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Vacuum 82 (2008) 623629 www.elsevier.com/locate/vacuum

Characterization of copper oxide thin lms deposited by the thermal evaporation of cuprous oxide (Cu2O)
M.F. Al-Kuhaili
Physics Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia Received 1 July 2007; accepted 2 October 2007

Abstract Thin lms of copper oxide were deposited by thermal evaporation of cuprous oxide (Cu2O) powder. The substrates were either unheated or heated to a temperature of 300 1C. The lms were also annealed in air at a temperature of 500 1C for 3 h. The lms were characterized by X-ray photoelectron spectroscopy, X-ray diffraction and UV-visible spectrophotometry. The effects of the substrate temperature and post-deposition annealing on the chemical, structural and optical properties of the lms were investigated. As-deposited lms on unheated substrates consisted of mixed cupric oxide (CuO) and Cu2O phases, with a higher concentration of the Cu2O phase. However, the lms deposited on heated substrates and the annealed lms were predominantly of the CuO phase. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Copper oxide; Cuprous oxide; Cupric oxide; Chemical properties; Structural properties; Optical properties; Annealing; Thermal evaporation

1. Introduction The CuO system has two stable oxides: cupric oxide (CuO) and cuprous oxide (Cu2O). These two oxides are semiconductors with band gaps in the visible or near infrared regions. These materials have several advantages: (i) availability and abundance of the starting materials, (ii) non-toxic nature, (iii) low production cost, (iv) band gaps lie in an acceptable range for solar energy conversion, and (v) n- and p-type conductivity [1,2]. As a result, copper oxides have found numerous applications in diverse elds such as solar cells and photovoltaic materials [2], electrochromic coatings [3], catalytic applications [4], and high-Tc superconductors [5]. Doped copper oxide thin lms have found applications such as in the fabrication of p-type transparent conductors [6]. Copper oxide thin lms have been deposited using various techniques including sputtering [510], chemical vapor deposition (CVD) [11], and electrodeposition [12,13]. Previous work on thermally evaporated copper oxide thin lms was mainly carried out by evaporating pure copper in an oxygen atmosphere [3,1417]. Only in one report was
Fax: +966 3 860 2293.

CuO powder directly evaporated [3]. Moreover, direct evaporation of Cu2O powder was only carried out using electron-beam evaporation [18]. Powders may be thermally evaporated using a resistively heated refractory metal boat. This method is direct, simple, and has less incorporation of impurities since it is carried out under high vacuum. Moreover, it is a low-temperature technique, and lms can be deposited on a variety of conducting or insulating substrates. In this work, copper oxide thin lms were deposited by direct thermal evaporation of Cu2O powder. The effects of substrate temperature and post-deposition annealing in air on the chemical, structural and optical properties of the lms are reported. 2. Experimental Thin lms were prepared using thermal evaporation from a tungsten boat. The starting material was red Cu2O powder (Cerac, 99.9% purity). The lms were prepared in a Leybold L560 box coater pumped by a turbomolecular pump. The material was slowly outgassed before evaporation. The system was initially pumped to a base pressure of 5 104 Pa. The lms were deposited on unheated

E-mail address: kuhaili@kfupm.edu.sa 0042-207X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2007.10.004

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624 M.F. Al-Kuhaili / Vacuum 82 (2008) 623629 Table 1 Reported values of the XPS binding energies (BE) and full-width at halfmaximum (G) of copper oxides in the Cu 2p3/2 and O 1 s core level regions Peak Cu 2p3/2 Form Bulk Film O1s Bulk Film Material Cu2O CuO Cu2O CuO Cu2O CuO Cu2O CuO BE (eV) 932.4933.3 933.6933.8 932.4933.7 933.6934.8 530.4 529.6530.0 530.4 529.8530.8 Refs. [4,15,19] [4,15,19] [7,11,15] [7,11,15,17] [19] [4,19] [28] [17] G (eV) 1.9 3.4 1.2 1.3 Refs. [15] [15] [19] [19]

substrates (RS lms) as well as substrates that were heated to 300 1C (HS lms). For each type, two sets of lms were simultaneously deposited, one set was used to the study the properties of the as-deposited lms and the other set was annealed in air at 500 1C for 3 h (RSA and HSA lms) and the lms were subsequently characterized. The substrates were rotating during the deposition, and the source-tosubstrate distance was 40 cm. The deposition rate was 0.1 nm/s. The evaporation rate and thickness of the lms were controlled by a quartz crystal thickness monitor. For different purposes of lm characterization, the lms were simultaneously deposited on BK7 glass (for X-ray diffraction, XRD), tantalum substrates (for X-ray photoelectron spectroscopy, XPS), and fused silica substrates (for optical measurements). XRD was performed using a JEOL JDX 3530 diffractometer employing Cu Ka radiation (1.54 A). The 2y range studied was 0801. The 2y step and step acquisition time were 0.021 and 1.00 s, respectively. XPS was performed using a VG Scientic MKII spectrometer with a monochromatic Al Ka (1486.6 eV) X-ray source. The instrumental resolution was 1.2 eV, with a slit width of 0.6 cm. Prior to the XPS analysis, the samples were transferred in air to the XPS analysis chamber. The C 1s peak of hydrocarbon contamination, at a binding energy (BE) of 284.5 eV, was used as an energy reference. During the XPS analysis, the samples were maintained at ambient temperature at a pressure of 5 107 Pa. Normal-incidence transmittance and reectance, over the wavelength range 2001200 nm, were measured using a Jasco V-570 double beam spectrophotometer. X-ray uorescence (XRF) was measured using a JEOL JSX-3201 spectrometer. No tungsten (from the boat) was detected in the lms, as measured by XRF. The surface morphology of the lms was checked using a JEOL 5900 scanning electron microscope (SEM). The SEM images revealed that the surfaces of the lms were smooth, uniform, and featureless. 3. Results and discussion 3.1. Chemical analysis (XPS) XPS has been extensively used in the chemical analysis of copper oxides. XPS is a surface technique that can probe only the few top surface layers of the lm. However, it can yield valuable information about the oxidation state of copper. The copper 2p level is split into two sublevels: 2p3/2 and 2p1/2. The reported values of the BE of the Cu 2p3/2 level in CuO and Cu2O are listed in Table 1. Moreover, the Cu 2p3/2 level in CuO is characterized by the presence of a shake-up satellite at about 9 eV higher BE than the 2p3/2 peak [4]. The O 1 s peak in copper oxides (as in other metal oxides) consists of two components. The rst, lower BE, component corresponds to the CuO bond. Reported values of the BE of this component are listed in Table 1. The second component, at a higher BE, is usually attributed to different chemical states of oxygen [17], such as surface hydroxide due to adsorbed water from the

atmosphere [4]. The BE of this component is in the range 531.2531.8 eV [4,17,19], and the full-width at halfmaximum is 2.2 eV [19]. A typical XPS spectrum of a copper oxide thin lm in the Cu 2p core level region is shown in Fig. 1a and Fig. 1b shows the Cu 2p3/2 spectra for the lms deposited under various experimental conditions. All the annealed lms showed an identical Cu 2p3/2 spectrum, as indicated by the RSA curve in Fig. 1b. In order to investigate the presence of different oxidation states of copper, the Cu 2p3/2 peak could be deconvoluted into three components. The rst component (A) corresponds to Cu2O, the second component (B) corresponds to CuO, and the third component (C) corresponds to the CuO satellite. These components were tted using a Gaussian/Lorenzian mixed function employing Shirley background correction. It was found that each type of lm could be tted with only two of these components, with the third component giving a contribution that was less than 1%. An example of such a t is shown in Fig. 1c. The BE, weight (or percentage of a component to the total peak), and the full-width at halfmaximum of the two components are listed in Table 2. For the lms deposited on unheated substrates (RS lms), Cu2O was the main constituent since it formed 67% of the composition of the lm. However, for the lms deposited on heated substrates (HS lms), the main constituent was CuO (90%). Similarly, the annealed lms did not show any Cu2O component. For these lms, the main component was CuO (484%). In addition, there was at least a 15% contribution from the high BE C component. Thus, it may be concluded from the analysis of the Cu 2p3/2 peak that Cu2O was formed in appreciable amount only in the as-deposited RS lms. All other samples (as-deposited on heated substrates, and annealed) showed a predominant CuO composition. The as-deposited copper oxide phase was found to be dependent on the deposition method. For example, lms deposited by the plasma evaporation technique on unheated substrates were found to contain the Cu and Cu2O phases [14]. Similarly, lms deposited by CVD at a substrate temperature of 300 1C were found to be a mixture

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4500

Cu 2p3/2 Cu 2p1/2 satellite

Cu 2p

3000

1500

0 925 4500 RS RSA 930 935 940 945 HS 950 955 Cu 2p3/2 960

Intensity (counts)

3000

1500

0 928 4500 Cu 2p3/2 3000 A 930 932 934 936 938

1500

0 928 930 932 934 Binding Energy (eV) 936 938

Fig. 1. XPS spectra of copper oxide thin lms in the Cu 2p core level region: (a) typical XPS spectrum showing the two sublevels of the Cu 2p peak along with the satellite structure, (b) Cu 2p3/2 spectra of the lms, and (c) deconvolution of the Cu 2p3/2 spectrum.

Table 2 Deconvolution of the Cu 2p3/2 and O 1s peaks of copper oxide lms with corresponding binding energy (BE), full-width at half-maximum (G) and weight (f) of each component Peak Type A BE (eV) Cu 2p3/2 RS HS RSA HSA RS HS RSA HSA 932.1 931.9 530.2 530.7 530.1 530.1 G(eV) 1.8 1.5 1.9 2.7 1.9 1.9 f 0.67 0.10 0.58 1.00 0.77 0.79 B BE (eV) 933.7 934.2 933.5 933.7 531.4 531.5 531.4 G(eV) 3.7 3.1 3.0 2.8 2.4 2.9 2.3 f 0.33 0.90 0.84 0.85 0.42 0.23 0.21 C BE (eV) 935.3 935.7 G(eV) 2.9 2.6 f 0.16 0.15

O 1s

of CuO and Cu2O [11]. However, copper oxide lms deposited by ion beam sputtering on substrates heated to temperatures in the range 25400 1C were found to be of

the CuO phase only [7]. Our results were in close agreement with previously reported results on copper oxide thin lms. Many previous studies showed that copper oxide thin lms

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O Intensity (counts) 300

CuO (010)

6000

400

400 350 300 250 200 150

4000

B 2000

Intensity (arb. units)

200

100 50 0 20 30 40 50 60

100

0 527 528 529 530 531 532 Binding Energy (eV) 533 534 0 20 30 40 2 (degrees) 50 60

Fig. 2. A typical XPS spectrum of the deposited lms in the O 1 s core level region and its deconvolution into two components.

Fig. 3. XRD spectrum of the annealed lms. The inset shows an XRD spectrum of the as-deposited lms.

deposited on unheated substrates were of the Cu2O phase but were transformed to the CuO phase at higher substrate temperatures [8,12,13,16]. Annealing the lms in air (TX300 1C) resulted in the formation of the CuO phase, irrespective of the initial phase [9,12,13]. It was pointed out that the annealing temperature necessary for the formation of the CuO phase was dependent on the initial crystalline orientation of the lms [13]. Once the CuO phase is formed, it is not affected by annealing [9]. The O 1s spectra were also deconvoluted into two components (Fig. 2). The BE and weight of the two components are listed in Table 2. No identication of the oxide phase can be inferred from the low BE component since this component for Cu2O falls well within the reported values for CuO (Table 1). However, the higher BE component (component B) was quite signicant in most of the lms. The intensity of the O 1 s B component is partly proportional to the amount of adsorbed water, which in turn is expected to increase with the porosity of the lm. The fact that the B component in the as-deposited HS lms was zero indicates that these lms were highly compact. 3.2. Structural analysis (XRD) XRD patterns of the as-deposited and annealed copper oxide thin lms are shown in Fig. 3. The background from the amorphous glass substrate was subtracted. The XRD pattern of the as-deposited lms did not show any peak, indicating that these lms were amorphous. However, the XRD pattern of the annealed lms showed a single dominant peak. According to the Joint Committee on Powder Diffraction Spectra (JCPDS) Card no. 41-0254, the XRD peak shown in Fig. 3 corresponds to the (0 1 0) peak of CuO. The grain size (D) was estimated from the CuO (0 1 0) peak using the Scherrer formula [20]: D 0.9l/(g cos y), where l is the Cu Ka wavelength, g is the fullwidth at half-maximum of the XRD peak, and y is the diffraction angle. The corresponding values of the grain size were 29 nm (for RSA lms) and 18 nm (for HSA lms).

This relatively small grain size was due to the low growth rate of the CuO phase [5]. Apart from the chemical phase information inferred from XRD, no comparison can be made regarding the crystallinity of lms deposited by different techniques. The crystallinity (or texture) of a thin lm is affected by many factors such as the growth method, the crystallinity and treatment of the substrate, deposition temperature, and the thickness of the lm. For example, copper oxide thin lms deposited on unheated substrates by ion-beam sputtering on silicon substrates [7], plasma evaporation on glass substrates [14], and evaporation of CuO powder onto glass substrates [3] were found to be amorphous. However, lms deposited by RF magnetron sputtering of Cu2O powder [6] or copper [9] on unheated amorphous glass substrates were highly crystalline. 3.3. Phase formation The equilibrium phase diagram of the CuO system is shown in Fig. 4. The phase diagram determines the boundaries of temperature and oxygen partial pressure for maintaining the stability of Cu, CuO, and Cu2O [2]. This diagram has been used to explain the formation of various phases of copper oxide. According to this diagram, CuO is the stable phase for temperatures p300 1C regardless of the oxygen partial pressure. Moreover, at atmospheric pressure, CuO is the stable phase for temperatures p1000 1C. Our results for the HS and annealed lms are well explained by this model. However, the formation of the Cu2O phase in the RS lms seems to be contradictory to the phase diagram. This contradiction was also observed in several previous works on copper oxides [2,8,12,13,16]. The conicting results may be explained by the fact that equilibrium conditions have not been achieved [2]. The formation of CuO is explained by the reaction [13]: Cu2 O 1O2 ! 2CuO: 2

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6 4
Atmospheric pressure

2 Log P (O2) (mm-Hg) 0 -2 -4 -6 -8 -10 -12 -14 200 400 600 800 Temperature (C) 1000 1200 Cu Cu2O CuO

crystallinity was accompanied by the alleviation of structural defects. The decrease in the number of structural defects resulted in less scattering, and thus increased transmittance. Because of their crystallinity and higher transparency, the annealed lms are suitable for optical analysis from which the thickness, absorption coefcient, and band gap may be determined. The transmittance of a thin lm, on a transparent substrate, was given by Manifacier et al. [24]: Tf with A n 12 k2 n ns k2 , B n 12 k2 n ns k2 , C n2 1 k2 n2 n2 k2 4k2 ns , s D 2kns n2 1 k2 2kn2 n2 k2 , s where n refractive index of the lm, k extinction coefcient of the lm, ns refractive index of the substrate, d thickness of the lm, l wavelength of light, and b exp(4pkd/l. In order to t the experimental transmittance spectra using Eq. (1), models for the dispersion of n and k must be implemented. The refractive index of the annealed lms was modeled by a single oscillator model [25]: !1=2 EoEd n 1 2 , (2) Eo E2 where Eo is the effective dispersion oscillator energy, Ed is the dispersion energy related to the interband transition strength, and E is the incident photon energy. The extinction coefcient is related to the absorption coefcient (a) by k al/4p. In the transparency region, absorption was assumed to originate from scattering, for which a p l4 [26]. Therefore, k ko/l3, where ko is a constant. The transparency regions, of the annealed lms, were dened as those for which R+T40.95. This corresponds to lX600 nm for the RSA lms, and lX1000 nm for the HSA lms. The transmittance of the annealed lms was tted using the above model, taking Eo, Ed, ko, and d as tting parameters. The correlation was excellent (40.995) and the thickness of the annealed lms was found to be 77.373.5 nm. Above the fundamental absorption edge (a4104 cm1), the dependence of the absorption coefcient on the incident photon energy is given by Taue [27]: aE ao E E g Z , (3) 16ns n2 k2 b A Bb2 2bC cos4pnd=l D sin4pnd=l (1)

Fig. 4. Pressure versus temperature equilibrium phase diagram in the copperoxygen system showing the stability domains of Cu, CuO, and Cu2O (from Ref. [2]).

Oxygen can be introduced by heating (substrate heating [8] or annealing [13]) since the Gibbs free energy for the above reaction is3.73 kcal/mol at 200 1C [8]. In this case, oxygen diffuses from the bulk of the lm into the surface to form CuO [9,13]. 3.4. Optical properties The normal-incidence transmittance (T) and reectance (R) spectra of the lms are shown in Fig. 5. The transmittance spectra were obtained by dividing the measured transmittance by that of the substrate. Ideally, for a non-absorbing lm, the sum R+T 1. In the infrared region (far from the fundamental absorption region), this sum is indicative of the transparency of the lm. For the as-deposited lms, R+To0.8, whereas the annealed lms had R+TX0.95. Therefore, the annealed lms showed higher transparency. The small residual absorption (o0.05) may be attributed to scattering. Moreover, the transmittance decreased for the higher substrate temperature. The reduction of transmittance for the higher substrate temperature may be attributed to two factors. First, as the substrate temperature increases, scattering losses increase. Scattering is caused by high roughness [21]. Second, increasing the substrate temperature causes the full transformation from the less-dense Cu2O phase to the more-dense CuO phase. The bulk densities of these phases are 6.0 g/cm3 for Cu2O and 6.36.49 g/cm3 for CuO [22]. A similar reduction in transmittance was observed in TiO2 lms upon their transformation from the less-dense anatase phase to the more-dense rutile phase [23]. The effect of annealing may be attributed to crystallinity. Upon annealing, the lms were transformed from amorphous to crystalline. This improvement in

where ao is a constant, Eg is the band gap, and Z is an exponent that depends on the type of transitions involved. The value of Z is 1 or 2 for direct allowed or indirect 2 allowed transitions, respectively. Therefore, a plot of (aE)1/Z as a function of photon energy should give a straight line. Moreover, in the fundamental absorption

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0.6

RS T

HS

0.4 R T 0.2 Reflectance or Transmittance R

0.0 1.0

RSA T

HSA T

0.8

0.6

0.4

0.2 R 0.0 200 400 600 800 1000 1200 200 400 Wavelength (nm) 600 800 1000 1200 R

Fig. 5. Normal-incidence reectance and transmittance spectra of copper oxide thin lms: (a) as-deposited lms on unheated substrates, (b) as-deposited lms on heated substrates, (c) annealed lms deposited on unheated substrates, and (d) annealed lms deposited on heated substrates.

region, the absorption coefcient is related to the transmittance and reectance of the lm as [10]: T 1 Read , a   1 1R Ln . d T (4a) (4b)

The best t to Eq. (3) was obtained with Z 2, indicating that the absorption edge was due indirect allowed transitions. Plots of (aE)1/2 on the vertical axis versus photon energy on the horizontal axis are shown in Fig. 6. The linear portions of the curves were tted using linear regression analysis, where the correlation coefcient was 0.997. An extrapolation of the linear regions of the plots gives the value of the band gap as the intercept to the horizontal axis (where a 0). The values of the band gaps were 2.16 and 1.76 eV for the RSA and HSA lms, respectively. The lower band gap for the HSA lms is consistent with the transmittance curves (Fig. 5), which

shows a shift of the absorption edge of these lms toward longer wavelengths compared to the RSA lms. The lower band gap of the HSA lms may indicate better oxidation since the band gap of bulk CuO was reported to be 1.21.3 eV [13,15]. Moreover, the HSA lms showed another lower energy gap of 1.08 eV. This lower energy gap may be due to absorption involving defect states. The reported values for the band gap of CuO lms were in the range 1.752.11 eV [6,9,12]. This scatter in the reported values may be attributed to two factors. First, the optical properties depend critically on the physical properties of the lms, which are subsequently affected by the deposition and post-deposition conditions. Second, different models have been used to extract the optical properties from measured quantities. For example, a, a2, (aE)2, (aE)2/3, and (aE)1/2 were all plotted against the photon energy to determine the band gap. This not only affects the value of the band gap but also affects the interpretation of the nature of the gap (i.e. direct or indirect).

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2000

RSA

2500 HSA 2000

1500 ( E)1/2 (eV/cm)1/2 1500 1000 1000 500 500

0 2 3 4 5 6 7

0 1 2 3 4 5 6 7 Photon Energy (eV)

Fig. 6. Variation of (aE) as a function of photon energy for the annealed copper oxide thin lms deposited either on unheated substrates (RSA) or heated substrates (HSA).

1/2

4. Conclusions Thin lms of copper oxide were deposited by the direct thermal evaporation of Cu2O powder on substrates at different temperatures. The lms were also subjected to post-deposition annealing in air. Chemical analysis indicated that only the as-deposited lms on unheated substrates had dominant Cu2O composition. Films deposited on heated substrates as well as annealed lms had a predominant CuO composition. The as-deposited lms were amorphous with poor transmittance in the visible and infrared. However, the annealed lms were more crystalline and had higher transparency. The band gaps of the annealed lms were in the range 1.762.16 eV. Acknowledgements The author acknowledges the support of this work by the Physics Department and the Research Institute of King Fahd University of Petroleum and Minerals. References
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