Effect of different dopant elements on the properties of ZnO thin films

Vacuum, Vol. 64

Up-conversion effect of Er- and Yb-doped ZnO thin films

Visible up-conversion in ZnO:Er and ZnO:Er:Yb thin films deposited by RF magnetron sputtering under different O2-rich atmospheres has been studied. Conventional photoluminescence (325 nm laser source) and up-conversion (980 nm laser source) have been performed in the films before and after an annealing process at 800 °C. The resulting spectra demonstrate that the thermal treatment, either during or post-deposition, activates optically the Er3+ ions, being the latter process much more efficient. Moreover, the atmosphere during deposition was also found to be an important parameter, as the deposition under O2 flow increases the optical activity of Er+3 ions. In addition, the inclusion of Yb3+ ions into the films has shown an enhancement of the visible up-conversion emission at 660 nm by a factor of 4, which could be associated to either a better energy transfer from the 2F5/2 Yb level to the 4I11/2 Er one, or to the prevention of having Er2O3 clustering in the films.

Effect of self assembly on the nonlinear optical characteristics of ZnO thin films

In the present work, we report the third order nonlinear optical properties of ZnO thin films deposited using self assembly, sol gel process as well as pulsed laser ablation by z scan technique. ZnO thin films clearly exhibit a negative nonlinear index of refraction at 532 nm and the observed nonlinear refraction is attributed to two photon absorption followed by free carrier absorption. Although the absolute nonlinear values for these films are comparable, there is a change in the sign of the absorptive nonlinearity of the films. The films developed by dip coating and pulsed laser ablation exhibit reverse saturable absorption whereas the self assembled film exhibits saturable absorption. These different nonlinear characteristics in the self assembled films can be mainly attributed to the saturation of linear absorption of the ZnO defect states.

Synthesis and characterization of 3d-transition metals doped ZnO thin films and nanostructures for possible spintronic applications

The objective of the present study is the formation of single phase Zn1−xTMxO thin films by PLD and increase the solubility limit of TM dopants. The TM doped ZnO nanostructures were also grown by hydrothermal method. The structural and morphological variation of ZnO:TM thin films and nanostructures with TM doping concentration is also investigated. The origin and enhancement of ferromagnetism in single phase Zn1−xTMxO thin films and nanostructures using spectroscopic techniques were also studied. The dependence of ablation parameters on the structural and optical properties of ZnO thin films were studied

On tuning the orientation of grains of spray pyrolysed ZnO thin films

Effect of varying spray rate on the structure and optoelectronic properties of spray pyrolysed ZnO film is analysed. ZnO films were characterised using different techniques such as X-ray diffraction (XRD), photoluminescence, electrical resistivity measurement, and optical absorption. The XRD analysis proved that, with the increase in spray rate, orientation of the grains changed from (1 0 1) plane to (0 0 2) plane. The films exhibited luminescence in two regions—one was the ‘near band-edge’ (NBE) (∼380 nm) emission and the other one was the ‘blue-green emission’ (∼503 nm). Intensity of the blue-green emission decreased after orientation of grains shifted to (0 0 2) plane. Scanning electron microscope (SEM) analysis of the films asserts that spray rate has major role in improving the crystallographic properties of the films. Moreover resistivity of the films could be lowered to 2.4×10−2 cm without any doping or post-deposition annealing

Reliable and Damage-Free Estimation of Resistivity of ZnO Thin Films for Photovoltaic Applications Using Photoluminescence Technique

This work projects photoluminescence (PL) as an alternative technique to estimate the order of resistivity of zinc oxide (ZnO) thin films. ZnO thin films, deposited using chemical spray pyrolysis (CSP) by varying the deposition parameters like solvent, spray rate, pH of precursor, and so forth, have been used for this study. Variation in the deposition conditions has tremendous impact on the luminescence properties as well as resistivity. Two emissions could be recorded for all samples—the near band edge emission (NBE) at 380 nm and the deep level emission (DLE) at ∼500 nm which are competing in nature. It is observed that the ratio of intensities of DLE to NBE ( DLE/ NBE) can be reduced by controlling oxygen incorporation in the sample. - measurements indicate that restricting oxygen incorporation reduces resistivity considerably. Variation of DLE/ NBE and resistivity for samples prepared under different deposition conditions is similar in nature. DLE/ NBE was always less than resistivity by an order for all samples.Thus from PL measurements alone, the order of resistivity of the samples can be estimated.

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 degrees C, and (ii) isothermal annealing at 450 degrees C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 degrees C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 degrees C. These results indicate that thermal annealing at the highest temperature (550 degrees C) induces a noticeable compaction effect on the structure of the studied thin films. (C) 2011 Elsevier B.V. All rights reserved.

Growth evolution of ZnO thin films deposited by RF magnetron sputtering

We study the surface morphology evolution of ZnO thin films grown on glass substrates as a function of thickness by RF magnetron sputtering technique. The surface topography of the samples is measured by atomic force microscopy (AFM). All AFM images of the films are analyzed using scaling concepts. The results show that the surface morphology is initially formed by a small grains structure. The grains increase in size and height with growth time resulting in the formation of a mounds-like structure. The growth exponent, beta, and the exponent defining the evolution of the characteristic wavelength of the surface, p, amounted to beta = 0.76 +/- 0.08 and p = 0.3 +/- 0.05. From these exponents, the surface morphology is determined by the nonlocal shadowing effects, that is the dominant mechanism, due to the incident deposition particles during film growth.

Structural electrical and optical properties of undoped and indium doped ZnO thin films prepared by the pyrosol process at different temperatures

The influence of the substrate temperature on the structural features and opto-electrical properties of undoped and indium-doped ZnO thin films deposited by pyrosol process was investigated. The addition of indium induces a drastic decrease (by a factor approximate to 10(10) for samples deposited at 300 degreesC) in the electrical resistivity of films, the lowest electrical resistivity (6 mOmega-cm) being observed for the film deposited at 450 degreesC. Films are highly transparent (>80%) in the Vis-NIR ranges, and the optical band gap exhibits a blue shift (from 3.29 to 3.33 eV) for the In-doped films deposited at increasing temperature. Preferential orientation of the ZnO crystallites with the c-axis perpendicular to the substrate surface and an anisotropic morphology of the nanoporous structure was observed for films growth at 300 and 350 degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effect of pressure-assisted thermal annealing on the optical properties of ZnO thin films

ZnO thin films were prepared by the polymeric precursor method. The films were deposited on silicon substrates using the spin-coating technique, and were annealed at 330°C for 32h under pressure-assisted thermal annealing and under ambient pressure. Their structural and optical properties were characterized, and the phases formed were identified by X-ray diffraction. No secondary phase was detected. The ZnO thin films were also characterized by field-emission scanning electron microscopy, Fourier transform infrared spectroscopy, photoluminescence and ultraviolet emission intensity measurements. The effect of pressure on these thin films modifies the active defects that cause the recombination of deep level states located inside the band gap that emit yellow-green (575nm) and orange (645nm) photoluminescence. © 2012 John Wiley & Sons, Ltd.

Structural transition of ZnO thin films produced by RF magnetron sputtering at low temperatures

Zinc oxide (ZnO) thin films were prepared using reactive radio-frequency magnetron sputtering of a pure metallic zinc target onto glass substrates. The evolution of the surface morphology and the optical properties of the films were studied as a function of the substrate temperature, which was varied from 50 to 250 C. The surface topography of the samples was examined using atomic force microscopy (AFM), and their optical properties were studied via transmittance measurements in the UV-Vis-NIR region. DRX and AFM analyses showed that the surface morphology undergoes a structural transition at substrate temperatures of around 150 C. Actually, at 50 C the formation of small grains was observed while at 250 C the grains observed were larger and had more irregular shapes. The optical gap remained constant at ∼3.3 eV for all films. In the visible region, the average optical transmittance was 80 %. From these results, one can conclude that the morphological properties of the ZnO thin films were more greatly affected by the substrate temperature, due to mis-orientation of polycrystalline grains, than were the optical properties. © 2013 Springer Science+Business Media New York.

Electrophoretic Deposition of Transparent ZnO Thin Films from Highly Stabilized Colloidal Suspensions

The parameters that control the stability of ZnO-nanoparticles suspensions and their deposition by electrophoretic deposition were studied, so as to organize the assembly and compaction of nanoparticles. The addition of cationic polyelectrolyte - Polyethylenimine (PEI) - with different molecular weights was investigated, in order to study their effectiveness and the influence of the molecular weight of the organic chain on suspensions dispersion. It was found that PEI with the highest molecular weight provided better dispersion conditions. Cathodic EPD was performed under previously optimized suspensions conditions and over electropolished stainless steel substrates. Experimental results showed that the EPD process in these conditions allows obtaining dense transparent ZnO thin films. Deposition times and intensities were optimized by analyzing the resulting thin films characteristics. Finally, the deposits were characterized by FE-SEM, AFM, and different spectroscopic techniques.

Effect of annealing on the spectral and nonlinear optical characteristics of thin films of nano-ZnO

The annealing effect on the spectral and nonlinear optical NLO characteristics of ZnO thin films deposited on quartz substrates by sol-gel process is investigated. As the annealing temperature increases from 300–1050 °C, there is a decrease in the band gap, which indicates the changes of the interface of ZnO. ZnO is reported to show two emission bands, an ultraviolet UV emission band and another in the green region. The intensity of the UV peak remains the same while the intensity of the visible peak increases with increase in annealing temperature. The role of oxygen in ZnO thin films during the annealing process is important to the change in optical properties. The mechanism of the luminescence suggests that UV luminescence of ZnO thin films is related to the transition from conduction band edge to valence band, and green luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies. The NLO response of these samples is studied using nanosecond laser pulses at off-resonance wavelengths. The nonlinear absorption coefficient increases from 2.9 ×10−6 to 1.0 ×10−4 m/W when the annealing temperature is increased from 300 to 1050 °C, mainly due to the enhancement of interfacial state and exciton oscillator strength. The third order optical susceptibility x(3) increases with increase in annealing temperature (T) within the range of our investigations. In the weak confinement regime, T2.4 dependence of x(3) is obtained for ZnO thin films. The role of annealing temperature on the optical limiting response is also studied.

Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Growth of zinc oxide thin films for optoelectronic application by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on quartz, silicon, and polymer substrates by pulsed laser deposition (PLD) technique at different oxygen partial pressures (0.007 mbar to 0.003 mbar). Polycrystalline ZnO films were obtained at room temperature when the oxygen pressure was between 0.003 mbar and .007 mbar, above and below this pressure the films were amorphous as indicated by the X-ray diffraction (XRD). ZnO films were deposited on Al2O3 (0001) at different substrate temperatures varying from 400oC to 600oC and full width half maximum (FWHM) of XRD peak is observed to decrease as substrate temperature increases. The optical band gaps of these films were nearly 3.3 eV. A cylindrical Langmuir probe is used for the investigation of plasma plume arising from the ZnO target. The spatial and temporal variations in electron density and electron temperature are studied. Optical emission spectroscopy is used to identify the different ionic species in the plume. Strong emission lines of neutral Zn, Zn+ and neutral oxygen are observed. No electronically excited O+ cations are identified, which is in agreement with previous studies of ZnO plasma plume.