DEPOSITION OF NANOSTRUCTURED ZnO FILMS BY SPRAY PYROLYSIS: REVIEW

PAPER PRESENTED BY

P. CHIRANJEEVI IV/IV MECH

Chiru.pokala@gmail.com

K. V. DURGA BABU III/IV MECH

kvenki.37@gmail.com

SWARNANDHRA COLLEGE OF ENGINEERING & TECHNOLOGY

SEETHARAMPURAM, NARSAPUR, W.G.DT

ABSTRACT

A study has been undertaken to establish the influence of the principle process variables governing the spray pyrolysis deposition of ZnO thin films on their physical properties. It shows the temp at which optimum ZnO thin films can be deposited by spray pyrolysis using a set of solute concentration and carrier gas flow-rate, invariant with the deposition conditions. The study also shows the optimization of the setup facilitates in procuring different deposition conditions which are specific with the desired film characteristics. A methodology is presented in calculating the substrate temperature, solute concentration and the carrier gas flow-rate that should obtain films with the best desirable quality possible for the given spraying system and a given type of ionized solution. Because of the similarities of most gas driven spray pyrolysis systems commonly used, the methodology presented here could be applied to characterize other spray pyrolysis processes.

INTRODUCTION

Zinc oxide (ZnO), a versatile wide band gap semiconductor material, has given much attention to the scientific community as a future candidate for device applications. ZnO is an II-VI compound n-type semiconductor with hexagonal wurtzite structure and has a direct band gap of about 3.3 eV, similar to GaN and ZnSe. ZnO has some advantages over other oxide materials such as In2O3, Cd2SnO4 or SnO2 due to its unique combination of attractive properties like nontoxicity, good electrical, optical and piezoelectric behavior and its low cost. Till today, many different techniques such as chemical vapor deposition, plasma-enhanced chemical vapor deposition, sol-gel, reactive evaporation, rf magnetron sputtering, spray pyrolysis, molecular beam epitaxy, pulsed laser deposition, metal organic chemical vapor deposition, etc. have been used for the deposition of ZnO thin films. Generally each method has its advantages and limitations. Among the various methods spray pyrolysis deposition (SPD) technique provides a simple route of synthesizing thin films because of its simplicity, low cost experimental setup from an economical point of view. In addition, this technique could be used for the production of large-area thin film deposition without any high vacuum system.

As transparent conducting oxide, ZnO thin films find wide applications in optics: coatings, sensors, integrated components for telecommunication, solar cells, etc. For all these applications, it is necessary to perform an accurate characterization of optical properties, which include refractive index and optical losses. Surface roughness, inhomogenity and intrinsic defects, etc. are the causes of the optical losses. From practical point of view, these properties can severely degrade or modify the performances of a component. Overall, the structural and optical properties of the thin films depend on the method of the preparation. Lot of works has been done on these materials but still new approach is coming up to find simple route and to synthesize quality films for better performance. In considering the importance of these materials in the field of optoelectronic devices, particularly solar cells, we have synthesized high purity ZnO films of different thicknesses using a homemade SPD system at relatively low temperature (200 C), so as to reduce the preparation cost and make it economically more viable. In this review, we report the observations of film characteristics that vary with the deposition conditions and the results of optical characterization of as-deposited ZnO thin films. The goal is to develop a methodology that would allow choosing a priori the deposition conditions and, conversely, to predict the film characteristics given a set of pre-established deposition conditions.

EXPERIMENTAL DEPOSITION SYSTEM

In the present work, the deposition of ZnO thin film was carried out by a locally made SPD chamber. The figure shows the schematic diagram of the spray pyrolysis set up. The deposition set up includes the precursor solution, carrier gas assembly connected to a spray nozzle, a furnace of heating surface, air compressor and thermocouple included temperature controller. The solution and other semiconductors if necessary vary with the characteristics that are desirable for the film.

The spraying system and furnace are kept inside an airtight metallic chamber of size that is capable of containing the substrate about 303030cm and the outlet of the box is fitted with an exhaust fan to remove the toxic gases produced during the decomposition of the spray solution. The inner surface of the box is painted by epoxy liquid to reduce the heat loss of the surface. To maintain the constant temperature of the substrate, a homemade furnace is used. This gives the temperature required for the decomposition. In order to measure the temperature during sample preparation, the chromel-alumel thermocouple is used. The nozzle is made of borocil glass, and consists of a solution tube surrounded by a glass bulb. Due to the air pressure of the carrier gas, a vacuum is created at the tip of the

nozzle to suck the solution from the tube after which the spray starts. The diameter of the solution tip of the nozzle is nearly mm. in many of the spary pyrolysis processes, the substrate is kept stationary, while the nozzle is free for to and fro motion. This can be achieved by using an electrical stepper motor. In order to optimize the setup for different deposition conditions, the substrate to nozzle distance is kept at a distance of 25-30cm. In most of the spraying systems it is not made clear if it is implied that relationship between one property and a certain deposition system will stay invariant when changing even one of the remaining deposition variables. This is because; in those systems it is impossible to evidence the particular influence of each one of the variables on the properties of the resulting films. In order to facilitate for all these purposes an advanced spraying system, Model 164JAU with 1A nozzle is employed.

The head contains an internal piston which can interrupt the flow of the solution without affecting the carrier gas flow. This feature allows a precise control of the substrate temperature since the gas can be kept flowing while heating the substrate to reach the required temperature, prior to commencing spraying. In this way, only the flow of the solution has to be initiated in order to start the spraying process. In the line of air that actuates this piston, there is an electronic on-off flow

valve controlled by the timer that determines the spraying time. The carrier gas line contains a pressure regulator and a flow control valve and meter. The solution reservoir is fitted in a Mariotte configuration that keeps the hydrostatic pressure independent of the amount of solution left in the reservoir, thus allowing setting a constant solution flow with the use of the flow meter and accompanying valve.

CHARACTERISATION
The surface properties of the films were examined by using HITACHI S-3400N Scanning Electron Microscope (SEM) attached with an EDX to measure quantitatively the sample stoichiometry. The optical transmission spectra for asdeposited thin films of different thicknesses were obtained in the visible region (300-1000 nm) using UV-VIS spectrophotometer (Model: 1201V, Shimazdu). The experimental accuracy of the transmittance is ( 0.005 %) and wavelength is ( 0.005 %). The observed transmittance data were recorded using an identical uncoated glass substrate as reference. The thicknesses of the films were measured using Fizeau fringe interferometric method.

RESULTS AND DISCUSSION

Surface morphology Scanning electron microscopy is a convenient technique to study the microstructure of thin films. Figures show the surface morphology of asdeposited ZnO thin film of thickness. The films were found uniform and well

covered on the glass substrate surface. SEM photograph reveals that sprayed particles (atoms) are adsorbed onto the glass substrate into clusters as the primary stage of nucleation and appears as spheroid shape. Under higher magnifications, clusters appear as nano fiber around the nucleation center. In this review we observed that after annealing, the fibers become clear and narrower. The average diameter of the fibers is found around 500 nm for the film thickness around 650 nm. This is the first time we observed nano fiber structure on undoped ZnO thin films deposited by spray pyrolysis method. Figure ,d shows the cross sectional view of the film annealed at 300 C. We believe that more studies are needed to understand the formation of nano fibers in the deposition process.

Optical band gap Figure, d shows the optical transmittance and absorption spectra of as-deposited ZnO films of different thicknesses. These spectra reveal that films grown under the same parametric conditions have low absorbance in the visible /near infrared region from ~ 450 nm to 1000 nm. However, absorbance is high in the ultraviolet region. Figure shows that absorption increases with the thickness of the film. Plots of A2 versus the photon energy (h) are shown in figure 5 in order to achieve the band gap for ZnO films. The band gap of the films varied between 3.31 eV to 3.40 eV and the band gap also decreases with the increase of the film thickness from 220 nm to 650 nm. The decrease of band gap with the increase of film thickness implies that ZnO is an n-type semiconductor. This decrease of band gap may be attributed to the presence of unstructured defects, which increase the density of localized states in the band gap and consequently decrease the energy gap. The type of the semiconducting nature of the thin films was determined using

the hot probe technique. The arrangement consists of a hot probe with which the film is touched and the direction of current implies whether the film is p-type or ntype as verified using a standard known sample. All the deposited films were tested by this technique and n-type conductivity is invariably observed for all the films. Our obtained band gap values are in good agreement with the band gap of ZnO films deposited by other techniques. The transmittance of the film from the incident wavelengths is shown in the graph.

The figure of merit of the obtained film is plotted against different deposition temperatures and seen for the optimum temperature at which the merit figure, F is minimum.

F = -Rs Ln Tp Where, Rs is sheet resistance TP is optical transmission

Thickness of the film is a function of deposition time. So that it is clear that as we proceed with the deposition time, the film obtained will be thick. This can be graphically denoted as shown.

This table provides comparative results for four groups and the corresponding errors made by the model in predicting the temperature of minimum. It is observed that the errors are only slightly larger than the experimental uncertainty in the measurement of substrate temperature.

CONCLUSIONS
In this review, ZnO nano fiber thin films of different thicknesses have been prepared by an economical and simple spray pyrolysis technique onto glass substrate at heated temperatures from a precursor zinc solution. EDX result reveals that the deposited films are stoichiometric. SEM micrograph shows that films are uniform and nano fiber structures appear around the nucleation center. The films show direct band gap in the range 3.3 3.4 eV. The films exhibit low absorbance in the visible / near infrared region from ~ 450 nm to 1000 nm. Variations in the optical constants with wavelength are found to be thickness dependent of the films. The optical properties viz. refractive index, optical band gap and low dielectric constant of the as-deposited and annealed films show the suitability of the deposited films for using them in optoelectronic devices and solar cells. The study of structural and annealing effect on the films are in progress and to be reported elsewhere soon. In conclusion, we can state that the SPD could be employed for large-scale synthesis because of its high yield and purity, simple reaction mechanism, simple apparatus and relatively low deposition temperature.

REFERENCES
Cryst. Res. Technol. 44, No. 3, 386-292(2009) C. Mazon, J. Muci, A. sa-Neto, A Ortiz-Conde and F. J. Garcia Dpto.de Electronica, Universidad Simon Bolivar, Caracaas 1080, Venezuela Jl.of Instrum. Soc.of India www.wikipedia.com Vol. 39 No. 1