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Thin Solid Films 516 (2008) 3893 3898 www.elsevier.com/locate/tsf

Growth and characterisation of electrodeposited ZnO thin films

J.S. Wellings a,, N.B. Chaure a , S.N. Heavens b , I.M. Dharmadasa a
a

Solar Energy Group, Materials & Engineering Research Institute, Sheffield Hallam University, Sheffield S1 1 WB, UK b Ionotec Ltd, 14 Berkeley Court, Manor Park, Runcorn, Cheshire WA7 1TQ, UK Received 14 November 2006; received in revised form 15 June 2007; accepted 15 July 2007 Available online 25 July 2007

Abstract The electrochemical method has been used to deposit zinc oxide (ZnO) thin films from aqueous zinc nitrate solution at 80 C onto fluorine doped tin oxide (FTO) coated glass substrates. ZnO thin films were grown between 0.900 and 1.025 V vs Ag/AgCl as established by voltammogram. Characterisation of ZnO films was carried out for both as-deposited and annealed films in order to study the effect of annealing. Structural analysis of the ZnO films was performed using X-ray diffraction, which showed polycrystalline films of hexagonal phase with (002) preferential orientation. Atomic force microscopy was used to study the surface morphology. Optical studies identified the bandgap to be 3.20 eV and refractive index to 2.35. The photoelectrochemical cell signal indicated that the films had n-type electrical conductivity and currentvoltage measurements showed the glass/FTO/ZnO/Au devices exhibit rectifying properties. The thickness of the ZnO films was found to be 0.40 m as measured using the Talysurf instrument, after deposition for 3 min. Environmental scanning electron microscopy was used to view the cross-section of glass/FTO/ZnO layers. 2007 Elsevier B.V. All rights reserved.
Keywords: Electrodeposition; ZnO; X-ray diffraction; IIVI compound semiconductor

1. Introduction Zinc oxide (ZnO) is a non-toxic, IIVI, wide bandgap semiconductor with Eg = 3.20 eV and natural n-type electrical conductivity. Among various other applications such as lightemitting diodes, laser diodes [1], piezoelectric transducers [2], transistors [3] and phosphors [4], ZnO is used as a transparent buffer layer in solar cell devices [5]. Various publications to date have suggested that the addition of a highly resistive intrinsic (i) ZnO layer in copper indium gallium diselenide (CuInGaSe2) solar cell devices drastically improves device efficiency, as it may prevent the leakage current [68]. The i-ZnO layer may also act as a pinhole plugging layer or work as an anti-reflection coating. ZnO absorbs the UV part of the solar spectrum and allows lower energy photons to travel to the absorber layer. Doping ZnO with group III elements such as B, Al, or In increases the n-type conductivity [9,10].

Corresponding author. Tel.: +44 114 225 5292; fax: +44 114 225 3433. E-mail address: jayne.s.wellings@student.shu.ac.uk (J.S. Wellings). 0040-6090/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2007.07.156

Numerous growth techniques have been used to produce ZnO, including molecular beam epitaxy (MBE) [11], electron beam evaporation [12], metal organic chemical vapor deposition (MOCVD) [13], and spray pyrolysis [14]. Drawbacks to using such techniques are high cost of equipment, only small material layer production, time consumption and complexity of operation. ZnO can also be grown by electrodeposition [9,15], which is a low cost technique that does not require expensive, sophisticated equipment and is simple to operate. Electrodeposition also has the advantage of having low temperature processing, allows various substrate shapes and controllable film thickness. This technique also avoids the use of vacuum systems allowing growth under normal laboratory conditions [16]. In the present work, electrochemical technique was used to grow ZnO thin films on fluorine doped tin oxide (FTO) coated glass substrates from aqueous solution. Optical, structural, morphological, electrical and opto-electrical properties have been studied using UVVis spectrophotometer, X-ray diffraction (XRD), atomic force microscopy (AFM), environmental scanning electron microscopy (ESEM), currentvoltage (IV),

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capacitancevoltage (CV) and photoelectrochemical cell (PEC) measurements respectively. 2. Experimental details Glass substrates coated with (FTO) having a sheet resistance of 15 / supplied by Pilkington Group Ltd were used as the working electrode for the electrodeposition of ZnO. Prior to the deposition, substrates were washed thoroughly with boiled, soapy, deionised water and rinsed before being cleaned ultrasonically. ZnO thin films were electrodeposited potentiostatically using a conventional three-electrode system, with graphite plate counter electrode and silver/silver chloride (Ag/ AgCl) (+ 220 mV vs normal hydrogen electrode) reference electrode. GillAC version 4, computerised potentiostat/galvanostat was employed to perform the potentiostatic deposition. The aqueous solution contained 0.1 M zinc nitrate, Zn(NO3)26H2O dissolved in 150 ml deionised water. The electrolyte was stirred constantly using a magnetic stirrer throughout deposition and kept at a temperature of 80 C ( 2 C). pH of the as-prepared solution was 5.0, without any alteration the same bath was used for the electrochemical experiments. An air-tight three electrode electrochemical cell was employed to electrodeposit the layers. The working and counter electrodes were held vertically using teflon tape. The reference electrode was fixed at one side of the electrochemical cell making an angle 45. This arrangement was used to keep the reference electrode as close as possible to the working electrode. Uniformity of electrodeposited materials is one critical issue, which depends on the current distribution and geometry of the electrodes. In order to produce a uniform thin film over the entire electrode area, the counter and working electrodes were the same size and positioned between high and low current density area. The schematic diagram for the electrodeposition cell is shown in Fig. 1.

Fig. 2. Voltammogram of 0.1 M zinc nitrate electrolyte with 10 mV s 1 sweep rate.

Voltammogram was used to decide the suitable region of growth potential. Samples with dimensions 15 30 mm2 were grown at various cathodic potentials between 0.900 and 1.100 V vs Ag/AgCl to study various properties. Optical absorption spectra were taken using UVVis spectrometer, Unicam UV-2, to determine the absorption edge and bandgap of the electrodeposited ZnO layers. XRD was carried out using a Philips X-Pert Pro-diffractometer with CuK 1 source ( = 1.5406 ) at a glancing angle of 0.5. AFM Digital Instrument Nanoscope III was used to study the surface morphology. The PEC cell was used to determine the electrical conductivity type of the electrodeposited ZnO by monitoring the polarity of the open circuit voltage (Voc) produced at the liquid/solid junction,

Fig. 1. Schematic diagram of the electrodeposition set-up.

Fig. 3. XRD spectra of as-deposited ZnO films electrodeposited at (a) 0.900 V, (b) 0.925 V, (c) 0.975 V, (d) 1.000 Vand (e) 1.025 V vs Ag/AgCl reference.

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The sharp rise in cathodic current observed beyond 1.050 V could be due to the metallic deposition of Zn and hydrogen (H2) evolution reaction. 3.2. X-ray diffraction (XRD) XRD studies have been carried out on ZnO layers in order to determine phase and crystallographic analysis. The films deposited at various potentials, shown in Fig. 3 (ae) are polycrystalline with hexagonal phase and (002) preferential orientation, except sample (b) deposited at 0.925 V vs Ag/ AgCl. The appearance of the film grown at 0.975 V was transparent, compact and uniform. Moreover, improved crystallinity was observed for the film grown at 0.975 V compared to the other growth potentials. The effect of annealing has been studied on the film grown at 0.975 V cathode potential, with annealing temperature of 550 C for 15 min. Typical XRD spectra for the as-deposited and annealed film is shown in Fig. 4 (a and b). Table 1 illustrates the XRD data obtained for both as-deposited and annealed ZnO films. No noticeable change was observed in XRD spectra for the as-deposited and annealed sample. The data obtained for XRD analysis was used to determine the mean grain size (t) and strain () using the Hull Eq. (4). b cos h k e sin h t 4

Fig. 4. The XRD patterns of ZnO thin films grown at 0.975 V; (a) as-deposited (b) annealed. The inset shows the solution of the Hull equation.

under illumination. Philips XL 30 ESEMField-Emission Gun with accelerating voltage of 20 kV was used to study the crosssection of the glass/FTO/ZnO. The thickness of the ZnO layer was obtained by Taylor-Hobson Tallysurf 1204 L instrument and compared with the ESEM cross-section. Selected samples were annealed to determine the effect of post-growth heat treatment. Annealing was achieved using a Bio-Rad furnace operating at a temperature of 550 C for 15 min in air atmosphere. Annealed samples were metallised with gold (Au) contacts to produce devices of 2 mm in diameter. The electrical properties were studied using IV and CV techniques. 3. Results and discussion 3.1. Voltammogram The electrochemical behaviour of ZnO was studied using voltammetry to optimise the growth potential, in conjunction with the X-ray diffraction technique. Fig. 2 shows the voltammogram for the solution containing Zn(NO3)2 at pH 5.0 with moderate continuous stirring vs Ag/AgCl reference electrode. The sweep rate was 10 mV s 1. For low cathodic potential the current increases slowly first and shows a rapid increase from about 0.650 V. A plateau is observed between 0.800 to 1.000 V where the ZnO deposition is expected by the following mechanisms. ZnNO3 2 Zn2 2NO 3
NO 3 H2 O 2e NO2 2OH

where is full width at half maximum (FWHM) intensity, is the Bragg angle and is the wavelength. The plot of cos
Table 1 Data obtained from XRD of ZnO film grown at 0.975 V vs Ag/AgCl (a) asdeposited (b) annealed 2 (deg) d spacing () Standard Observed FWHM (degree) Miller indices (hkl) (100) (002) (101) (102) (110) (103) (112) (201) (004) (202) Phase assignment

As-deposited 31.87 2.8179 34.48 2.6049 36.28 2.4786 47.56 1.9128 56.77 1.6269 62.92 1.4784 68.93 1.3799 69.10 1.3601 72.82 1.3024 77.02 1.2393 Annealed 31.84 34.50 36.28 47.64 56.72 62.98 68.10 69.28 72.82 77.12

2.8096 2.5987 2.4778 1.9141 1.6266 1.4762 1.3790 1.3593 1.3009 1.2385

0.36 0.33 0.27 0.29 0.24 0.33 0.40 0.42 0.30 0.24

ZnO hexagonal

1 2 3

Zn2 2OH ZnO H2 O

2.8179 2.6049 2.4786 1.9128 1.6269 1.4784 1.3799 1.3601 1.3024 1.2393

2.8095 2.5993 2.4763 1.9113 1.6230 1.4719 1.3793 1.3563 1.2980 1.2372

0.20 0.22 0.26 0.29 0.28 0.39 0.52 0.48 0.40 0.56

(100) (002) (101) (102) (110) (103) (112) (201) (004) (202)

ZnO hexagonal

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the strain reduces after annealing the sample, which could be due to the restructuring of the crystal lattice. The lattice parameter of a and c calculated using Eq. (5) for the asdeposited and annealed ZnO films grown at 0.975 V are close to the standard values a = 3.253 , c = 5.209 [17,18].   1 4 h2 k 2 hk l2 5 d2 3 a2 c2

3.3. Atomic force microscopy AFM technique was used to investigate the surface morphology of as-deposited and annealed ZnO thin films grown at 0.975 V vs Ag/AgCl. As-deposited samples show compact, uniform and void-free surfaces as shown in Fig. 5 (a). Small clusters of size 100 nm formed by agglomeration of smaller individual grains of size 40 to 50 nm. After annealing at 550 C for 15 min the morphology of the deposit changed and can be seen in Fig. 5 (b). The grains have formed large clusters of various sizes ranging from 200 nm to 1.5 m size. The rms roughness values obtained for as-deposited and annealed ZnO films were 41.2 nm and 49.5 nm. These results obtained using AFM are in agreement with Nunes et. al. [19]. 3.4. Optical absorption The optical absorption studies have been carried out on selected ZnO films deposited at various growth potentials. The most uniform and transparent films were observed to be grown at 0.975 V vs Ag/AgCl. The film deposited at 0.975 V showed a sharp optical absorption edge, with bandgap for asdeposited film of 3.22 eV as illustrated by Fig. 6 (a). After annealing at 550 C for 15 min the absorption edge was red shifted to 3.20 eV as shown by Fig. 6 (b). This agrees with previously reported bandgap for ZnO [20]. High optical transparency is essential for ZnO if it is to be used as a buffer layer in solar cell devices. In addition the refractive index of

Fig. 5. AFM micrograph of ZnO film grown at 0.975 V vs Ag/AgCl (a) asdeposited (b) annealed at 550 C for 15 min.

against sin inset in Fig. 4 (a and b) was found to be linear. The values obtained for strain and mean grain size for the asdeposited and annealed ZnO films were 9.32 10 3 and 42.7 nm and 2.09 10 3 and 55.0 nm respectively. Note that

Fig. 6. Typical optical absorption curve for (a) as-deposited and (b) annealed at 550 C for 15 min of ZnO layer electrodeposited at 0.975 V vs Ag/AgCl.

Fig. 7. Typical IV curve for glass/FTO/ZnO/Au device showing rectifying behaviour.

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Fig. 8. A typical 1 / C2 vs voltage curve for glass/FTO/ZnO/Au structures.

Fig. 9. Variation of thickness of ZnO thin films grown at 0.975 V vs Ag/AgCl as a function of deposition time. Note the linear growth up to 10 min and a reduced growth rate beyond this limit.

zinc oxide was calculated using Eq. (6) [21] to be 2.35, which is close to the value in the literature [22,23]. q n2 1 1 E g =20 n2 2 3.5. Electrical properties The dark currentvoltage (IV) characteristics of glass/FTO/ ZnO/Au structures were measured using fully automated system and a typical curve is shown in Fig. 7. These structures showed good rectification properties with rectification factor of 103 at 1.0 V, ideality factor of 3.0 and barrier height of N 1.08 eV. Since the diodes are non-ideal, accurate barrier height cannot be estimated. The series resistance (Rs) of the structure was estimated using the high forward biased region of the IV curve and this was found to be about 1.6 k. Making use of the known contact area and the film thickness, the bulk resistivity () and the electrical conductivity () were found to be 1.67 106 (cm) and 5.98 10 7 (cm) 1 respectively. In order to accurately estimate the electrical properties of these films a low work function (m) metal, silver (Ag) was used to make electrical contacts, expecting ohmic behaviour. However the IV curves of glass/FTO/ZnO/Ag also exhibit rectifying characteristics similar to those of Au contacts. This indicates that ideal Schottky behaviour is not observed for ZnO/ metal interfaces.
Table 2 PEC signal of ZnO films illustrating n-type electrical conductivity of the layers Material n-Si p-Si ZnO ZnO ZnO ZnO ZnO Deposition potential (V) Standard sample Standard sample 0.900 0.925 0.975 1.000 1.025 Vdark (mV) 0.390 0.360 0.305 0.315 0.340 0.364 0.375 Vlight (mV) 0.530 0.320 0.356 0.350 0.428 0.410 0.455 V (mV) 140 40 51 35 88 46 80 Conductivity type n p n n n n n

Capacitancevoltage measurements of glass/FTO/ZnO/Au devices were taken as a function of bias voltage with a detection signal frequency of 1 MHz. In order to estimate doping concentration of ZnO, 1 / C2 vs V plots were generated and a typical curve is shown in Fig. 8. Using the gradient of the curve and taking the dielectric permittivity of ZnO to be s = 9.26 [24] yields 2.8 1012 cm 3 for donor concentrations. It should be noted that the CV measurements are prone to effects of defects and hence produce doping concentrations away from accurate values. Assuming the above value for doping concentration and electrical conductivity of 5.98 10 7 (cm) 1, 1.25 cm2/V s has been obtained for the mobility of electrons in the electrodeposited ZnO layers. 3.6. Opto-electrical properties Electrical conductivity type was determined by PEC measurements. The glass/FTO/ZnO substrate and a graphite rod were immersed in a sodium chloride, NaCl solution and the difference between the observed dark and light voltages was recorded using a voltmeter. The polarity of the PEC signal demonstrates the electrical conductivity type of the material.

Fig. 10. ESEM cross-section of glass/FTO/ZnO structures showing ZnO layer thickness of 0.4 m after growth for 3 min.

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The magnitude of the signal indicates the suitability of the doping concentration (Nd) of the semiconductor layers for device application. The PEC system was standardised using known samples of n and p-type silicon. All ZnO films demonstrated n-type electrical conductivity as summarised in Table 2. 3.7. Thickness measurements Talysurf measurements were carried out on as-deposited ZnO films grown at 0.975 V for different growth periods to determine the thickness. Fig. 9 illustrates an almost linear relationship up to 10 min and reduced growth rate there-after. Reduction in deposition rate could arise from dissolution of the electrodeposited ZnO film in the acidic electrolyte. The information has vital importance in depositing ZnO layers with desired thicknesses for device structures. Electrodeposition therefore provides an excellent method of depositing submicron thick ZnO layers within a few minutes using normal laboratory conditions, in order to reduce underlying cost of solar cells. To confirm the film thickness determined by the Talysurf measurement the glass/FTO/ZnO cross-section was examined by ESEM as shown in Fig. 10. The thickness of the ZnO layer electrodeposited for 3 min was shown to be 0.4 m, in agreement with Fig. 9. 4. Conclusion Polycrystalline, hexagonal ZnO layers with (002) preferential orientation have been deposited from aqueous solutions using an electrochemical technique onto FTO-coated glass. The deposition potential was optimised to be 0.975 V vs Ag/AgCl resulting in smooth, compact, uniform and well adhered films. The grain size calculated by Hull equation for as-deposited and annealed sample was 42.7 and 55 nm, which are close to the values obtained by AFM. The PEC cell measurements confirm n-type conductivity of the ZnO films. Optical absorption indicated the bandgap to be 3.20 eV and refractive index to be 2.35. The thickness of the ZnO layer had a linear relationship for shorter periods of growth and saturated when grown for longer periods. Acknowledgment The authors would like to acknowledge the UK Government's Department of Trade and Industry (DTI) for providing

funding for this research. Pilkington Group Ltd are acknowledged for their contribution to this project. Mr Leon Bowen is also gratefully acknowledged for his technical support. References
[1] S.Y. Lee, E.S. Shim, H.S. Kang, S.S. Pang, J.S. Kang, Thin Solid Films 473 (2005) 31. [2] D.C. Look, Mater. Sci. Eng., B 80 (2001) 383. [3] E. Fortunato, T.P. Barquinha, A. Pimentel, A. Goncalves, A. Marques, L. Pereira, R. Martins, Thin Solid Films 487 (2005) 205. [4] E. Hosono, S. Fujihara, T. Kimura, Electrochem. Solid-State Lett. 7 (2004) C49. [5] D. Hariskos, S. Spiering, M. Powalla, Thin Solid Films 480 (2005) 99. [6] K. Ramanathan, M. Contreras, C. Perkins, S. Asher, F.S. Hasoon, J. Keane, D. Young, M. Romero, W. Metzger, R. Noufi, J. Ward, A. Duda, Prog. Photovolt. Res. Appl. 11 (2003) 225. [7] M. Contreras, K. Ramanathan, J. Abushama, F. Hasoon, D.L. Young, B. Egaas, R. Noufi, Prog. Photovolt. Res. Appl. 13 (2005) 209. [8] S. Ishizuka, K. Sakurai, A. Yamada, K. Matsubara, P. Fons, K. Iwata, S. Nakamura, Y. Kimura, T. Baba, H. Nakanishi, T. Kojima, S. Nikki, Sol. Energy Mater. Sol. Cells 87 (2005) 541. [9] D. Lincot, Thin Solid Films 487 (2005) 40. [10] M. Kemell, F. Dartigues, M. Ritala, M. Leskela, Thin Solid Films 434 (2003) 20. [11] H.W. Liang, Y.M. Lu, D.Z. Shen, J.F. Yan, B.H. Li, J.Y. Zhang, Y.C. Liu, X.W. Fan, J. Cryst. Growth 278 (2005) 305. [12] N.R. Aghamalyan, A. Gambaryan, E.K. Goulanian, R.K. Hovsepyan, R.B. Kostanyan, S.I. Petrosyan, E.S. Vardanyan, A.F. Zerrouk, Semicond. Sci. Technol. 18 (2003) 525. [13] B.P. Zhang, K. Wakatsuki, N.T. Binh, N. Usami, Y. Segawa, Thin Solid Films 449 (2004) 12. [14] M.T. Mohammad, A.A. Hashim, M.H. Al-Maamory, Mater. Chem. Phys. 99 (2006) 382. [15] T. Mahalingham, V.S. John, M. Raja, Y.K. Su, P.J. Sebastian, Sol. Energy Mater. Sol. Cells 88 (2005) 227. [16] R.K. Pandey, S.N. Sahn, S. Chandra, Handbook of Semiconductor Electrodeposition, Marcel Dekker, New York, 1996. [17] B.D. Cullity, S.R. Stock, Elements of X-ray Diffraction, 3rd ed, Prentice Hall, New Jersey, 2001. [18] Powder Diffraction File, Joint Committee on Powder Diffraction Standards, ASTM, Philadelphia, PA, 1997 card 80-0075. [19] P. Nunes, E. Fortunato, R. Martins, Thin Solid Films 383 (2001) 277. [20] R.E. Marotti, D.N. Guerra, C. Bello, G. Machado, E.A. Dalchiele, Sol. Energy Mater. Sol. Cells 82 (2004) 85. [21] V. Dimitrov, S. Sakka, J. Appl. Phys. 79 (1996) 1736. [22] D.R. Lide, CRC Handbook of Chemistry and Physics, CRC press, 2005, p. 230, section 10. [23] E. Cetinorgu, S. Goldsmith, R.L. Boxman, Surf. Coat. Technol. 201 (2007) 7266. [24] D.R. Lide, CRC Hand of Chemistry and Physics, CRC press, 2005, p. 56, section 12.