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Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films

Yuming Xue, Shipeng Zhang, Dianyou Song, Liming Zhang, Xinyu Wang, Lang Wang and Hang Sun

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 Corresponding author: Yuming Xue, orwellx@tjut.edu.cn; Dianyou Song, youdiansong@163.com

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Abstract: Cd1–xZnxS thin films were deposited by chemical bath deposition (CBD) on the glass substrate to study the influence of cadmium sulfate concentration on the structural characteristics of the thin film. The SEM results show that the thin film surfaces under the cadmium sulfate concentration of 0.005 M exhibit better compactness and uniformity. The distribution diagrams of thin film elements illustrate the film growth rate changes on the trend of the increase, decrease, and increase with the increase of cadmium sulfate concentration. XRD studies exhibit the crystal structure of the film is the hexagonal phase, and there are obvious diffraction peaks and better crystallinity when the concentration is 0.005 M. Spectrophotometer test results demonstrate that the relationship between zinc content x and optical band gap value Eg can be expressed by the equation Eg(x) = 0.59x2 + 0.69x + 2.43. Increasing the zinc content can increase the optical band gap, and the absorbance of the thin film can be improved by decreasing the cadmium sulfate concentration, however, all of them have good transmittance. At a concentration of 0.005 M, the thin film has good absorbance in the 300–800 nm range, 80% transmittance, and band gap value of 3.24 eV, which is suitable for use as a buffer layer for solar cells.

Key words: CIGS thin film solar cellCBD (chemical bath deposition)buffer layerCd1–xZnxS thin filmscadmium sulfate



[1]
Abza T, Ampong F K, Hone F G, et al. Preparation of cadmium zinc sulfide (Cd1−xZnxS) thin films from acidic chemical baths. Thin Solid Films, 2018, 666, 28 doi: 10.1016/j.tsf.2018.09.011
[2]
Zellagui R, Dehdouh H, Adnane M, et al. Cd1–xZnxS thin films deposited by chemical bath deposition (CBD) method. Optik, 2020, 207, 164377 doi: 10.1016/j.ijleo.2020.164377
[3]
Ma L, Ai X, Wu X. Effect of substrate and Zn doping on the structural, optical and electrical properties of CdS thin films prepared by CBD method. J Alloys Compd, 2017, 691, 399 doi: 10.1016/j.jallcom.2016.08.298
[4]
Bae D, Gho J, Shin M, et al. Effect of zinc addition on properties of cadmium sulfide layer and performance of Cu(In, Ga)Se2 solar cell. Thin Solid Films, 2013, 535, 162 doi: 10.1016/j.tsf.2012.11.077
[5]
Zhou L M, Li Y L, Dong Y J. Preparation and characterisation of Cd1–xZnxS thin films grown in chemical bath deposition. Mater Res Innov, 2015, 1088, 86 doi: 10.4028/www.scientific.net/AMR.1088.86
[6]
Guo W, Xue Y M, Gu Y, et al. Influence of solution pH value on structural properties of CdS thin films. J Optoelectron Laser, 2013, 24(11), 2169 doi: 10.16136/j.joel.2013.11.012
[7]
Oliva A I, Corona J E, PatiñO R, et al. Chemical bath deposition of CdS thin films doped with Zn and Cu. Bull Materials Sci, 2014, 37(2), 247 doi: 10.1007/s12034-014-0642-9
[8]
Offiah S U, Agbogu A N C, Nwanya A C, et al. Influence of cadmium precursor concentrations on the structural, optical and electrochemical impedance properties of Cd1–xZnxS thin films. Vacuum, 2019, 160, 246 doi: 10.1016/j.vacuum.2018.11.041
[9]
Yao H, Shen H, Zhu X, et al. Influence of Cd source concentration on photo-current response property of Cd1–xZnxS film prepared by chemical bath deposition. Ceram Int, 2016, 42(2), 2466 doi: 10.1016/j.ceramint.2015.10.047
[10]
Munna F T, Chelvanathan P, Sobayel K, et al. Effect of zinc doping on the optoelectronic properties of cadmium sulphide (CdS) thin films deposited by chemical bath deposition by utilising an alternative sulphur precursor. Optik, 2020, 218, 165197 doi: 10.1016/j.ijleo.2020.165197
[11]
Carreón-Moncada I, González L A, Pech-Canul M I, et al. Cd1–xZnxS thin films with low Zn content obtained by an ammonia-free chemical bath deposition process. Thin Solid Films, 2013, 548, 270 doi: 10.1016/j.tsf.2013.10.024
[12]
Liu J, Wei A, Zhao Y. Effect of different complexing agents on the properties of chemical-bath-deposited ZnS thin films. J Alloys Compd, 2014, 588, 228 doi: 10.1016/j.jallcom.2013.11.042
[13]
Kaleli M. Effect of sulphurization and Al doping on Cd0.25Zn0.75S thin films deposited by ultrasonic spray pyrolysis technique. Optik, 2019, 207, 163781 doi: 10.1016/j.ijleo.2019.163781
[14]
Zhou Z, Guo L. Cd1–xZnxS energy band calculated by the first-principle method. Journal of Xi'an Jiaotong University, 2008, 42(2), 248
[15]
Salem A M. Structure, refractive-index dispersion and the optical absorption edge of chemically deposited ZnxCd1–xS thin films. Appl Phys A, 2002, 74(2), 205 doi: 10.1007/s003390100877
Fig. 1.  SEM images of Cd1–xZnxS thin films prepared with different concentrations of cadmium sulfate.

Fig. 2.  (Color online) Element distribution diagrams of Cd1–xZnxS thin films deposited with different concentrations of cadmium sulfate.

Fig. 3.  XRD patterns of Cd1–xZnxS thin films deposited at different concentrations of cadmium sulfate.

Fig. 4.  Plots of (a) absorbance vs wavelength and (b) transmittance vs wavelength for the Cd1–xZnxS thin films prepared with different concentrations of cadmium sulfate.

Fig. 5.  Band gap of Cd1–xZnxS thin films deposited with different concentrations of cadmium sulfate.

Fig. 6.  The value of Cd1–xZnxS thin film band gap changes with x.

Table 1.   Deposition conditions of CBD-Cd1–xZnxS.

ReagentConcentration (M)
ZnSO40.020
(NH4)2SO40.025
SC(NH2)20.015
NH3·H2O25%
CdSO40.003, 0.004, 0.005, 0.006, 0.007
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Table 2.   Thickness of Cd1–xZnxS thin films with different cadmium sulfate concentration.

Concentration of cadmium sulfate (M)Thickness (nm)
0.00371.13
0.00473.28
0.00564.73
0.00662.46
0.00766.51
DownLoad: CSV

Table 3.   The atom ratios of S, Zn and Cd in Cd1–xZnxS thin films prepared with different concentrations of cadmium sulfate.

Concentration of cadmium sulfate (M)Atom ratio of S, Zn and CdZn/(Zn+Cd)
0.00330.40 : 36.81 : 32.790.529
0.00431.87 : 34.34 : 33.790.504
0.00522.17 : 55.83 : 22.000.717
0.00622.61 : 57.24 : 20.150.739
0.00728.82 : 37.92 : 33.260.533
DownLoad: CSV

Table 4.   Film element content, zinc-cadmium content ratio and band gap.

Cd (at.%)Zn (at.%)S (at.%)Zn/CdCd1–xZnxSEg (eV)
32.7936.8130.401.12Cd0.48Zn0.52S2.95
33.7934.3431.871.02Cd0.50Zn0.50S2.93
22.0055.8322.172.54Cd0.28Zn0.72S3.24
20.1557.2422.612.84Cd0.26Zn0.74S3.27
33.2637.9228.821.14Cd0.47Zn0.53S2.97
DownLoad: CSV
[1]
Abza T, Ampong F K, Hone F G, et al. Preparation of cadmium zinc sulfide (Cd1−xZnxS) thin films from acidic chemical baths. Thin Solid Films, 2018, 666, 28 doi: 10.1016/j.tsf.2018.09.011
[2]
Zellagui R, Dehdouh H, Adnane M, et al. Cd1–xZnxS thin films deposited by chemical bath deposition (CBD) method. Optik, 2020, 207, 164377 doi: 10.1016/j.ijleo.2020.164377
[3]
Ma L, Ai X, Wu X. Effect of substrate and Zn doping on the structural, optical and electrical properties of CdS thin films prepared by CBD method. J Alloys Compd, 2017, 691, 399 doi: 10.1016/j.jallcom.2016.08.298
[4]
Bae D, Gho J, Shin M, et al. Effect of zinc addition on properties of cadmium sulfide layer and performance of Cu(In, Ga)Se2 solar cell. Thin Solid Films, 2013, 535, 162 doi: 10.1016/j.tsf.2012.11.077
[5]
Zhou L M, Li Y L, Dong Y J. Preparation and characterisation of Cd1–xZnxS thin films grown in chemical bath deposition. Mater Res Innov, 2015, 1088, 86 doi: 10.4028/www.scientific.net/AMR.1088.86
[6]
Guo W, Xue Y M, Gu Y, et al. Influence of solution pH value on structural properties of CdS thin films. J Optoelectron Laser, 2013, 24(11), 2169 doi: 10.16136/j.joel.2013.11.012
[7]
Oliva A I, Corona J E, PatiñO R, et al. Chemical bath deposition of CdS thin films doped with Zn and Cu. Bull Materials Sci, 2014, 37(2), 247 doi: 10.1007/s12034-014-0642-9
[8]
Offiah S U, Agbogu A N C, Nwanya A C, et al. Influence of cadmium precursor concentrations on the structural, optical and electrochemical impedance properties of Cd1–xZnxS thin films. Vacuum, 2019, 160, 246 doi: 10.1016/j.vacuum.2018.11.041
[9]
Yao H, Shen H, Zhu X, et al. Influence of Cd source concentration on photo-current response property of Cd1–xZnxS film prepared by chemical bath deposition. Ceram Int, 2016, 42(2), 2466 doi: 10.1016/j.ceramint.2015.10.047
[10]
Munna F T, Chelvanathan P, Sobayel K, et al. Effect of zinc doping on the optoelectronic properties of cadmium sulphide (CdS) thin films deposited by chemical bath deposition by utilising an alternative sulphur precursor. Optik, 2020, 218, 165197 doi: 10.1016/j.ijleo.2020.165197
[11]
Carreón-Moncada I, González L A, Pech-Canul M I, et al. Cd1–xZnxS thin films with low Zn content obtained by an ammonia-free chemical bath deposition process. Thin Solid Films, 2013, 548, 270 doi: 10.1016/j.tsf.2013.10.024
[12]
Liu J, Wei A, Zhao Y. Effect of different complexing agents on the properties of chemical-bath-deposited ZnS thin films. J Alloys Compd, 2014, 588, 228 doi: 10.1016/j.jallcom.2013.11.042
[13]
Kaleli M. Effect of sulphurization and Al doping on Cd0.25Zn0.75S thin films deposited by ultrasonic spray pyrolysis technique. Optik, 2019, 207, 163781 doi: 10.1016/j.ijleo.2019.163781
[14]
Zhou Z, Guo L. Cd1–xZnxS energy band calculated by the first-principle method. Journal of Xi'an Jiaotong University, 2008, 42(2), 248
[15]
Salem A M. Structure, refractive-index dispersion and the optical absorption edge of chemically deposited ZnxCd1–xS thin films. Appl Phys A, 2002, 74(2), 205 doi: 10.1007/s003390100877
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    Received: 12 April 2021 Revised: 20 April 2021 Online: Accepted Manuscript: 10 June 2021Uncorrected proof: 11 June 2021Published: 01 November 2021

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      Yuming Xue, Shipeng Zhang, Dianyou Song, Liming Zhang, Xinyu Wang, Lang Wang, Hang Sun. Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films[J]. Journal of Semiconductors, 2021, 42(11): 112101. doi: 10.1088/1674-4926/42/11/112101 Y M Xue, S P Zhang, D Y Song, L M Zhang, X Y Wang, L Wang, H Sun, Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films[J]. J. Semicond., 2021, 42(11): 112101. doi: 10.1088/1674-4926/42/11/112101.Export: BibTex EndNote
      Citation:
      Yuming Xue, Shipeng Zhang, Dianyou Song, Liming Zhang, Xinyu Wang, Lang Wang, Hang Sun. Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films[J]. Journal of Semiconductors, 2021, 42(11): 112101. doi: 10.1088/1674-4926/42/11/112101

      Y M Xue, S P Zhang, D Y Song, L M Zhang, X Y Wang, L Wang, H Sun, Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films[J]. J. Semicond., 2021, 42(11): 112101. doi: 10.1088/1674-4926/42/11/112101.
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      Effect of concentration of cadmium sulfate solution on structural, optical and electric properties of Cd1–xZnxS thin films

      doi: 10.1088/1674-4926/42/11/112101
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      • Author Bio:

        Yuming Xue is an associate professor at the School of Electrical and Electronic Engineering, Tianjin University of Technology, Tianjin, China. He received a PhD degree in Microelectronics and Solid State Electronics. He has been engaged in research on thin film semiconductor materials and their devices for 21 years

        Shipeng Zhang (1997–), male, born in Huai’an, Jiangsu. Master candidate of integrated circuit engineering, School of Electrical and Electronic Engineering, Tianjin University of Technology. Research direction: CIGS thin film solar cell buffer layer

        Dianyou Song is a professor at Tianjin University of Technology. He received his PhD degree in optoelectronic technology from Tianjin University in China. He has been engaged in research on the development and application of optoelectronic technology for 21 years

      • Corresponding author: orwellx@tjut.edu.cnyoudiansong@163.com
      • Received Date: 2021-04-12
      • Revised Date: 2021-04-20
      • Published Date: 2021-11-10

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