Prog. Crystal Growth Charact.1981,Vol. 4, pp. 221 - 248.

OPergamon Press Ltd. Printed in Great Britain

0146- 3535/B1/0701

-0221$05.00/0

SPRAY

PYROLYSIS

IN SOLAR CELLS AND

M. S. Tomar and F. J. Garcia

GAS SENSORS

Dpto. de Fisica, Universidad Simon Bdivar, Apartado 80858 Caracas, 1 .OBOA Venezuela &&rJ&ed 17th Februwy 1981)

ABSTRACT The present article offers a review of the technique of spray pyrolysis deposition of thin films. General aspects of the method, such as its inherent simplicity and low energy consumption, are briefly considered. The basic process and apparatus utilized in spray pyrolysis are described in general and also for particular applications. Specific techniques used to deposit thin films of metal oxides, oxide semiconductors, sulfide and selenide semiconductors and related compounds, and the properties of the resulting deposited films are discussed. The most cornnon applications of these sprayed films are presented, with special reference to recent results in gas detection and photovoltaic solar energy conversion, including thin film solar cells, solar cell antireflection coatings, and thin film gas sensors. A general review of the published work in these areas is also included, together with a number of pertinent references. 1, INTRODUCTION

Bigh quality single crystals of semiconductor materials are generally prepared by several established crystal growth techniques (1, 2). &I a parallel line thin films of these materials are usually produced by vacuum evaporation, sputtering, electron beam evaporation and CVD etc. (3) to mention a few. All these techniques have their advantages and disadvantages, depending on a particular application. In the present review we want to focus attention on a simple though useful technique termed "SPRAY PYROLYSIS" which has been used to produce several compound semiconductors whose utility in various devices e.g. solar cells, gas sensors, antireflection coatings etc., have been realized. Chamberlin et al (4, 5) used the spray pyrolysis (SP) to produce several II-VI compounds in search of low cost photoconductors. With this technique these authors also prepared for the first time a heterojunction solar cell of Cu sleds (6). A reactive spray technique has long been used to prepare transpafent conducting oxide layers (7-14), but a serious attention (15-20) to produce high quality oxide films such as Sn02,CdSn04, In203, Ti02, etc., has been given around mid seventies onwards due to their applications in conductive transparent electrodes,particularly in solar cells and gas sensing elements. It perhaps is the demand of time to search for low cost techniques and their utility in this 221

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M. S. Tomar and F. J. Garcia

period of energy crisis. It is therefore assumed that the discussion in this article is concerned with the materials and their devices produced by spray pyrolysis technique if not otherwise mentioned.

2, SPRAYPYROLYSIS TECHNIQUE (SP>

In principle, spray pyrolysis is a simple technique where an ionic solution (prepared by starting materials in appropriate stoichiometric proportions) containing the constituent elements of the compound, is sprayed over a heated substrate (T around 300C to 5OO'C). Generally the metals are in solution as their chl%%ies , nitrates or acetates. Sulphur and selenium are present in the forms of N,N dimethylthiourea or thiourea and N,N dimethyl selenourea. Several sulphides and selenides: binary, ternary and even complex sphalerite solid solutions (4, 21-24) have been prepared using this technique. The ionic solution produces complex ions (4) presumbly (Metal chloride + Ureas) i.e. CdC12(SCN H4) or CdC12(SeCN2H4) in the case of CdS or CdSe products (4, 25), these sulphi e -3 and selenide ions do not precipitate in the solution. When the solution is sprayed over a heated substrate, the complex ions then decompose and the inorganic sulphide/selenide deposits on the substrate in the form of very adherent films. The organic products of the chemical reaction do not hold the temperature encountered on the substrate and subsequently evaporate along with other gaseous species. Nitrogen is used as carrier (flushing) gas but compressed dry air was used frequently for oxides. Sometimes a rotating substrate was also used to acquire uniform films. The typical schematic diagrams of SP setup are shown in Fig. 1 which are generally used (4,27,28). The approximate chemical reactions during the deposition process are given in Fig. 2A. Table 1 shows some of the important starting materials used in various spray deposited films. The quality of the deposited film seems to depend strongly on substrate temperature, spray rate, degree of atomization, anion to cation ratio and the substrate environment (4). A reactive spray technique as mentioned above to produce oxide films utilizes similar chemical solutions but allows the spray constituents to react with the ambient (say oxygen) (15-18) or helps in hydrolysis and sometimes a preheater is used (15) which helps in fast oxidation process. The problems encountered presently in sprayed films are due to non-uniform droplet sixes formed at the outlet of the spray nozzle which contribute to the poor grain size and hence lower transparency. This effect has been treated by Lampkin (29) through an investigation of the aerodynamics of the spray nozzle and by Som and Mukharjee (30) with a study on the coefficient of discharge and spray cone angle of the swirl spray atomizing nozzle.

3, PREPARATION PROPERTIES AND (SUPHIDES, SELENIDES, ETC,>

As mentioned above, several sulphide, selenides and oxides were prepared by SP. In this section we will give an account of the preparation and characterization of these films. 3.1. II-VI. Inorganic Compounds

An extensively studied material among all the II-VI compounds is CdS due to its utility in heterojunction solar cells as a large bandgap window material. 3.1.1. Cadmium Sulphide (CdS). The starting materials generally used to prepare CdS were an equimolar ionic solution of CdCl, N,N dimethyl thiourea (or thiourea) (4). This solution was sprayed over a fieated substrate around 300C to 5oo"c. The spray rate was generally maintained in the range of 2mlfmin to

Spray Pyrolysis in Solar Cells and Gas Sensors

223

I:.

FlhCES

B.

COMPRESSEDAIR

TC Cr/AI

0 0 OUTLETCARBON HEATER c

TZ

FPg. 1.

Spray Pyrolysis Techniques A- Rorizontal Configuration B - Vertical Configuration

224

M. S. Tomar and F. .I.Garcia

START TNG MATER lALS Starting Materials FOR

TABLE-I
FOR

SPRAY

PYROLYSIS Spray Rate

Substrate Temperature

Cd

Cadmium Cadmium Cadmium Cadmium

Chloride Nitrate Acetate Formate

CdS-350"to 45O'C with N2 or air as carrier gas

In the range of 2 mllmin. to 30 mllmin. for sulphides and selenides

Zn

Zinc Chloride Zinc Nitrate Zinc Acetate Cuprous Chloride Copper Acetate Indium Chloride

ZnCdS 400-45O'C with N or air as car?ier gas Ternaries like CuInSe2,CuInS2 300 to 400C in excess of selenourea and N2 as carrier gas,/ excess of Thiourea In the range of 20 mllmin. to 150 mlimin. for oxides Oxides like SnO ,In 0 :Sn 4502600zC3

cu

In

Pb

Lead Chloride Lead Acetate Lead Nitrate + Alcohol Gallium Chloride Gallium Nitrate + Alcohol Tin Chloride (SnC14.5H20) Tetramethylin Thiourea N,N dimethylThiourea Ammonium Thiocyanate N,N dimethylselenourea Titanium Isoproxide Tetraisopropyl titaanate + H20

Ga

Sn

:zfao&
TiO - 46ooc

Se

SnO2 - 400-5oo"c

Ti

Spray Pyrolysis in Solar Cells and Gas Sensors

225

170C 6SCN2 II4+ 18NH4SCN 24SCN2H4 = 180C 6CH5N3HSCN+ 3 ( N2H8CS3) + 9 (NH4SCN) 6SCN2 I-I4 18NH4 SCN 2 + 180-270C 2 C6HgNllHSCN+ 2 (NH31 + 5 (NH4ScY)

6CH5N3HSCN

I3<CdC12SCN2H4' I
24O'C I [<CdS> + 2 <CdC1+iCN2H4> ICH2N2.2HC1j] + I 4 I <CdS> + < Cd2C16CN2H4 '+ 1 (N2F8 CS3) +; 3 290c I 2 <CdC127 + I 1 I<CHN - <NH4 Cl> + 5 (HCl) + + <C6HgNll= + 12 6 9 11' 2 I [
+,li(HSCN)

( NH4SCN) + ; (NH3 )~2<C6HgNl~HSCN>]

<Cd?,> + I

350c
I

<CdS> + 2 <CdC12> +

1 + (.NH4C1)

1 I Il <C6H6N10' +a 5 I <C6H3N9'+ I ( NH3>

+ ( NH3)

<>-solid.

Cl-

liquid, ( ) - gas.

Fig. 2-A. Scheme of the proposed decompositionof the complex CdC12(SCN2H4), (from Ref. 25).

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M. S. Tomar and F. J. Garcia

3Oml/min depending on the nature of the study one is interested in (31-33). The formation of CdS over the heated substrate was assumed (4) to occur by the decomposition of the intermediate complex ion (formed in the solution) CdCl (SCN H4). In most of the work reported, this assumption was taken fcr granted (4:31,333. In recent reports (25,26) however the authors demonstrated that an intermediate reaction path was involved to form the final product. The composition of the final m;.terial depended on the temperature of preparation. The decomposition paths proposed are shown in Fig. 2A and the thermogram of the film (during preparation) is shown in Fig. 2.B. The proportion of cholorine to cadmium in the film as a function of the temperature is shown in Fig. 3 (25,26,34). It can be seen from these results that the chlorine content decreases as fast as the preparation temperature of the substrate increases. 3.1.1.A Electron Transport. The spray deposited films generally have high carrier concentration and high resistivities. Micheletti and Mark (31) showed that the absorption of oxygen on CdS films reduced both the Hall mobility (u) and electron density (n), the former by a larger factor than the latter. The films were photosensitive. An activation energy of 0.03eV for electron density was not affected by chemisorption, whereas the values of activation energy for Hall mobility increased by chemisorption essentially from a zero value to values between 0.08 and 0.21 eV, due to the additional scattering introduced by chemisorption (31,34). Bube and co-workers in their extensive studies (32,33) on these films observed that the dark electron mobility was thermally activated. The photoconductivity was caused primarily by an increase in electron mobility. During photoexitation the holes are trapped at grain boundaries and the electrons thus contribute to n-type photoconductivity. When the average grain size in the film is less than the mean free path in the grain, the scattering seems to dominate. The grain size of these films are small (" l-Z-urn)as observed by several workers (28,35, 36). The holes trapped at the grain boundaries decrease the barrier height and barrier width. The decrease in the barrier height was indicated by a decrease of mobility activation energy with photoexitation (31,33) and the decrease in barrier width increases the tunneling probability of electrons through the barrier. Therefore the tunneling process seems to dominate the electrical trans-

I.C

0.6 400
Fig. Z-B,

To(C)

Thermogram of complex CdCl2(SCN2H4), (from Ref. 25,26).

Spray Pyrolysis in Solar Cells and Gas Sensors

227

Fig. 3.

WC) 400 300 Quantity of Chlorine in the film versus temperatureof preparationa) at the end of spray, b) post-treatment: successiveannealing for one hour for a film prepared at 260C, c) after annealing at 500C for one hour. (from Ref. 34,261.

228

M. S. Tomar and F. J. Garcia

port at high photoexcitation and at low photoexcitation both tunneling and thermal excitations are parallel processes as observed by Wu and Bube (33). The independence of dark electron density on temperature indicates that the donor level (assumed to be due to the un-compensated chlorine donors) was shallow (- 0.03eV) in these films (31,33). However, it was observed that there seems to exist insulating grain boundaries which played an important role in the measured variations of the mobilities (37). These insulating grain boundaries were formed due to chemisorption of oxygen at the grain boundaries. Under photoexcitation this chemisorbed oxygen at the grain boundaries and on the film surface acts as additional recombination centers and reduces photoexcited electron lifetime. The insulating grain boundaries produced by oxygen absorption thus decreases the tunneling probability for electron transport through the intergrain barriers. Therefore, when the film was exposed to air (absorption of oxygen) after deposition, both the electron mobility and density were observed to be reduced (31,35,38) with the mobility decrease being larger (both under dark and light). As a result the observed increase in resistivity was justified (33). Fig. (4) shows the measured average crystal grain size versus film deposition time (37). Both dark and light electron mobilities vary with the thickness and it was estimated to be due to the grain size variations. Kwok (37) predicted that the conventional thermoelectric power equation (38) can only be applicable as long as intergranular separations in the film are small. 3.1.lB Temperature Effects. In the films deposited at a substrate temperature lower than 350C (T < 350C) the cubic phase dominates but if the preparation temperature was 350gtb< T < 500C a preferred orientation from cubic to hexagonal was.observed (28,3!Yb The cubic phase was due to the highly faulted hexagonal grains. These films also showed higher optical transmission and low resistivity when prepared at higher substrate temperature ( 28,36). The surface morphologies consisted of nodular and serpentine structures on the surface (35) and the grain size was about l-2pm.

1 8

lo TIME (min.)

.lo

flLU

UWOSITION

Fig. 4.

Film grain size versus deposition time, (from Ref. 37).

Spray Pyrolysis in Solar Cells and Gas Sensors

229

Some of these observations may be related to the formation of intermediate compounds pig. 2) due to the change in the temperature of the substrate as observed by Dutault and Lahaye (26), where the composition of the final product depends on the temperature of the preparation (Fig. 2). A similar type of reaction process seem% to take place in a chemical bath deposition method for the preparation of CdS (39). At a lower substrate temperature (< 350C) the films contain some chlorine dominated product which produces the highly resistive films with poor optical transmission and at a higher substrate temperature (' 408C to 5OO'C) the chlorine dominated material was minimum (Fig. 3), therefore the deposited product was CdS. Thus the observed high optical transmission and lower resistivity (33,36) for the films deposited at the substrate temperature around 400C is obviously justified. At a slow cooling rate of the films (prepared at Tsub - 45O'C) both the electron density and mobility (chemisorption effect) were decreased. If they were annealed again (34) the characteristics were not the same as observed before this treatment (6). The heat treatment at about 300C in H atmosphere reduced the resistivity of the film by three orders of magnitude, w & ile at the higher temperatures the film becomes degenerate (36). heat treatment in hydrogen reduces the excess chlorine donors, increases the free electron density in the grains, reduces intergrain barrier height and remwes any vestige of chemisorbed oxygen, thus the low resistivity CdS films suitable for solar cells can be obtained. The studies of cation to anion ratio indicate (28) that excess thiourea was required to compensate the sulphur escape in the form of H2S gas. The Cd to S ratio of 1:3 was estimated to get high optical transmission for the films deposited at 480C with a spray rate of 3Omlfmin. The fast spray rate introduced defects, such as stacking faults+ dislocations, vacancies and reduced the grain size in the film. By carefully controlling the experimental conditions, such as lower spray rate, substrate temperature (-_t50C) ayd heat tfeatment in H etc., room temperature conductivities between 10 and optica 1 transand 10 (Q cm) mission around 40% to 70% (in optical region) were obtained (;8,36). A partial substitution of Zn for Cd in CdS increases the optical window of the heterojunction and also the diffusion potential (41,42) and seems to improve the lattice mismatch with Cu2S. Several investigators (43-47) used an equimolar water/acidic solution of one part ZnC12, CdCl and two parts N,N dimethylthiourea and sprayed it over a heated substrate (' 250'C) to obtain an adherent film of Zn Cd S. Molar concentrations in the range of 0.02M to 0.2M and different sub&&g temperatures have been tried. The process of film formation is similar as in the case of CdS. As deposited films showed an increase in both the band gap (43) and resistivity (43,44,47) with the Zn concentration (i.e. x-value). The ZnfCd ratio in the film was found same as that in the starting ionic solution (46) but a decrease in mobility was observed (47). The films with x > 0.3 were found to be highly resistive (45,46) and the optical transmission was higher for the films with 0.1 < x < 0.3; Kwok and Chau (46) in their extensive studies of the Zn Cd S films prepared around 3OO'C observed that the mobility value of the film ae&ses to a very low value when the Zn and Cd concentration are equal. Bube and co-workers (47) however observed a sharp increase in resistivity ( specially for 0.1 < x < 0.2) which was attributed to the measured sharp decrease in mobility exactly in the same region and the composition independence of mobility (43) did not hold (46). In case of single crystal work (48) this was attributed to an increase in donor activation energy from 0.03eV in CdS to 0.3eV in the sample with higher Zn c.oncentration. The electron density increased with Zn to about 40% and a further increase of Zn made the film degenerate (46,47). Other workers (44,45) did not observe sharp increase in resistivity with x and degenerate films of ZnxCdl_x S were obtained with a very high Zn concentration 3.1.2. ZnxCdl_xS Films.

230

M. S. Tomar and F. J. Garcia

(x = 0.8). X-ray diffractionand electron microscopic studies (45) showed that the cryatallinityquality was best for a Zn concentrationabout 10%. The films were dominated by hexagonal (00.2) phase with a film growth perpendicularto the film surface but stacksng faults were frequentlyobserved in the films. The results compared with evaporated films (43,42) show nearly same increase of resistivity with Zn, as expected. Heat treatment in H atmosphere decreased appreciably the resistivityof these Zn Cd S films. 'R esistivityvalues of 6.9 Q cm and 400 $7cm were obtained after a aea&'?reatmentin R2,increase& the electron density but did not appreciably insrease the electron mobility (47). A heat treatment in high vacuum (_ lo- Torr at 300C) also decreased considerablythe resistivityfor the films containing low Zn concentrationand a reduction of chlorine donors to obtain low resistivityfilm of Zn Cd S was believed (44). The variations inxthi?esistivity for different Zn concentrations observed by several authors (43-47),appeared to be depending on the preparation conditions such as spray rate, substrate temperature,thickness of the film, substrate's environment etc. Considering the single parameter of substrate temperature one can observe that the films prepared at temperaturesbelow 350C contain high concentrationsof chlorine which acts as donor to CdS or ZnCdS providing a

Fig.5.

Resistivity (o,) versus ZnS concentration,PRT is after heat treatment in H2, for ZnxCdi_xS Film (from Ref. 47).

Spray Pyrolysis in Solar Cells and Gas Sensors

231

very high carrier concentrationand poor optical transmission (due to poor grain size). The heat treatment in air increases the resistivitydue to the oxygen absorption at the film surface and at the grain boundaries near the surface. A heat treatment in H2 was found very effective not only to decrease the resistivity but also to improve the grain size of the film hence increasing the Optical on transmission. Fig. 5 shows the effect of heat treatment in l-l2 the resistivity. 3.1.3. CdSxSel x and PbS Films. These solid solutionswere also prepared and investigatedusing thequimolar CdC12, N,N dimethyl selenoureaand N,N dimethylthiourea in appropriateproportions. The complete solid solution of CdS Sel_x was formed over the entire compositionrange (43) which followed Vegard's faw (50). The band gap increasedmore or less linearly with x. The observed values of band gaps of 1.7eV and 2.4eV for these films (43) with x.= 0 and x 3:1 respectively, represent the correspondingband gaps of CdSe and CdS, as expected. Films were founa deficient of selenium, the resistivitiesdid not vary appreciably with increasingx and a small variation in resistivitywas attributed to experimentalparameters. The electron densities in the range of selenium concentrations, probably were due to the incorporatedchlorine donors (43) and also due to the environmentcontaminationduring deposition. CdSe films were recently used as a photoanode in photochemicalsolar cells (49) with promising results. An attempt was also made to make PbS films with O.lM lead acetate and thiourea solution. Although lead sulphide films were found highly resistive, the results on PbS/CdS cells are optimistic (51). 3.2. Complex Compounds On the basis of the successfulattempts to prepare II-VI compounds by SP, Pamplin and Feigelson initiated a series of experiments to prepare a whole range of solid solutions of I-III-VI2 compounds (21-23). They used freshly prepared saturated ionic solutions containing Curpous, Gallium, Indium, Cadmium and Zinc Chlorides, N,N dimethyl thiourea and N,N dimethyl selenourea in the appropriate stoichiometricproportionsand sprayed over the heated substrate (- 350" to 500C) to deposit the desired material. In a particular caee of CuInSe these authors used (21) an ionic solution with CuCl:O.O2M, InCl :0.0&l and N,i'dimethyl selenourea in the ratio 4~1~112. Various experimentsw&e carried out at preparation temperaturesbetween 2OO'C to 600' in 5O'C intervals. They observed that the films prepared at a substrate temperatureabwe 45O'C and below 200C were poor. Sharp absorption edges were observed (21) at a value of about 0.95eV for the specimen prepared at a substrate temperaturearound 350'C,showingthe expected band gap of CuInSe2 (52). Heat treatment in air caused a increase in resistivityby two orders of magnitude, showing the effect of oxygen absorption similar as observed in CdS films (31). AgInS and AgIn S films were also prepared (23,24). Both were prepared wit p-and n-type conductivities. The repreeen28 he quinary adamanttne system CuGaS2-CuInS2-CuInSe2-CuGaSe2 and other stannfte &Lid solutionswere prepared (21,22). These materials were p21,22 show the retype with resi8tivPtieein the range of O.LZOfkm. Pefs. sults on these complex compounds prepared by spray pyrolysis. The large range of sphaleritecompounde Based on PITT-VT compound8 predicted earlier (53) has been must be tairealized by SP. The properties like band gap and latticeparameters lored by further extensive research programs and are yet to be seen.

4, APPLICATIONS
To date, the semieonducthg films prepared by spray pyrolysis technique have specially in heterojunctionsolar cells, photobeen uoed in various dwieo,

232

M. S. Tomar and F. 3. Garcia

chemical cell electrodes, gas sensing elements, antireflection coatings, thermal coatings etc. This section deals with the performance of the devices; particularly the photovoltaic solar cells. 4.1. Photovoltaic Devices.

Photovoltaic device is a semiconductor device which converts the sunlight directly into electricity. The operation of this device is based on the photovoltaic effect. In principle, it is a p-n junction (homojunction or heterojunction) whose theory and governing factors based on particular semiconductor have been treated (54) by numerous authors. Absorbed photons produce minority carriers at the junction which can be collected. This device acts as a constant current source in first approximation. The theoretical calculations have shown that the absorber semiconductors with band gaps in the range of 0.9-1.7eV are suitable (55,56) considering the ideal conditions. Most suitable semiconductors are those who have band gaps around 1.5eV with direct transition. Commercially available silicon p-n junction cells are leaders today but thin film solar cells with electrical conversion efficiency more than 10% is a question of time, since 9.15% efficiency of Cu2S/CdS solar cell has been reported (77) using vacuum evaporated CdS films, and is a hope for the future low cost and large area cells. Heterojunction theory applied to CdS/Cu2S cell has been treated by several authors (57,58) recently. These cells are generally made (57) by forming an absorbing layer of Cu S over the CdS by an ionexchange reaction between CuCl and CdS, where the Ed was replaced by two Cu ions and S was practically intact. The reaction product CdCl dissolvesin solution and a Cu2S layer was deposited over CdS, which makes a p-Cu g/n-CdS heterojunction. After a proper heat treatment and other precautions (57f this heterojunction has shown very strong photovoltaic effect and the large area cells with efficiencies 6% to 9% have been made (77) with vacuum evaporated CdS films. The CdS and Zn Cdl_xS films prepared by spray pyrolysis have also been used to make a CdS/Cu2S geterojunction in a similar way (6,39,59,62). A scheme for large scale production using spray technique was initiated by Jordan (60,61). Singh (59) reported a solar cell of CdS/Cu S produced by spray pyrolysis with conversion efficiency of 5.9%. Siu and Kwok ?39), and other authors (27) also used sprayed film but a low conversion efficiency - 1% was obtained. The heterojunction showed good rectifying curve and an open circuit voltage (V > about 0.3V was observed. The films were resistive. Recently, Banerjee et al (@) used sprayed S films to produce the solar cells and an efficiency of 5.6% with small ~~$~%~?ls was claimed. The higher Zn concentration (x > 3) reduced the open circuit voltage (V ), fillfactor (ff) and short circuit current (JsC). For a Zn and ff were concentration 0PCx - 0.1, the VOC was at peak value while the J somewhat reduced as compared to pure CdS/Cu2S cell (62). The r&ction in JsC was also observed for such cells prepared by vacuum evaporaeither using an ion exchange method (41,32) or by solid state 27) with efficiencies of 5-6X. S/Cu S heterojunction showed that the dominant transThe analysis of Zn Cd port mechanism was interfa&Gxrecoibination and the observed increase in open circuit voltage by increasing Zn concentration (x < 0.2) was due to the reduction in the reverse saturation current caused primarily by an increase in the barrier height at the interface (63). In a recent investigation of composition analysis S film S heterojunction (where Zn Cd of the junction region of the Cu2S/ZnxC was prepared by vacuum co-evaporation o i-2nS and CdS) demonstrated t&t'tffe participation of zinc in the ion-exchange reaction was incomplete (64). Zinc was reS just under the intertained in the junction region and was found mainly Zn Cd face which could account for some of the basic differ&c&Ybetween CdS and S based solar cells. They observed that the actual Zn Cdl_xS composition interface differs from that of the starting film. E$en for moderately 4.1.1. CdS/Cu2S Reterojunction Cells.

Spray Pyrolysis in Solar Cells and Gas Sensors

233

low zinc content films, this phenomenon could result in a potential spike at the interface or a reduced value of mobility, with a subsequent reduction in photogenerated current and the cell model needs to be modified accordingly. This also indicates that a technique other than ion exchange might be necessary for Cu2S S film (probably sputtering (65) or solid state reaction (78) formation on Zn Cd bifazial-f! etc.) or nCdS-CdS layers be formed to convert all CdS into Cu2S in ion exchange (79). The composition of Cu2S layer obtained over spray deposited CdS or ZnxCd1_x S have not been investigated, though the Zn retention seems to take place which grves rise to a spike resulting in the reduction of short circuit current (Jsc) and fillfactor (63). Bb'er in a recent theory (58) took into considsration

Culn

Se,:%

SnOgln,O, Pyrrr Glass

hV

Fig. 6.

A - Configuration of the solar cell (CuTnSe2/CdS) prepared entirely by SP, B - Dark and Light, current-voltage characteristics of CuInSe2/CdS cell.
Scale, HorizontalO.lV/Div., Vertical SmA/Div.

234

M. S. Tomar and F. J. Garcia

some aspects of the junction chemistry of Cu2S/Zn Cdl S solar cells. Photovoltaic properties of CdS/CdTe and Zn C$ SrCdTe (where CdS and Zn Cd S were prepared by SP, and CdTe was a szngiGxcrystal) were investigated (6%,6#f.The open circuit voltages as high as 0.74V and 0.84V have been reported for n-CdSfp-CdTe and n-Zn Cd S/p-CdTe cells, respectively. The other parameters of the cells are gi& &?Eef. 66,67. Similar cells have also been recently prepared using a simple screen printing technique (68-70) which show a promise in low cost devices. PbS/CdS (Zn Cd S) heterojunctions prepared entirely by SP were reported to give VOC - 0.49Vxan!l-5.38V respectively (51). The high resistivity of PbS film was the cause of the resulting low values of V and ff. The spray deposited films of CdSe have been used as photoanodes in'$hotoelectrochemical solar cell (Indium Tin Oxide/CdSe/Na2S-S-NaOH/Pt) whiSh showed an energy conversion effiency of 7.8% at 640nm and 5.2% under 5OmW/cm white light illumination (49). The CdS photoanode showed a very weak energy conversion due to its high band gap and was not considered suitable as a photoanode in electrochemical cells. These results on CdSe photoanodes are inspiring if its stability could be maintained. Severalternary compounds both in single crystal and vacuum evaporated thin film forms have demonstrated high efficiency photovoltaic cells (73,74), thus showing the potentiality of I-IFHI compounds in solar cells. Very weak photovoltaic effect was observed using sprayed CuInS2 films (24). We prepared a heterojunction of CuInSe2/CdS(Zn) entirely by the spray pyrolysis technique which showed good rectifying junction with weak(V 528) nhotovoltaic effect (Fig. 6B). Electrical conversion efficiency of 0.8% to'!.iidhave been obtained (75). The cell was prepared on a Pyrex glass substrate covered by sprayed Sn02:In O3 solid : Se were also deposited by SP technique TFig. 1). solution. A heat treatment in N re at 35O'C followed by appropriate etching, the structure was prepare in a configuration of Fig. (6A). An ionic solution of o.lM CuC12, InC13 and N,N dimethyl seleneourea for CuInSe and O.lM CuC12, ZnC12 and N,N dlmethylthiourea for (Zn) CdS films was use 2 . Low efficiency of this heterojunction cell was perhaps due to highly resistive CdS and CuInSe2 films of small grain size (< 0.5um). The x-ray spectra of spray deposited CuInSe2 is shown in Fig. 7 Sprayed CuInSe2/CdS (single crystal) heterojunction

Fig. 7.

X-ray spectra of spray deposited CuInSe2 films.

Spray Pyrolysis in Solar Cells and Gas Sensors

235

small area cell showed VOC = 0.3V, JSC = hnA/cm2 and ff = 0.3 in a recent publication (76).

5,

OXIDE SEMICONDUCTOR FILMS

As mentioned in section 1, the use of transparentelectricallyconductive coatings has been developingperhaps since the beginning of this century. The fact that transparencyand high electrical conductivitycan be achieved concurrently in some materials has led to the utilieation of transparentelectrodes in a variety of applicationssuch as photodetectors,glass heating elements, electrodes in electroluminescent devices and liquid crystal displays, and more recently in photovoltaicsolar cells. The realization that wide-gap semiconductive metal oxides can be prepared with relative ease in the form of highly conductive and transparent. thin films prompted the replacement of the previously used metal thin films by these semiconductorsin many transparentelectrode applications. Transparentmetal electrodes suffer from the inherent reduction of the mean free path from its bulk value, which occurs up to film thicknessesabove which the films cease to be sufficientlytransparent (80-82). The relative usefulness of a transparentconductive film can be quantized considering its two fundamentalrequirements: high optical transmissionand high electrical conductivity. Haacke (83) has proposed a figure of merit which permits a comparison between different transparentconductors,both metals and semiconductors. This figure of merit can be expressed as: OTC - T10/R* where R is the electrical sheet resistanceand T is the optical transmission. The fi&re of merit can also be written in terms of the electrical conductivity u, the optical absorption coefficienta and the film thickness t as follows tC - ut exp(-lout). Utilizing known values of the parameters involved in this equation the figures of merit of different materials can be calculated and, by plotting this figure of merit as a function of film thickness, the optimum thicknessesfor specific materials can be found. Comparison of the results show that wide-gap semiconductors are better materials than metals for transparentconductive coating applications (83,84). Basic considerationsindicate that materials with long mean free path should produce larger figures of merit. Long mean free paths in metals are obtained with relatively thick films and consequentlyopaque ones. This conflicting situation is not so prevalent in semiconductors where, if the band-gap is sufficientlyhigh (- 3eV), thicker films with high transmissionare possible. This is a result of the low absorption at wavelengths beyond the optical absorption edge, which for large band-gap semiconductorsencompassesmost of the visible spectrum. Tf In addition to having a large band-gap the semiconductorhas a high carrier mobility and low effective mass, figures of merit considerably higher than those obtainablewith metals can be achieved with these materials. Since the mean free paths of semiconductorsand metals can be of the same order of magnitude, semiconductorfilms ten to a hundred timtathickerthan metal films can be produced with correspondinglylower sheet resistancesand equal optical transmission (84). A more detailed discussion of this subject can be found in the references cited. Semiconductorsused as transparentelectrodes include cadmium oxide, tin oxide, indium oxide, cadmium stannate and zinc oxide. Different methods are used to deposit these semiconductorsin the form of thin films : R.F. sputtering (85-87),D.C. diode sputtering (85), reactive sputter&g in 0 (88,89),chemical vapor deposition (90,91) oxidation under vacuum (93,94), flas evaporation (95) t and spray pyrolysis (84,92,95-103,139).Gas phase hydrolysis (spray) of volatile indium tin compounds is the earliest method of depositing indium oxide and

236

M. S. Tomar and F. J. Garcia

tin oxide films. This method that was first used by McMaster (104) in 1942, produces a wide variety of results since the final composition and resulting structure of the films are very much dependent on deposition conditions such as: the spraying solution used, the temperature of the substrate, rate of spraying, etc. 5.1. Tin Oxide Films.

Sn02 is a degenerate wide gap (- 3.5eV) n-type semiconductor with a tetragonal crystal structure tis?electrical conductivity can be enhanced by appropriate doping. Tin oxide was the first and has been one of the most widely used transparent conductors due to its adequate electrical and optical properties, environmental resistance and the ease with which it can be fabricated by simple and inexpenslve methods. The deposition of the tin oxide films can be carried out by spraying a hydroalcoholic solution of tin tetrachloridetogether with a suitable dopant onto a heated substrate. The following endothermic reaction takes place at the substrate surface: SnC14 + Hz0 2 Sn02 + 4HCl To lower the resistivity of the SnO film, fluor is customarily added to the solution in the form of trifluoroace & ic acid (CF CO H) (97,105) or amonium chlgride (NH4F) (97). Antimony can also be used in zhe germ of the chloride (10 M SbC13 relative to SnC14) (99). Gas phase spray pyrolysis is achieved by utilizing a vaporizing preheater and a separate substrate heater. The temperature of the preheater ranges roughly from 2OO'C (100) to 5OO'C (15), while the substrate temperature is the range of 300C (25) to 600C (15,99-102). Manifaicier, et al (97) have found the optimum substrate temperature to be 500C. Typical spray flow rates allow fast deposition rates up to 0.2 to 0.4nm/min (92,93). Consequently films with thicknesses in the range of 0.1 to 0.3um are deposited at low temperatures in a relatively short time compared with other fabrication methods. Weight concentrations of dopant NH4F in the range of 0.75% to 2% result in the lowest values of sheet resistance at the optimum substrate temperature of 5OO"C, as reported by Manifaicier, et al (97), who employed the following solution to obtain films of maximum transparency and electrical conductivity: SnC14,5H20(32.9%) + CH3CH20H(32.9%) + H20(32.9%) + NH4F (1.3%). The deposited tin oxide films present granular polycrystallinity with a tetragonal rutile structure (97) which coincides with that observed in sputtered and CVD deposited films (86,106). The measured atomic ratios of the dopant impurity in thedenosited films are lower than those of the starting solution (97) making it necessary to compensate for this deficiency. In addition, it is possibzg that the resistiv_isy of this n-type film, which typically ranges from Ocm (100) to 2x10 Oan(99), becomes higher when borosilicate glass is 0.6x10 used for the substrate, as it can contribute contaminating p-type impurities in the form of alkali cations, 5.2. Indium Oxide and Indium-Tin Oxide Films.

In203 like Sn02 is an n-type oxide semiconductor with a wide band gap and degenerate doping. When depositing In 0 by pyrolysis the following well known reversible endothermic reaction is pro 23 uced at the surface of the substrate: -?2InCl + 3H 0 + In203 + 6HCl 2 3 Several solutions are used for spraying this semiconductor. Indium oxide is usually mixed with tin oxide in varying proportions to improve the electrical conductivity of the resulting films. Some authors refer to this mixture as indium-tin oxide (ITO), while others consider the addition of tin in small

Spray Pyrolysis in Solar Cells and Gas Sensors

237

weight percentages simply as doping and denote the material as In 0 :Sn. Manifaicier and Szepessy (lQ2) have produced films with a 0.023 Sn/Xn a omit ratio 29 glass solution sprayed, through a preheating furnace at 560C, onto borosill.cate at 498'C yielding a sheet refhstan e of 10,9Q/sq, resistivity25,$x&f Qcm, car-5 rier concentratEonof 7.4x10 cm Hall mobility of 16.1 cm v s and transmission of 80 to 90%. When the suhbtrate temperature is lowered to 435'C and the Sri/In atomic ratio increased to40.25 the resulting film shows a sh48t resistance of 420 R/sq, refisflt7ity 51x10 ncm, carrier concentrationof 4x10 , Hall mobility of 3 cm2v- s- and transmissionof 0.8-0.95. Raza, et al (92) sprayed a solution consisting of 293.3 g of InC13. 4H20 dissolved in 1 liter of but-&$ acetate onto a glass substrate at SOO'C followed by a 300C annealing in 10 torr vacuum to eliminate the effect of excess oxygen which acts as electron traps. Agnihotri, et al (101), using the same solution have investigatedthe effect of tin addition to In 0 and found that additions of up to 10 mole % of tin decrease the resisttiityof2tie film. Additions above this percentage produce the reverse effect increasingagain the resistivity. The influence of the substrate temperature to 600.C causes only a slight increase in the film resistivity (101). The lowest sheet resistancesare obtained with weight concentrationsof SnC14. 5H20 between 0.15% and 0.5%. Manifaicfer, et al (97) obtained optimum properties of the films spraying the following solution: InC13(8.17%)+ H20(42.04%)+ CH3CH20H(42.04%) SnC14.5H20(0.24%) HC1(7.51%). + + The solution is sprayed through a preheating furnace at 56O'C onto substrates at 506'C. For solar cell applicationshigher concentrationsand lower substrate temperatures (' 44O'C) are recommended. A similar solution has been used by Schunck and Cache (96) but with a 2% concentrationof SnC145H20which was sprayed onto substrates at 500C producing fily% 0,34nm thick with a sheet rqsiftspce of 20 Glsq, carrier concentrationof 7x10 cm , Hall mobility of 13 cm V s and average transmissionof 0.9. Films of In203 without tin chloride addition were similarly depofa 'ted_Sesulting a sheet resistaqce ff 359n/sq, carrier concentrain tion of 0.8x10 cm and Hall mobility of 10 cm V- s- . Ashok, et al (139) have produced films by spraying equal amounts of water, ethyl alcohol and indium chloride-tinchloride mix onto substratesat 400C. The composition of the mix was varied from 2.5% to 50% by changing the proportion of SnC14.5H20to InCl . 2.5% weight concentrationof tin chlorickproduces optimum properties of the 1. Illll.5. These films present a cubic b.c.c. structure and a (111) orientation (97) in accordancewith that generally observed in sputtered films (98). The Sri/In atomic ration of the deposited film is lower than that of the solution for borosilicate glass substrates (97) but almost the same for silicon substrates (97,101). 5.3. Zinc Oxide and Cadmium Stannate Films. Zinc oxide is an oxide semiconductorthat crystallizesin the wurzite structure which can be prepared in the form of thin films with degeneraten-type doping. Its high band gap (- 3.2eV) makes it a candidate for transparentelectrode applications. High transparencyand low resistivity films of ZnO can be produced by spray pyrolysis starting with an aqueous solution of a zinc salt and spraying it over a heated substrate. Solutions containing Zn(N03)2, Zn(C H 0 ) and 2 3 g.2 ZnC12 are generally utilized. Films made from ZnC12 containing star mg solutions show a significantCl concentrationwhich decreases with substrate temperatureand air flow rate in the sprayer (150). Therefore, high substrate temperaturesare necessary to obtain high transparency. The incorporationof hydrogen peroxide to the starting solution also seems to increase the optical transmissionof the films as H O2 reduces the amount of Cl in the film by forming volatile compounds. Regard1ess of the starting solution high optical transmission (- 90%) can be achieved by manipulating the other parameters of the fabricationprocess. For films made from ZnC12 as well as Zn(C2H302)2 starting solutions a 420C substrate temperaturehas been found to give minimum resistivitywhich,after a necessary

238

M. S. Tomar and F. J. Garcia

post-deposition annealing in hydrogen to cre$e oxygen deficiency conditions, is further reduced to values of the order of 10 Qcm (152). Spray pyrolysis deposition of ZnO films compares favorably with other methods of deEqsition (1X&155) which have produced films with resistivities in the range of 10 Rem to 10 Ccm and optical transmissions of about 90%. The deposition of cadmium stannate films by spray pyrolysis requires a more precise control of the spraying parameters to obtain quality films, as the possible formation of more than one phase of cadmium stannate precludes achieving the electrical and optical properties necessary in good transparent electrodes (83). The best starting material seems to be an aqueous solution of CdC12 and SnC14 with CdfSn ratio of the order of l/5. Higher Cd/Sri ratios have produced better reproducibility of the electrical and optical properties (153). Cd2Sn04 or CdSnO phases can be produced by various experimental conditions, but lower sheet resis ?ante (lo-20Rcm) and good optical transparency (> 80%) have been obtained with CdSnO3 films (153). An advantage of sprayed cadmium stannate films over sputtered ones is the elimination of the post-deposition annealing step required in sputtered films.

6, APPLICATIOMS OXIDE OF FILMS

6.1. Solar Cells Using Oxide Semiconductors. The benefits of using a wide band gap semiconductor as the top material in heterojunction solar cells have been recognized for some time. Such a semiconductor acts as an optical window for most of the solar spectrum thus allowing the radiation to reach the bottom absorber semiconductor with little attenuation. Because of this transparency the electron-hole pairs produced by the incoming radiation are created in a large proportion inside the depletion region of the junction, resulting in a noticeable improvement of the spectral response of the cell at short wavelengths relative to the spectral response of most diffused junction cells. Similarly, metal-insulator-semiconductor (MIS) cells also exhibit this type of behavior, and with a suitable thickness of the interfacial insulating layer they are capable of producing open circuit voltages comparable or higher (141) than those obtained with diffused junctions. On the,other hand, the high sheet resistance associated with the small thickness (- 5OA) required for good transparency of the metal in the usual MIS configuration has led to the use of wide band gap transparent oxide semiconductors with degenerate doping as substitutes of the metal thin film, Cells incorporating such an oxide semiconductor and an absorber (smaller band gap) semiconductor generally contain also an interfacial insulating layer (SIS structure) which improves the performance of the cell as in the case of MIS cells. The behaviour of this type of SIS cell, which is roughly similar to that of the MIS structure, has been widely studied and a considerable amount of related work has been done and reported in different publications (100,108,135,139,141). Wide gap (> 3eV) oxide semiconductor films present several properties which make them attractive for use in solar cell applications: a> They are highly conductive and transparent for most of the solar spectrum. b) The indices of refraction of these materials have values (1.2-2.1) which are in the appropriate range for antireflection coating applications. c) The fabrication of these films can be carried out by simple deposition processes, at low temperature and low cost as in the case of spray pyrolysis deposition. The oxide semiconductor, to form a solar cell, can at the same time complete the junction creating the necessary potential barrier, act as a transparent collector of carriers, serve as an antireflection layer and provide environmental protection of the cell. The usual methods of fabrication of this kind of cell allow the utilization ofpolycrystalline absorber semiconductors, instead of monocrystalline, without many of the problems encountered when a diffused junction is formed in polycrystalline material. All these characteristics represent significant advan-

Spray Pyrolysis in Solar Cells and Gas Sensors

239

tages of oxide semiconductor-absorber semiconductorsolar cells over the more common diffused junction cells. Using this type of structure it appears feasible to produce high efficiency solar cells at lower costs than are presently possible with diffused junction technology. One of the most important considerationsin the fabricationof oxide semiconductor-absorber semiconductorsolar cells is the choice of appropriatecombination of materials. According to theoreticalband diagram considerations, to achieve significantphotovoltaicbehaviour with p-type absorber semiconductors, the work function of the oxide semiconductor must be less than or equal to the electron affinity of the absorber semiconductor. Converselywith n-type semiconductors the work function of the oxide semiconductoris to be greater than or equal to the electron affinity plus the band-gap of the absorber semiconductor (107). Following this idea indium-tinoxide (ITO) and ZnO should be adequate for p-type silicon and Sn02 for n-type. In theory these two combinationsproduce minority carrier diodes which are ideal for photovoltaicconversion since they present Schockley type behaviour. This fact is generally confirmed in the literature (108-135) specially in the case of sputtered cells, but not in all spraydeposited cells. Work in this field has been mainly confined to ITO, In 03, and Sn02, usually with silicon as the absorber, and a few experimentsusing Ed2Sn04 and ZnO. InP (136), GaAs (129), CdTe (71), etc., have also been utilized as absorbers but they have shown up until now very modest performance except in the cases of InP (132,136,137) where an efficiency of 14.4% (AM2) has been reported in a cell using ITO, and ZnO (sprayed)/CdTe(single crystal) cell with efficiency of 8.8% has been reported (71,72) in spite of a large lattice mismatch (Table II). About 3% efficiency has also been demonstratedwith an ITO/GaAs cell (129). Shewchun et al (138) present in Table III of that reference properly chosen combinations of oxide semiconductors and the above mentioned absorber semiconductors including theoreticalpossible efficiencies. As noted earlier some cells fabricated by spray pyrolysis of the oxide semiconductorexhibit a behaviour opposite to the theory and to the experimentalresults obtained with other methods of deposition. In this respect, there have been reports of ITO/n-Si and SnO /psi cells made by pyrolysis. Silicon cells with sprayed IT0 show photovolt ic behava. iour only when n-type Si is used, since p-type Si produces an ohmic contact with sprayed IT0 (139). Ashok et al (139) propose that contrary to what happens in sputtered ITOfp-Si cells, where minority carriers generated in the absorber (electronsin the conductionband of silicon) simply slide down to the conduction band of ITO, in sprayed ITOfn-Si cells the photogeneratedcarriers (holes in the valence band of silicon) reach the IT0 by recombinationwith electrons in the conduction band of IT0 via interface states which are necessarily required for this process. At the same time, the existence of an interfacial insulatingoxide layer is fundamentalfor the proper operation of the oxide semiconductorabsorber semiconductor (SIS) cell for the same reason as in the MIS cell. This interfacialinsulatingoxide allows the creation of a strong inversion layer in the surface of the absorber semiconductor which diminishes the effect of the lattice mismatch that may exist between the oxide semiconductorand the absorber semiconductor. This inversion layer behaves as a pseudo p-n junction if proper attention is given to the choice of the electron affinity of the insulating interfacial oxide layer. One advantage of the SIS cell over the MIS cell is that the presence of an energy band gap in the oxide semiconductorblocks majority carrier flow if there are no interfacialstates in the insulating oxide to absorber semiconductor interface. To avoid Tunnel-limitedflow of the photogeneratedcarriers the thickness,ofthe interfaciallayer must be carefully controlled to values less than 10 A. In practice, only a small range of lo-15 1 seems to be useful for good photovoltaicbehaviour (138). Generally this interfacialoxide is grown from the absorber semiconductorby oxidation, producing a native oxide, which has the advantage over deposited oxides of inducing less trap-producingdislocations of the crystal structure together with simpler fabricationand easy control of the oxide thickness. Using this SIS structure a number of oxide semiconductor-absorber semiconductorcells have been constructed,many of them with efficiencies

240

M. S. Tomar and F. .I.Garcia

around 10%. Ion-beam sputtered IT0 on SiO -p-Si cells have shown an efficiency of 16.5% (140), already approaching near t%e limit efficiency of silicon and indicating a good perspective for sprayed type cells. Similarly spray deposited cells with SIS structure have produced above 10% efficiences. Several recent results with this type of cells using n-type silicon as the absorber semiconductor are presented in Table TI. The values of efficiency reported are comparable to sputter-deposited SIS silicon cells and in the same range as n-p diffused silicon cells. As can be seen from the table the work on In 0 and IT0 has been in n-type silicon, structure that when fabricated by sputter ng does not produce significant efficiency. How2a ever, a recent report (134) has shown an efficient electron-beam deposited ITO/nSi solar cell similar to the sprayed ITOfn-Si SIS cell. This not yet completely understood behavior of ET0 on both n and p-type silicon and the influence of the deposition technique still requfre further investigation. Several factors are limiting the efficiency of these cells. Shewchun et al (138) estimate that 10% to 20% reflection loss takes place at the surface of sputtered ITO. Non-degeneracy and work function alteration due to the fabrication method of the oxide semiconductor together with interfacial layer losses due to interfacial layer defect states are the other mechanisms that tend to lower the efficiency of these SIS cells. In conclusion it can be said that the spray pyrolysis method of deposition has demonstrated its usefulness in the production of high efficiency solar cells in a relatively simple, fast, and inexpensive way without the need of vacuum or the use of high temperature processes. In general the use of IT0 presents several advantages over Sn02 since it has better chemical stability and affords the possibility of modifying the alloy composition thus permitting a certain amplitude in the electrical properties of the material. For large scaleimplementation however, Sn02 might be a better candidate since there have been some questions as to the availability of sufficient indium to satisfy the possible demand. Other oxide semiconductors still require further research to fully ascertain their potential. 6.2. Gas Sensors.

Gas sensors based on semiconducting metal oxides can experiment a change in their electrical conductance when gases like carbon monoxide, alcohols, and hydrocarbons are present at high temperatures. The sensor consists typically of a film of an oxide semiconductor on an insulating substrate with two metal electrodes attached. This type of detection was first used to detect gases in air in 1962 (142). One of the most appropriate oxide semiconductors for this application seems to be Sn02 (143-145). There are two models that can explain the change in conductance of the oxide semiconductor: Transfer of electrons from the absorbed gas molecule to the oxide semiconductor, and release into the conduction band of the oxide semrconductor of electrons captured by the previously chemisorbed oxygen which reacts with the absorbed gas (146). The second model seems to represent better observed experimental results (147). Since the detection mechanism relies on the oxygen absorption ability of the oxide semiconductor surface, a high area to volume ratio is desirable. This requirement clearly favors the use of thin film oxide semiconductors in this type of detectors. Long life operability of the sensor depends on maintaining a disordered surface during its working life at the elevated temperatures encountered in the environment. Several gas sensors utilizing films of SnO have been reported in the literature -$ (142-145,148,149). Sn02 sensors exhibi a dependence of their conductance on the square root of carbon monoxide partial pressure and require the presence of oxygen and also operation within a certain temperature range to properly absorb and desorb the gas (147). The times rec@ad by the sensor to detect the gas and to regenerate are of special importance since the measurement of gas concentrations usually need small values of these times. pink et al (149) have produced fast spray deposited sensors with SnO2 as the

OXIDE

SEMlCONOUCTOR

I
A&OR SEfllCONOUCT.

I
(a)
Interfacial oxide Ar a 4 cm "Oc Volt FF JSC mn/cm2

Dopant "C 0.77n O.l3.8 Si o., NR 0.615 o,<685 20 <29 Si POIY O.lSi o., 10.1 Si boo 0.3 (d) Si 3 .OOlTorr "aCt"R o,l Sinole _ n 2 _ 3 (c) Single _ " no iz:f;:ionar o.3 2 _ 3 nNR 1 26.6 0.56 0.68 I 0.4 Sinsle _. n 0.2 _ 0.4 nNR 29.1 0.615 0.685 ethyl 0.77n of SnC14 ethyl acetate 400 in 400 600 300 _ in 300 _ acetate 400 of SnCl4 in 300 _ Sinole 0.2 pm

resist. )kncm Solution Tstfhck.

res. ncm

Sn02 NR

NR

(b)

sno2

NR

NR

Sn02.

NR

NR

0.77n of SnC14 ethyl acetate

sno2

NR

6x10~

alcoholic solution of SnC14.SH20

0.32

0.52

6.7

1979

IO0

SnO 4' 19% 9xlo-4 Si 6 500 0.24 " 2

NR

6x10-~

al;h;;;;

s;;u;ron

4oooc anneal for 2min in

21.0

0.52

0.53

7.2

1979

100

n203

2% SnC14.5H20

IllCl) + 41C Hz0 + 40% C2H50H + 41:: Hz0 C2H50H Si 500 0.24 n 5

Single -

2 -

500C llnneal for 1Omin in air

41.0

0.534

0.47

II.31

1979

Qb -1 36.0 0.50 0.46 9.1 1979 96 0.1 32.0 0.46 0.66 10.2 1517

19%. InCl 9x10-4 + 40x 3

n203

2% SnC14.5t120

Poly -

500C anneal for 1Omin in air

5,x,o-4 435NR I Si alcoholic solution <,r ~~c1~.5H~o+inc1 Sifiolc n2 possible uninterltionJl thin I.!vcr

"0 2 3

0.25 Sn/tn dlomic r3liu

rar
-

"2'3 3 equal 1x10 -3 ethyl 400+ (lnCI3*snCl4.5ti*0) 10-3 2~~12 or Zn acetate propwtions of alcotwl + H20 0.3 0.4 460 0.5

0.25 Sn/ln Jrvmic jiltio 5lxlO 435 NK Si

-4

alcohulic wlution ,of SnC14.5H20+lnC1

Single -

pobsible uninlentiwul thin layer

1.5

32.0

0.48

0.5(

9.1

1977

101

2.5 n203with

0 0 t

Sinulc Si

II 0.5

500C JnnCJl in oxyucn 15 A Sin le p 1.0 possible Cd% thermal thin layer 0

w14.5~ w;';"" 3

0.3

31.5

0.57

0.7(

11.5

19EO

139 140

.:o

17

t9.5

0.54

0.72

8.8

1980

72

TABLE II.- SPRAY DEPOSITED OXIDE SEMICONDUCTOR SOLAR CELLS Notes:a) Illminat'ion lOO~#/cm~ of and room temperature, unlessotherwise indicated. Not reported. Illumination 25 n&V/cm2. b) c) of d) Illumination 80 mW/cm2. of

242

M. S. Tomar and F. J. Garcia

active element. They report that the rise time to the 90% final value of the measurement Is about 30 QS and that regenerationoccurs in about 10 s. Their best results wrth respect to sensEtivityand response time were obtained by spraying, with oxygen as the carrier gas, an organic solution of (CH,COOO),SnC12 in ethylacetate,wEth the equivalent of 15 mg of Sn in 1 ml of solution, onto quartz, glass and Al 0 ceramic substrates,heated to 3OO'C. Because of the present interest in po23 lution control and in the monitortng of different combustionprocesses and small concentrationsof hazardous gases, it appears reasonable that this field of thin film oxfde semiconductorgas sensors will experiment a considerable development in the near term. Sprayed oxide semiconductorsensors will undoubtedly play an importantpart in the future of this area of detection. 6.3. AntlreflectionCoatings (A.R.). Spray pyrolysis deposition of antireflection(AK) coatings for solar cell applications represents a simple and fast method for mass production of inexpensive solar cells. Several oxides, deposited in thin film fonnby differentmethods, are presently used for this purpose. The choice of the appropriatematerial is based on well known AK coat2ng equations,which indicate the required index of refraction of the AK film for quarter wavelength optical thicknessmode operation. The equations are based on the refractive indices of the environmentand the substrate to be covered by the coating. Silicon and gallium arsenide solar cells should have coatings wfth indices of about 2 and with good optical transmission in the spectral range from 0.4 to l.lum. For solar cell applications,around 0.6um is generally chosen as the opt3mizationwavelength used in the calculations. Another considerationthat must be taken into account is the possible detrimental effect of the AK material and the fabricationprocess on the solar cell and its metallizatlon. A material that seems appropriatefor coating single crystal silicon solar cells, with a refractive Index of 3.6 - 3.9, is titanium dioxide. This oxide has an index of about 2, depending on the method and the conditions of fabrication,and can be deposited by the convenientmethod of spray pyrolysis (19,154-156). Hovel (19) has used a spraying arrangementconsistingof passing nitrogen through both heated (85'C) tetraisopropyltitanate and water, and then b@nging together the resulting gases at the nozzle of the sprayer head. A 2 to 5Afs deposition rate was obtained at a spraying distance of 1 cm. It was found that the index of refraction of the deposited film varies as a function of substrate temperaturefrom 1.9 below 1OO'C to a saturationvalue of 2.4 above 4oo"c. In this same study it was shown that the Ti02 film experimentsa phase transition from amorphous to polycrystalline a temperaturebetween 200 and at 3oo"c. Deposition onto s$lfcon at 150C produces films with a refractive index of 2 resulting In less than 0.1% minimum reflectanceat a wavelength of 0.6pm. Similar results were obtained w?th GaAs substrates. Kern and Tracy (20) report spray deposited onto polished silicon wafers, prothat 670& thick films of TIO duce a reflectionminimum of2;.3% (absolute)at a wavelength of 0.611. They used a mixture of titanium (TV) fsopropoxideand an organic liquid to form films of anneal2.1 to 2.2 refractive index. The films were subjected to post-deposition ings at 70DC, 200C and 450C in air to promote oxidation and densification. In accordancewith previous work, Kern and Tracy observed that extended exposure to 45O'C temperaturesinduced a transitlon to a crystallinephase (anastase)of the films. The performanceof TiO spray deposited films on solar cells seems to be better than that of sputtered 5. 10 and spin-on Ti02-Si02 AK coatings. The ease of fabricationreprgsentedby this method of AK coating deposition together with the excellent results already reported can be one more step in reducing the production cost of solar cells. The method also has the possibility of being integrated into a production line type of solar cell fabricationprocess, which could include spray deposited semiconductors and AK coatings, thus providing a cost effective and energy saving way for large scale production of solar cells for terrestr$alapplications. The work reported and an overall

Spray Pyrolysis in Solar Cells and Gas Sensors

243

review of the work fn this article on spray deposited films indicates that an extensive research program is needed to improve the quality of sprayed films so that the devices cancompete with the others, prepared by more conventionaltechniques of vacuum evaporation,R.F. sputtering,CVD etc. and is eagerly awaited.

ACKNOk!LEDGEME!JT
The authors express their sincere thanks to Dr. Julign Chela Flores, Dean of Research, Universidad Sim&r Bolfvar, for encouragement.

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248

M. S. Tomar and F. J. Garcia

THE AUTHORS

M. S. Tomar

F. J. Garcia

Maharaj S. Tomar was born on Jan. lst., 1948 in Jhabiran, U.P., India, and earned his M.Sc. and Ph.D. in Physics from the University of Roorkee, India in the years of 1968 and 1973 respectively. His Pn.D. thesis was on ellipsometry of Blodgett-Langmuir films. He has been a teaching staff member of Universidad Tom&s Frias, Bolivia and Universidad de Los Andes, Mirida, Venezuela, where he worked on infrared ellipsometry and ESCA techniques for surface analysis. He joined Universidad Sim& Bolivar, Caracas, Venezuela, in Feb., 1977 and presently holds a position of Associate Professor of Physics. He has worked on thin film photovoltaic devices of binary and ternary semiconductors using vacuum evaporation, spray pyrolysis and R.F. sputtering techniques. He is actively involved in amorphous/poly and semi-crystalline silicon using R.F. glow-discharge of silane and silicon casting process for solar cell applications. His research interests include solar cells, infrared ellipsometry, switching devices, light emitting diodes, material preparation and characterization, and molecular beam epitaxy. Dr. Tomar is a member of the American Physical Society and the Institute of Electrical and Electronics Engineers. Yrancisco J. Garcia received the B.E.E., M.E.E., and Ph.D. degrees in Electrical Engineering from the Catholic University of America, Washington, D.C., U.S.A., in 1970, 1971 and 1976 respectively. He is currently a Professor of the Department of Electronics at Universidad Simhn Bolivar, Caracas, Venezuela, where he has been working since 1977. Before joining Sim& Bolfvar University, his research activities included work on applications of ferroelectric ceramics and piezoelectri polymers, solar energy conversion, and thin film processing equipment. Since 1977 he has been engaged in development of optoelectronic structures, solar cells, varistors, VCNR's, and other solid state devices. Presently his main line of resea is on the use of binary, ternary, and oxide semiconductors in the production of sol cells by techniques such as sputtering, vacuum evaporation, solid state reaction, screen printing, spray pyrolysis, etc. Dr. Garcia is a member of Sigma Xi, the Institute of Electrical and Electronics Engineers, the International Solar Energy Society, and the New York Academy of Sciences.