Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application

Accepted Manuscript Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application M.A. Yewale, A.K. Sharma, D.B. Kamble, C.A. Pawar, S.S. Potdar, S.C. Karle PII:

S0925-8388(18)31531-7

DOI:

10.1016/j.jallcom.2018.04.208

Reference:

JALCOM 45846

To appear in:

Journal of Alloys and Compounds

Received Date: 17 January 2018 Revised Date:

16 April 2018

Accepted Date: 18 April 2018

Please cite this article as: M.A. Yewale, A.K. Sharma, D.B. Kamble, C.A. Pawar, S.S. Potdar, S.C. Karle, Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application, Journal of Alloys and Compounds (2018), doi: 10.1016/j.jallcom.2018.04.208. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application

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M. A. Yewale1, 2*, A. K. Sharma1, D. B. Kamble1, C. A. Pawar1 , S. S. Potdar1, S. C. Karle2 1

Thin film, Earth and Space Science Laboratory, Department of Physics,

Department of physics, New arts commerce and science college, Ahmednagar 414001

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Shivaji University, Kolhapur, India

Corresponding Author *: [email protected]

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Graphical Abstract

XRD of uSxSe1-x thin films (x = 0.0 – 1.0).

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Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application M. A. Yewale1, 2*, A. K. Sharma1, D. B. Kamble1, C. A. Pawar1 , S. S. Potdar1,

1

Thin film, Earth and Space Science Laboratory, Department of Physics,

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Shivaji University, Kolhapur, India 2

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S. C. Karle2

Department of physics, New arts commerce and science college, Ahmednagar 414001

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Corresponding Author *: [email protected] Abstract

The CuSxSe1-x thin films were deposited on conducting substrates using copper sulphate sodium thiosulfate and selenium dioxide as a source of Cu, S, and Se by

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electrodeposition(ED) technique. The effect of the change in composition S and Se the structural and electrical properties of the CuSxSe1-x thin films was studied. The crystallite

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size, composition, microstructure, contact angle and capacitance studied using XRD, EDAX, SEM, CA, and CV. The X-Ray diffraction (XRD) graph reveals that the CuSxSe1-x films were

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polycrystalline in nature and CuS0.6Se0.4 shows crystallite size of 34 nm, Energy dispersive analysis X-Ray (EDAX), scanning electron microscopy (SEM) show the elemental composition and microstructures were changes with S and Se composition. The CuS0.6Se0.4 film show 310 contact angle and specific capacitance of 159 F/g Keywords: CuSxSe1-x thin films; Electrodeposition; X-ray Diffraction (XRD); Scanning Electron Microscopy (SEM); Energy dispersive analysis X-Ray (EDAX); Supercapacitor.

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1 Introduction CuS and CuSe are vital p-type semiconductors, they are used in various applications

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such as solar cells [1,2], Supercapacitor [3], photo-catalysts [4–6] Li-ion batteries [7], medical devices [8,9], gas sensors [10] due to their good optical, electrical, chemical, physical and biochemical properties. These properties of material were depend on surface morphology [11,12]. The precise preparation of CuS and CuSe are assumed to be essential

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and CuSe have extensive requests in recent years.

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for extensive requests. Specially, preparation of nano rods, nanogranuals, nano flakes-of CuS

Cu-S-Se is a ternary semiconducting material have interesting physical, chemical and optical property over a binary. The properties of the ternary material are changed with altering the atomic composition [13]. Gopi et al. [14] prepared the CuS electrode to improved photovoltaic efficiency in QDSCs. Solar cell shows highest efficiency 4.67 % in sulfide and

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poly sulfide electrolyte. Sabah et al. [15] synthesised multi-layered CuS thin film by spray pyrolysis method. Flower like microstructure cover whole surface of the substrate films

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which is found to exhibit the high recovery and response time for hydrogen and other gas sensing. Gosavi et al. [16] prepared the CuSe films with the help of SGT method. XRD study

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show polycrystalline nature. Grain size is 145 nm, band gap is 2.03 eV and roughness of CuSe film is 13.1 nm. Electrical properties displayed film were utilised in optoelectronic application. Gao et al. [17] synthesized a series of CuSxSe1-x in non-aqueous medium by reflux method. The synthesis mode is useful for the CuSxSe1-x ternary material with a different content of sulfur and selenium compositions. X-ray data shows that lattice parameter deviates with variation of sulfur and selenium content. Optical spectra reveals that absorption changes according to deviation of chemical content. CuSxSe1-x ternary material were display very good photocatalytic activity for photodegradation of RhB in aqueous

ACCEPTED MANUSCRIPT solution, decomposition is dependent on composition of compound. CuSe1-xSx nanoflakes have effectively been prepared by Ni et al. [18] using copper chloride, Selenium and Sulfur powder as precursor materials through hydrothermal method. FESEM study reveals that for composition in CuSe1-xSx hexagonal nanoflakes shows the same morphologies in the range

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200-600 nm while the thickness is 15-50 nm and all nanoflakes have smooth surfaces. The band gap energy of CuSe1-xSx nanoflakes was altered by change in sulfur and selenium composition. The CuSe1-xSx material was utilised to study the photo degradation of methyl

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blue in a non-aqueous solvent. The performance of CuSe1-xSx was very good and the MB was degraded within 15 min.

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Xu et al. [19] prepared homogeneous ternary hexagonal CuSySe1−y nanoplates and fcc Cu2−xSySe1−y nanoplates through a simple and low-temperature solution scheme. As phase changes hexagonal CuSySe1−y to fcc Cu2−xSySe1−y an optical study observes red shift in absorption. The peak corresponding to the vibrational mode of S−S, S−Se, and Se−Se, was

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observed in Raman study. Resonance peak was shifted with altering the chemical composition. Prepared CuSySe1−y and Cu2−xSySe1−y was utilised as counter electrode in QDSC and shows PCEs of 4.63 and 5.01 % respectively. Phase identification and quantitative

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analysis of mixed crystals by abrasive stripping voltammetry was stated by Meyer et al. [20].

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Dilena et al. [21] prepared cubic & hexagonal Cu2-x(SySe1-y) nanocrystals having same Cu/S/Se stoichiometry by varying the reaction parameter. Wang et al. [22] prepared monodispersed ternary alloyed Cu2-xSySe1-y nanocrystals using a facile one-pot method. The structure of the synthesized nanocrystals change from hexagonal to cubic by varying the reaction parameter. The morphology and size of the cubic phase nanocrystals depend on amount of dodecanethiol and the type of copper precursors. The compositions of both the hexagonal and the cubic nanocrystals also depend on quantities of diphenyl diselenide and dodecanethiol. UV-vis absorption study displays the band gap of the Cu2-xSySe1-y

ACCEPTED MANUSCRIPT nanocrystals can be altered by the chalcogen ratio in the ternary alloyed nancrystals, as well as the crystal structure. Liu et al. [23] prepared CuSxSe1-x NCs. The nanocrystals used in numerous applications, such as photothermal therapy, photoacoustic imaging, and plasmonic photodetectors.

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In present work CuSxSe1-x thin films are prepared by electrodeposition technique. Electrodeposition technique is beneficial because this technique has some advantages over other deposition technique. Experiments were performed under the distinct composition ratio

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of sulfur and selenium and studied their electrical, morphological, physical properties.

2 Experimental

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2.1 Substrate cleaning

Fluorine doped Tin Oxide (FTO) glass slides (75 mm × 25 mm × 1 mm) were used as substrates. The FTO glass substrates were first cleaned by a detergent, and then were rinsed into labogent, acetone and deionized water each for 10 min by using an ultrasonic cleaner.

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Finally, substrates were dried in alcohol (methanol) vapours. 2.2 Preparation of solution Bath - 1

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Bath - 1 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 20ml aqueous

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solution of 0.1M SeO2 and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid. Bath -2

Bath - 2 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 16ml aqueous

solution of 0.1M SeO2, 4ml aqueous solution of 0.3M Na2S2O3.5H2O and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid. Bath -3

ACCEPTED MANUSCRIPT Bath - 3 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 12ml aqueous solution of 0.1M SeO2, 8ml aqueous solution of 0.3M Na2S2O3.5H2O and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid. Bath -4

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Bath - 4 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 8ml aqueous solution of 0.1M SeO2, 12ml aqueous solution of 0.3M Na2S2O3.5H2O and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid.

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Bath -5

Bath - 5 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 4ml aqueous solution

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of 0.1M SeO2, 16ml aqueous solution of 0.3M Na2S2O3.5H2O and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid. Bath -6

Bath - 6 contains 20 ml aqueous solution of 0.1M CuSO4.5H2O, 20ml aqueous

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solution of 0.3M Na2S2O3.5H2O and the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % sulphuric acid.

The fine cleaned conducting SS substrate were used for electrodeposition of CuSxSe1thin films. The deposition was performed for the distinct composition of Sulfur and

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x

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Selenium. CuSxSe1-x films were prepared with the help of three electrode electrodeposition arrangement in which graphite, SS substrate, and SCE are used as a counter, working and a reference electrode. Prepared films were placed in air tight box for further characterization. The different characteristics like structural, compositional and electrical properties of

the electrodeposited CuS thin films were studied by various techniques. X-ray diffraction (XRD) study was done by a Rigaku Rint-2000 X-ray diffractometer using Cu/30kv/ 15 mA radiation with a scan step of 0.001. The compositional analysis of CuS was confirmed by energy-dispersive X-ray analysis, using JEOL model, JSM-6300 (LA). The surface

ACCEPTED MANUSCRIPT morphology of the as synthesized CuS films were studied by using scanning electron microscopy (SEM) using JEOL model, JSM-6360 (LA). 2.3 Growth process and formation mechanism Electrodeposition process depends on electrolysis of material at a boundary of

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electrode-electrolyte because of a pathway of current through an electrolyte and form solid layer on substrate. It contains four steps ionic transport, discharge, nucleation and growth. Seeing the development of dipped films, the probable reaction in electrolyte represented by

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following eq.

CuSO4 → Cu++ + SO4−− ---------------------------------(1)

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next step (S2O3)2- ions are released from Na2S2O3 represented by following eq.

Na2 S2O3 + H 2O → 2Na+ + (S2O3 ) −− ----------------(2) Meanwhile electrochemical reduction of SeO2 becomes

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SeO2 + 6H + + 6e− → H2 Se+ H2O ------------------(3) And sulphur and selenium atom combine with copper by following reaction Cu 2 + + xS 2 − + (1 − x ) Se

2−

→ CuS x Se1− x ------------ (4)

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2.4 Cyclic Voltammetry (CV)

CV is an important electro analytical procedure to analyse electro active kinds.

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Generally this technique is utilised to study qualitative knowledge of chemical reaction. CV is the demonstration of current vs potential of depositing material. The CV curves are repeated after every scan. It is a dominant tools to analyse proper reduction and oxidation potential of material, kinetics study of chemical reaction. Fig. 1 shows the CV of CuSxSe1-x thin film deposited on SS substrate in aqueous electrolyte having 0.1M CuSO4, 0.3M Na2S2O3 and 0.1M SeO2 as a source of Cu, S and Se respectively, the pH of the mixture is maintained at 2-3 by drop wise addition of 10 % H2SO4 in order to find an appropriate

ACCEPTED MANUSCRIPT deposition potentials of CuSxSe1-x. The deposition potential of CuSxSe1-x were found to be 1.0 V/SCE for all composition of Sulfur and selenium. All composition of CuSxSe1-x were deposited by electrodeposition method at -1.0

substrate and prepared films were used for characterizations.

3 Results and discussion

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3.1 XRD study

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V/SCE. Uniform CuSxSe1-x films were deposited at room temperature on SS and FTO

The XRD patterns of CuSxSe1-x films deposited with different composition of S & Se

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with deposition time are shown in Fig. 2(a). The phases of CuSxSe1-x were studied by analysis of XRD patterns, peaks were indexed as (100), (006), (104), (107), (114), (204), (104), (206), (207) and (214) reported as cubic CuS (JCPDS Card No.03-65-3929) and cubic CuSe (JCPDS Card No.00-034-0171). Various patterns indicates the formation of

x.

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polycrystalline CuSxSe1-x. XRD study shows that the precursors were converted into CuSxSe1The crystallite size were obtained with the help of Scherer’s formula. If we change the

Fig 2 (b).

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composition of the sulphur and selenium the intensity of peak at 65˚ also changes as shown in

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The average crystallite size is 67 nm, 51 nm, 56 nm, 34 nm, 42 nm, 29 nm for bath (1), bath (2) bath (3) bath (4) bath (5) and bath (6) respectively. The crystalline size of the material changes with change in composition of the sulphur and selenium. The growth occurs with multiple nucleation centres changes with composition. The crystallite size of the composition is enlisted in table 1 3.2 SEM study Fig. 3 display SEM micrograph of CuSxSe1-x thin films deposited by Electrodeposition for diverse composition of Sulfur and Selenium. From SEM observation it

ACCEPTED MANUSCRIPT is clear that as we alter the composition of S and Se in CuSxSe1-x, the surface morphology of the films also changes with composition. The nanograins of the CuSxSe1-x were smoothly covered over a whole surface of substrate. At lower concentration of the sulfur, the CuSxSe1-x particle was small and spherical, if we increase the Selenium percentage the particle size and

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shape also changes. The film of CuSxSe1-x at X = 0.6 shows the porous morphology at this composition the nanograins were slightly separated and form void space. The porous

particle size of CuS0.6Se0.4 composition is 0.57 µm. 3.3 EDAX study

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structure of the material alter the electrochemical performance of material. The average

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Compositional study of CuSxSe1-x were done with the help of EDAX analysis. Element analysis of as synthesized CuSxSe1-x thin film for different compositions of sulphur and selenium with respect to deposition time as shown in Fig. 4. The ratio between the sulphur and selenium changes with variation of S and Se. EDAX spectra of CuSxSe1-x

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observed that the peak intensity of element were alter with variation of S and Se content in CuSxSe1-x films. The result of atomic and weight percentage is given in table 2. From observation of EDAX, conform that weight percentage of Cu, S, Se were nearly equal to

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atomic percentage. The CuSxSe1-x films were approximately stoichiometric for all

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composition of S and Se. 3.4 FT-IR Study

Fig. 5 display FT-IR spectra of CuSxSe1-x film at different composition of sulphur and

selenium from 550 to 1600 cm-1 range. Peak at 1110 cm−1 and 615 cm-1 indicates the vibrational peaks of Cu-Se and Cu-S stretching modes [24–28], Intensity of FTIR peak were vary with change in S and Se composition in CuSxSe1-x. This peak may confirm the formation CuSxSe1-x at various composition. 3.5 Contact angle study

ACCEPTED MANUSCRIPT Relation between material surface and liquid were expressed by wettability study. Wettability performance of material was measured using contact angle measurement. The wettability of the material is inversely proportional to the contact angle and by the measurement of the contact angle, material was categorized. Fig. 6 gives the contact angle

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measurement of CuSxSe1-x films at the distinct composition of S and Se. The nanograins like CuSe thin film shows a CA of 100°, it may be due to the surface morphology of CuSe films. The contact angle of CuSxSe1-x films altered with a variation of composition. The contact

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angle changes from 100˚ to 66˚ for different composition of S and Se resp. This specifies that with composition variation the contact angle changes as shown in Fig. 7. As we vary

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composition from Se to S the contact angle is also decreased upto x = 0.6 and again contact angle increases. For x = 0.6 composition contact angle is 31˚ it may be due to porous morphology of the films. At this composition, the large amount of electrolyte interact with electrode and enhance electrical property. The material having minimum contact angle are

3.6. Cyclic voltammetry

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the main necessities for supercapacitor study.

Fig 8 (a,b,c,d,e,f) shows CV of the CuSxSe1-x nanograins electrodes electrodeposited

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at different deposition time and different composition of S and Se. CV of the material were

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obtained using three electrode system in 1M NaOH aqueous electrolyte. The CV curve were obtained between a potential windows from -0.4 to 0.8 V. Inside a potential window a minute hump was observed. That hump were equivalent to an anodic and cathodic peak demonstrate supercapacitive behaviour of CuSxSe1-x thin films in aqueous electrolyte. The probable reaction may be completed conversion from Cu (0) to Cu(II) species [29][30]. An oxidation of CuSxSe1-x to Cu (III) kinds may happen in selected potential window of -0.4 to 0.8 V [30]. The CVs of the CuSxSe1-x nanograins were noted in aqueous 1M NaOH electrolyte at different scan rates. If we rise scan rate the cathodic and anodic peak shift near negative and

ACCEPTED MANUSCRIPT positive potential respectively showing a quasi-reversible reaction. The capacitance are calculated from CV equation in chapter II. The capacitance at different compositions are enlisted in table 3. Fig 8 (a,b,c,d,e,f) shows CV of CuSxSe1-x electrode for different composition of S and Se ranging from x = 0.0 to x = 1.0, all the electrodes showing that the

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deposited electrode are proficient electrodes for supercapacitor application. The values of super capacitance calculated from the CVs are 67, 86, 104, 159, 141 and 138 F/g for composition of sulphur and selenium. From table 3 it is clear that as selenium percentage

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decreases. The super capacitance of CuSxSe1-x electrode increases up to 159 F/g and this composition shows maximum capacitance this may be due to porosity and wettability of the

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CuSxSe1-x electrode. At CuS0.6Se0.4 composition the contact angle very less and electron electrolyte interaction higher at small contact angle which increase the capacitance value 3.7 EIS study

Charge transport dynamics of supercapacitor cells was examined by using EIS

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technique. An effect of S and Se composition on the charge carrier dynamics has been observed by execution EIS measurement for CuS0.6Se0.4 composition using 1 M NaOH electrolyte. The measurement is carried out in the AC frequency range 100 KHz–20 Hz. Fig.

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9 shows the nyquist plots for CuS0.6Se0.4 composition. The spectra have been fitted in a

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corresponding circuit shown in inset of Fig. 9. Zsimpwin 3.21 software has been used to fit plots. At maximum frequency a cut off to real axis is termed as equivalent series resistance Rs. The series resistance for CuS0.6Se0.4 composition may be due to the combine resistance of substrate, electrolyte and depositing material which is about 4.1 Ω

5 Conclusions The synthesis of CuSxSe1-x thin films are accomplished by electrodeposition using CuSO4, Na2S2O3 and SeO2 precursors onto stainless steel Substrates. The XRD spectra of CuSxSe1-x thin films reveal polycrystalline nature and the crystallite size changes with sulfur

ACCEPTED MANUSCRIPT and selenium content. The SEM images indicate that porous nature of CuSxSe1-x thin films with spherical grains are agglomerated throughout the surface of thin film. The FT-Raman studies also confirm the deposition of CuSxSe1-x. The contact angle of CuSxSe1-x changes with change in sulfur and selenium content. Contact angle have minimum value at x = 0.6 due to

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the porous morphology of film. The cell corresponding to x = 0.6 exhibited high specific

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capacitance value of 159 F/g having minimum charge resistance 4.1 Ω.

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ACCEPTED MANUSCRIPT Table 1 crystallite size of CuSxSe1-x thin film Deposition

Composition

No. time(min.) 15

X=0.0

2

17

X=0.2

3

19

X=0.4

4

21

X=0.6

5

23

X=0.8

6

25

X=1.0

size (nm) 67 61 56

34

42

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1

crystallite

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Sr.

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29

Table 2 Chemical composition of Cu, S and Se in CuSxSe1-x (X=0.0 -1.0) Atomic percentage of bath

Film

sition

composition

Cu

0.0

CuSe

50

0.2

CuS0.2Se0.8

0.4

Atomic percentage of films

Se

Cu

S

Se

00

50

49.54

00.00

50.46

50

10

40

52.02

09.16

38.62

CuS0.4Se0.6

50

20

30

49.18

21.07

29.12

0.6

CuS0.6Se0.4

50

30

20

52.21

27.16

20.63

0.8

CuS0.8Se0.2

50

40

20

51.16

38.19

10.65

1.0

50

50

00

53.60

46.40

00.00

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S

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Compo

CuS

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Table 3 Specific capacitance of CuSxSe1-x thin film for different composition Composition

Film

Specific capacitance

of film x

composition

F/g

0.0

CuSe

67

0.2

CuS0.2Se0.8

86

0.4

CuS0.4Se0.6

104

0.6

CuS0.6Se0.4

159

0.8

CuS0.8Se0.2

141

1.0

CuS

138

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Fig. 1 CV of CuSxSe1-x thin film on SS substrate

Fig. 2 (a) XRD patterns of CuSxSe1-x films for composition (0.0
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Fig. 2 (b) XRD patterns of CuSxSe1-x thin films

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Fig. 3 : The SEM image of CuSxSe1-x thin films for composition (0.0
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Fig. 4 : The EDAX spectra of CuSxSe1-x films for composition (0.0
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Fig. 5: FTIR of CuSxSe1-x films for composition (0.0
Fig. 6 Contact angle of CuSxSe1-x films for composition (0.0
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Fig. 7. Contact angle of CuSxSe1-x films for composition (0.0
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Fig. 8-a CV of CuSe electrodes in 1 M NaOH.

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X=0.2

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Fig. 5.8-a CV of CuSe electrodes in 1 M NaOH.

Fig. 5.8-b CV of CuS0.2Se0.8 electrodes in 1 M NaOH Fig. 8-b CV of CuS0.2Se0.8 electrodes in 1 M NaOH

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X=0.4

X=0.6

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Fig. 8-c CV of CuS0.4Se0.6 electrodes in 1 M NaOH

Fig. 8-d CV of CuS0.Se0.2 electrodes in 1 M NaOH

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Fig. 8-e CV of CuS0.8Se0.2 electrodes in 1 M NaOH

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Fig. 5.8-d CV of CuS0.6Se0.4 electrodes in 1 M NaOH Fig. 5.8-e CV of CuS0.8Se0.2electrodes in 1 M NaOH

Fig. 8-f CV of CuS electrodes in 1 M NaOH

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Fig. 9 Electrochemical impedance spectra of CuS0.6Se0.4 electrode.

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Electrochemical synthesis of CuSxSe1-x thin film for supercapacitor application

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M. A. Yewale1, 2*, A. K. Sharma1, D. B. Kamble1, C. A. Pawar1 , S. S. Potdar1, S. C. Karle2 1

Thin film, Earth and Space Science Laboratory, Department of Physics,

Department of physics, New arts commerce and science college, Ahmednagar 414001

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Shivaji University, Kolhapur, India

Corresponding Author *: [email protected]

Research Highlights

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Electrochemical synthesis of CuS, CuSe and CuSxSe1-x thin films
Nanograins like structure.

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Supercapacitive study

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XRD of CuSxSe1-x thin films (0.0 – 1.0).