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CHEMICAL PROBLEMS 2018 no. 3 (16) ISSN 2221-8688
331
UDC 541.13.544.65
EFFECT OF VARIOUS FACTORS ON THE COMPOSITION OF ELECTROLYTIC THIN FILMS Sb-Se
V.A. Majidzade
Institute of Catalysis and Inorganic Chemistry named after Acad.M.Nagiyev H.Javid ave., 113, Baku AZ1143, Azerbaijan Republic; e-mail: vuska_80@,mail. ru
Received 30.06.2018
The effect to various factors such as temperature, concentration of components in the electrolyte, current density on the composition of thin electrodeposited semiconductive Sb-Se films were viewed in the work. Results obtained indicate that the stibium content in the deposited compounds increases as temperature and concentration of SbOCl rise. As the current density, H2SeO3 and C4H6O6 concentration rises, the stibium content in the films obtained goes dpwn respectively. It revealed that black, uniform, crystalline and lustrous coatings of Sb2Se3 compound are generated in temperature interval 298-318K, current density 20-60 MA/cm2 out of electrolyte 0,01-0,09 M SbOCl,0,01-0,09 MH2SeO3, and compounds of0.001- 0.007M tartaric acid. Keywords: electrodeposition, Sb-Se thin films, current density, semiconductors
iNTRODUCTiON
Recently, the interest has been growing in thin film materials [1-5]. Note that thin films with varied physicochemical properties are applied widely in the capacity of various functional coatings for increasing stability, corrosion resistance, improving magnetic and electrical properties. The application of the thin film materials in aeronautics and space technology, mechanical engineering, medicine, solar energetic, accumulation of energy; as supercapacitors, digital microelectronics, etc. helps to decrease the bulk of materials in various devices [6-8]. Along with these, the nano-structural films have attracted much attention because of their unique properties in functional materials.
The Sb2Se3 films arouse interest from their application in microwave and thermo-electrical chilling devices, optic electronic mechanisms, etc. In this respect, Sb2Se3
compound is a laminated structural semiconductor with orthorhombic crystalline configuration where each Sb and Se atoms are bonded with three opposite atoms which, in turn, are connected through weak subordinate bonds in the crystal [9].
The thin Sb2Se3 semiconductive films are obtained by different methods, including chemical precipitation from solutions, electrodeposition, jet pyrolysis, vacuum thermal evaporation and so on.
In our work, the thin Sb2Se3 semiconductive films were synthesized by a chemical method from the tartaric electrolyte. The electroreduction of each initial component was tested individually before the study of Sb-Se electrodeposition [10, 11].
The goal of the work is a study an effect of some factors on the composition and quality of thin semiconductive Sb-Se films.
EXPERIMENTAL PART
Experimental procedures based on the use of electrochemical method for production of Sb-Se thin films were carried out as follows.
At first, the tartaric acid was dissolved in bidistilled water for the preparation of electrolytes of initial components. Then SbOCl (analytical grade) and H2SeO3 (analytical grade) with required concentration were dissolved in the background solution of the tartaric acid, respectively.
The polarization curves were recorded by IVIUMSTATEl electrochemical Interface potentiometer. The electrochemical triode glass cell was used for this purpose. A Pt electrode with an area of 0.02 sm was utilized as a working electrode. A silver chloride electrode served as a reference electrode,
2
whereas a platinum disk with 4.0 sm area was an auxiliary electrode. Also, a universal ultra thermostat UTU-4 was used to arrange temperature in the electrolyzer.
The electrochemical deposition processes proceeded through the use of potentio-dynamic and galvanostatic methods. In this case, Ni electrode with an area of 2.0 sm2 was used.
The composition of Sb-Se cathodic deposits was determined by using JEOL JSX 3222 Element Analyzer with energy-dispersive X-ray fluorescence spectroscopy (EDXRF) system (JEOL, Japan). It is an analytical technique used for the elemental analysis or chemical characterization of a sample (metals and alloys).
RESULTS AND DISCUSSION
The potentiodynamic polarization investigations were carried out to determine a potential region where antimony and selenium co-deposited. The obtained results are given in
Fig. 1 which shows that the simultaneous electrodeposition process of stibium with selenium takes place within -0.42 - (-0.7) V.
Fig. 1. The cyclic polarization curves of the electroreduction of stibium, selenium and Sb-Se. Electrolyte (M):
1- 0.05 SbOCl + 0.007 C4H6O6
2- 0.05 SbOCl + 0.05H2SeO3 + 0.007 C4H6O6
3- 0.05 H2SeO3 + 0.007 C4H6O6 T=298K, EV = 0.02 V/s.
Following the identification of potential region for electrodeposition of Sb-Se, the effect of some factors on the composition of the films has been studied.
The effect of temperature on the composition of the films has been studied within 298-358 K intervals (fig. 2.).
As it is seen from the figure, the stibium content in the composition of cathodic films increases as the electrolyte temperature rises.
Moreover, the qualities of electrodeposited films are also changed. At 298-318 K temperature intervals a black, uniform, crystalline, shiny coating of Sb2Se3 compound is formed. But at high temperatures, the black, uneven, loose films are formed on the cathode with a weak clutch on the surface of the electrode. Therefore, all next experiments to obtain thin films of Sb2Se3 compound were accomplished at 298 K temperature.
Fig. 2. The dependence between stibium content in the electrodeposited thin films and temperature. Electrolyte (M): 0.05 SbOCl + 0.05 H2SeO3 + 0.007 C4H6O6. The current density (mA/sm2): 1- 30;
Moreover, the concentration of the initial components effects on the composition of the electrodeposited thin films.
In Fig. 3, the effect of concentration of basic component SbOCl on deposited composition is shown. As follows from Fig. 3, the effect of SbOCl concentration was studied
within 0.01-0.09 M intervals, and its increase in electrolyte affects compositions and qualities of the obtained deposits. Despite this, the rise in the current density reduces the stibium content in the composition of thin films.
Fig. 3. The dependence between stibium content in the electrodeposited thin films and concentration of SbOCl in electrolyte. Electrolyte (M): 0.05 H2SeO3 + 0.007 C4H6O6. The current density (mA/sm2): 120; 2- 30; 3- 40; 4- 60. T=298K.
The effect of current density on the stibium content in the obtained films was studied within 20-60 mA/sm intervals. Note that the experiments were carried out with various concentrations of the initial components. According to Fig. 4, the increase of current density during the electrodeposition of Sb-Se has an effect on compositions and qualities of the obtained thin films. The results
indicate that the thin films closer to stoichiometric composition were formed from an electrolyte with contents of 0.05 MSbOCl + 0.05M H2SeO3 + 0.007M C4H6O6 and at 20-30 mA/sm current density. Thus, the stibium and selenium contents in the deposits are 51.4 % and 48.6 % respectively. However, as the current density increases up to 60 mA/sm2, the stibium content in the deposits decreases sharply down to 18.8 %.
Sb,%n 8060 4020-
20 30 40 50 60 it, mA/sr
Fig. 4. The dependence between the stibium content in the electrodeposited thin films and current density.T=298K, Electrolyte (M):
1. 0.01 SbOCl + 0.05 H2Se03 + 0^.007 C4H606
2. 0.25 SbOCl + 0.05 H2Se03 + 0.007 C^Oe
3. 0.5 SbOCl + 0.05 H2Se03 + 0.007 C^Oe
4. 0.75 SbOCl + 0.05 H2Se03 + 0.007 C4H606
5. 0.09 SbOCl + 0.05 H2Se03 + 0.007 C^Oe
Changes in the concentration of H2SeO3 in the electrolyte also notably affect on the composition of the electrodeposited thin film.
The dependence of the influence of this factor is shown in Fig. 5.
Fig. 5. The dependence between stibium content in the electrodeposited thin films and the concentration of H2SeO3in electrolyte. Electrolyte (M): 0.05 SbOCl + 0.007 C4H6O6. The current density (mA/sm2): 1 -20; 2 - 30; 3 - 40; 4 - 60. T=298K.
Investigation of the effect of this factor shows that as H2SeO3 concentration in the electrolyte rises, the stibium content in the films decreases. Thus, at 20-60 mA/sm2
Sb,%Jl 80 60 40 20
According to Fig. 6, as the concentration of tartaric acid in the electrolyte rises from 0.001 to 0.007 M, the stibium content in
current density in terms c H2SeO3 concentration rise in electrolyte from 0.01 to 0.09 M, the stibium content in the deposits decreases from 60.7 to 19.2 %.
Fig. 6. The dependence between the stibium content in the electrodeposited thin films and the concentration of C4H6O6 in electrolyte. Electrolyte (M): 0.05SbOCl + 0.05 H2SeO3. The current density (mA/cm2): 1 - 20; 2 - 30; 3 - 40; 4 - 60. T=298K.
electrodeposited thin films decreases depending on current density from 67.2 to 30.1 %.
CONCLUSIONS
The simultaneous deposition process of stibium with selenium on the Pt electrodes from tartaric electrolytes has been studied by electrochemical method.
The effect of concentrations of the initial components, temperature and current density on electrodeposition process of the Sb-Se thin films was also investigated. The results of all experiments indicate that the increase in the temperature and concentration of SbOCl leads to the rise in the stibium content of the
films. Also, when the current density, H2Se03 and C4H606 concentrations increase the stibium content in the obtained films decreases respectively. The optimal condition and electrolyte composition for electrodeposition process of Sb-Se compound were chosen due to the use of these results. Uniform, crystalline, shiny coatings of Sb2Se3 are reproduced within temperature intervals 298-318К, current density at 20-60 мА/cm2 from electrolyte of 0.01-0.09 М SbOCl, 0.01-0.09 М H2Se03 and 0.001- 0.007 М compounds of tartaric acid.
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ELEKTROKiMYdVi YOLLA ALINMI§ Sb-Se NAZiK TdBdQdLdRiMN TdRKiBiNd MÜXTdLiF AMiLLdRiN TdSiRI
V.A. M9cidzad9
AMEA-nin akad. M.Nagiyev adina Kataliz vd Qeyri-üzvi Kimya institutu AZ1143, Baki, H.Cavid pr., 113; e-mail: vuska_80@mail.ru
Tdqdim edildn i§ elektrokimysvi üsulla gökdürülmü§ Sb-Se nazik tdbdqdldrinin tarkibina müxtdlif amillarin - temperaturun, elektrolitdd komponentldrin qatiliginin, carayan sixliginin tdsirinin tadqiqina hasr edilmi§dir. Naticalar göstarir ki, temperaturun va SbOCl-in qatiliginin artmasi ila gökan nümunalarda sürmanin miqdari artir. Digar faktorlarin tasiri zamani isa alinan nümunalarda sürmanin miqdari azalir. Müayyan edilmi§dir ki, Sb2Se3 kimyavi birla§masinin qara rangli, eyni qalinliqda, kristallik, pariltili örtüklari 298-318 К temperaturda, 20-60 mA/sm2 carayan sixliginda, 0.01-0.09М SbOCl, 0.01-0.09М H2SeO3 va 0.001-0.007 М gaxir tur^usu tarkibli elektrolitdan alinir.
Agar sözldri: elektrogökma, Sb-Se nazik tabaqalari, carayan sixligi, yarimkegiricilar
ВЛИЯНИЕ РАЗЛИЧНЫХ ФАКТОРОВ НА СОСТАВ ЭЛЕКТРОЛИТИЧЕСКИХ
ТОНКИХ ПЛЕНОК Sb-Se
В.А. Меджидзаде
Институт катализа и неорганической химии им. акад. М.Нагиева Национальной АН Азербайджана AZ1143 Баку, пр.Г.Джавида, 113; e-mail: vuska_80@mail.ru
В работе изучено влияние различных факторов - температуры, концентрации компонентов в электролите, плотности тока на состав электроосажденных тонких полупроводниковых пленок Sb-Se. Результаты показывают, что с повышением температуры и концентрации SbOCl содержание сурьмы в осадках увеличивается. А при увеличении плотности тока, концентрации H2SeO3 и СНбОб содержание сурьмы в полученных пленках соответственно уменьшается. Установлено, что черные, равномерные, кристаллические, блестящие покрытия соединения Sb2Se3 получаются в интервале температур 298-318К, плотности тока 20-60 мА/см2 из электролита состава 0.01-0.09МSbOCl, 0.01-0.09МH2SeO3 и 0.001-0.007М винной кислоты. Ключевые слова: электроосаждение, тонкие пленки Sb-Se, плотность тока, полупроводники
