future work. The thiosulfatocuprate(I) complex is a stable complex for Cu+ ions. In our synthesis process the main reason for varying the mole ratios of the Cu+ ions to OH ions was to nd a suitable conditions for lm synthesis process with tailor-made defect concentrations, if any. From the SEM study it was revealed that the mole ratio of the NaOH bath plays a pivotal role in the nal lm composition and continuity. Phase evolution study by XRD showed only Cu2 O phase in all these lms (supplementary Fig. s2). Combined results from PL and XPS studies have also shown that the mole ratio of the NaOH bath is also very important for optimising the defect/vacancy concentrations of these lms.

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The presence of aky ribbon like nanostructures is in abundance for sample A (1:4) and in reduced quantity for B (1:7) probably indicates the formation of Cu(OH)2 . The reaction mechanism for the formation of the Cu2 O thin lms can be summarised as: [Cu (S2 O3 )] Cu+ + S2 O3 2 Cu+ + OH CuOH 2CuOH Cu2 O + H2 O (1) (2) (3)

in relation to optimum copper vacancies against severe lattice distortions which degrade lm properties at very high ratios (beyond 1:15). These lms coated on steel can be readily integrated for all types of large area electronic and mechanical applications where role of Cu2 O can be utilised as an interface. Acknowledgement AC is grateful to Prof. Anushree Roy and Ms Barnita Paul for their help in carrying out the Raman experiments at their laboratory at IIT Kharagpur. AC and PKB also extend their thankfulness to Prof. Samit Kumar Ray and Ms Tamita Rakshit for necessary help in conducting the room temperature photoluminescence spectroscopy experiments at IIT Kharagpur. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.apsusc. 2013.10.183. References
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The concentration of the alkali bath here plays an important role in the supply of OH ions in the solution which in turn controls the rate of reactions. In SILAR methods, all reaction precedes via selective adsorption method. In other words, when the supply of OH ions is low, the free Cu+ ions react with water during washing of the lms and while drying by hot air blower they get converted to Cuhydroxide, i.e., the reaction sequence (Eqs. (1)(3)) is not followed. As the alkali concentrations increased (for samples C, D and E), all the Cu+ ions get combined with enough number of OH ions to ascertain the formation of Cu2 O only (according to Eq. (3)). However, this higher concentration of OH ions for sample C (1:10) and D (1:15) also plays a crucial role in changing the defect concentration in those lms. More number OH ions is also expected to increase the supply of more oxygen atoms in the Cu2 O lattice and thereby changing the effective Cu:O ratio of the parent structure. Finally, this leads to an increase in the Cu vacancies along with the possible formation of oxygen interstitials and thereby changing the stoichiometry of these lms as Cu2- O. Apart from the change in alkali concentration, other processing parameters were same for all the lms. Also from SEM study, we do not see any drastic changes in microstructure between samples B (1:7), C (1:10) and D (1:15) and hence correlate all the changes in the properties to the alteration of the Cu vacancy concentrations. Researchers have also investigated this issue to understand this non-stoichiometry and structural defects present in cuprous oxide system [6668]. We tried to nd out this value of by XPS but it was not possible due to the involvement of the carbon tapes which was also interfering with the oxygen atoms. In other words, it would have been erroneous to correlate the oxygen contribution completely to the Cu ions for the XPS experiment. Beyond a certain point, as observed in sample E (1:20), this concept fails. The concentration of defects is decreased and the SEM micrograph also depicts a porous and non-uniform lm (supplementary Fig. s3). This is probably due to severe lattice distortions occurred during the synthesis of the Cu2 O thin lms due to very high alkali concentrations. Therefore, the whole study conrms that the mole ratios of the Cu+ ions to OH ions is ideal between 1:10 and 1:15 for optimised lm properties. These defects are found to be stable, i.e., the properties were reproducible when measured between different time periods in weeks. This gives a unique opportunity for these Cu2 O thin lms to be integrated directly with steel and a range of other substrates for advanced technological applications. 4. Conclusions A simple economic method has been derived for synthesising Cu2 O thin lms with modulated surface reactivity by altering the defect concentrations in the lms. The XPS analyses showed an increasing trend in binding energy with the increase in the Cu+ ion to alkali bath concentration below 1:15. The PL results depicted various possible transitions due to enhancement of copper vacancies and illustrated most intense response for sample D (1:15). A dense microstructure with uniform grains were observed for sample C (1:10) and D (1:15). The gradual fall of the curves in UV-visible spectra indicates that the band gap of Cu2 O lms is mostly associated with trap states. The role of alkali bath has been explained

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