||In our study, we have prepared Ag-In-S semiconductor thin film by ultrasonic chemical bath deposition. The effect of various molar ratio in solutions on the crystal, morphological and photoelectrochemical (PEC) properties of the samples was measured. According X-ray diffraction studies, it was found that when [Ag]/[In]=1 in the solution, AgInS2 was be prepared after annealed for 1h in a nitrogen environment at 400℃ in a quartz tube. However, the crystal structure will become polycrystalline AgIn5S8 gradually with increase [Ag]/[In] molar ratio. The film thickness、flat band potentials、energy band gaps of the samples were between 0.38 and 0.89 μm, -1.09 and -1.23 V vs. SCE, -1.90 and -2.05 eV, respectively. All films had appropriate absorption coefficient which upper than 105 cm-1. Under the visible light irradiation with intensity of 100mW/cm2, the photocurrent density can achieve 1.45 mA/cm2 when [Ag]/[In]=3 with applied potential of 1.0 V vs. SCE in the three-electrode system. Form EIS, the results show all of samples had surface state, with 1.0 V bias, surface state resistances will decrease quickly and capacitances will increase. Indicate the minority carriers can across the interface between thin film and electrolyte with applied potential. IMPS measurements show that first quadrant semicircle reduces with applied potential, and it can be attributed to the rate constant of minority carriers recombination with electrons or react with electrolyte. The simulation results exhibit thin film parameters, like: diffusion coefficient、electron lifetime、surface state lifetime, etc. Among these parameters, the electron lifetime has clear rise when applied bias. [Ag]/[In]=3 has longest electron lifetime, so according the function Ln=(Dnτn)1/2, the electron diffusion length can be calculated.|
||1. Fujishima A, Honda K. Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature. 1972;238(5358).|
2. Wikipedia-Sunlight. http://en.wikipedia.org/wiki/Sunlight.
3. Diwald O, Thompson TL, Zubkov T, Goralski EG, Walck SD, Yates JT. Photochemical activity of nitrogen-doped rutile TiO2 (110) in visible light. The Journal of Physical Chemistry B. 2004;108(19):6004-6008.
4. 李芳紜. 超音波輔助化學水浴法製備AgInS2薄膜之電化學阻抗頻譜分析. 中央大學. 2013.
5. Krishnan R. Fundamentals of Semiconductor Electrochemistry and Photoelectrochemistry. Encyclopedia of Electrochemistry: Wiley-VCH Verlag GmbH & Co. KGaA; 2007.
6. Linsebigler AL, Lu G, Yates JT. Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results. Chemical Reviews. 1995/05/01 1995;95(3):735-758.
7. Shay J, Tell B, Schiavone L, Kasper H, Thiel F. Energy bands of AgInS2 in the chalcopyrite and orthorhombic structures. Physical Review B. 1974;9(4):1719.
8. Cheng K-W, Liu P-H. Photoelectrochemical performances of AgInS2 film electrodes fabricated using the sulfurization of Ag–In metal precursors. Solar Energy Materials and Solar Cells. 2011;95(7):1859-1866.
9. Aguilera MLA, Hernández JRA, Trujillo MAG, López MO, Puente GC. Photoluminescence studies of chalcopyrite and orthorhombic AgInS2 thin films deposited by spray pyrolysis technique. Thin Solid Films. 2007;515(15 SPEC. ISS.):6272-6275.
10. Cheng K-W, Huang C-M, Pan G-T, Chang W-S, Lee T-C, Yang TCK. The physical properties and photoresponse of AgIn5S8 polycrystalline film electrodes fabricated by chemical bath deposition. Journal of Photochemistry and Photobiology A: Chemistry. 2007;190(1):77-87.
11. Wang C-H, Cheng K-W, Tseng C-J. Photoelectrochemical properties of AgInS2 thin films prepared using electrodeposition. Solar Energy Materials and Solar Cells. 2011;95(2):453-461.
12. Delgado G, Mora A, Pineda C, Tinoco T. Simultaneous Rietveld refinement of three phases in the Ag-In-S semiconducting system from X-ray powder diffraction. Materials research bulletin. 2001;36(13):2507-2517.
13. Bisquert J, Vikhrenko VS. Interpretation of the time constants measured by kinetic techniques in nanostructured semiconductor electrodes and dye-sensitized solar cells. The Journal of Physical Chemistry B. 2004;108(7):2313-2322.
14. Dloczik L, Ileperuma O, Lauermann I, et al. Dynamic response of dye-sensitized nanocrystalline solar cells: characterization by intensity-modulated photocurrent spectroscopy. The Journal of Physical Chemistry B. 1997;101(49):10281-10289.
15. Soedergren S, Hagfeldt A, Olsson J, Lindquist S-E. Theoretical Models for the Action Spectrum and the Current-Voltage Characteristics of Microporous Semiconductor Films in Photoelectrochemical Cells. The Journal of Physical Chemistry. 1994/05/01 1994;98(21):5552-5556.
16. Franco G, Peter LM, Ponomarev EA. Detection of inhomogeneous dye distribution in dye sensitised nanocrystalline solar cells by intensity modulated photocurrent spectroscopy (IMPS). Electrochemistry Communications. 1999;1(2):61-64.
17. Li J, Peat R, Peter L. Surface recombination at semiconductor electrodes: Part II. Photoinduced “near-surface” recombination centres in p-GaP. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 1984;165(1):41-59.
18. Peter L, Li J, Peat R. Surface recombination at semiconductor electrodes: Part I. Transient and steady-state photocurrents. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 1984;165(1):29-40.
19. Li J, Peter LM. Surface recombination at semiconductor electrodes: Part III. Steady-state and intensity modulated photocurrent response. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 1985;193(1–2):27-47.
20. Li J, Peter LM. Surface recombination at semiconductor electrodes: Part iv. Steady-state and intensity modulated photocurrents at n-GaAs electrodes. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 1986;199(1):1-26.
21. Peter LM, Li J, Peat R, Lewerenz H, Stumper J. Frequency response analysis of intensity modulated photocurrents at semiconductor electrodes. Electrochimica Acta. 1990;35(10):1657-1664.
22. Ponomarev EA, Peter LM. A comparison of intensity modulated photocurrent spectroscopy and photoelectrochemical impedance spectroscopy in a study of photoelectrochemical hydrogen evolution at p-InP. Journal of Electroanalytical Chemistry. 1995;397(1–2):45-52.
23. Lin Y, Zhang J, Yin F, Xiao X. Interfacial Charge Transfer Behaviors of Nanoparticulate CdSe Thin Film Electrodes. ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-FRANKFURT AM MAIN THEN WIESBADEN THEN MUNCHEN-. 1999;213:1-8.
24. Songyuan LWHLHZD. Development and Application of Intensity Modulate Photocurrent Spectroscopy and Intensity Modulate Photovoltage Spectroscopy. Progress in Chemistry. 2009;21(6):1085.
25. Krüger J, Plass R, Grätzel M, Cameron PJ, Peter LM. Charge Transport and Back Reaction in Solid-State Dye-Sensitized Solar Cells: A Study Using Intensity-Modulated Photovoltage and Photocurrent Spectroscopy. The Journal of Physical Chemistry B. 2003/08/01 2003;107(31):7536-7539.
26. Ponomarev EA, Peter LM. A generalized theory of intensity modulated photocurrent spectroscopy (IMPS). Journal of Electroanalytical Chemistry. 1995;396(1–2):219-226.
27. Chen Y, Huang G-F, Huang W-Q,, Wang L-L, Tian Y, Ma Z-L, Yang Z-M. Annealing effects on photocatalytic activity of ZnS films prepared by chemical bath deposition. Materials Letters. 2012;75(0):221-224.
28. Cheng K-W, Jhuang C-H, Yeh L-Y. Influence of gallium on the growth and photoelectrochemical performances of AgIn5S8 photoelectrodes. Thin Solid Films. 2012;524(0):238-244.
29. Lin L-H, Wu C-C, Lai C-H, Lee T-C. Controlled Deposition of Silver Indium Sulfide Ternary Semiconductor Thin Films by Chemical Bath Deposition. Chemistry of Materials. 2008/07/01 2008;20(13):4475-4483.
30. Chrysikopoulos CV, Kruger P. Chelated indium activable tracers for geothermal reservoirs, Stanford University; 1986.
31. Cheng K-W, Wang S-C. Effects of complex agents on the physical properties of Ag–In–S ternary semiconductor films using chemical bath deposition. Materials Chemistry and Physics. 2009;115(1):14-20.
32. Huang M-C, Wang T, Chang W-S, Wu C-C, Lin J-C, Yen T-H. Influence of dipping cycle on structural, optical and photoelectrochemical characteristics of single phase polycrystalline AgInS< sub> 2 thin films on ITO prepared by aqueous chemical reaction. Journal of Alloys and Compounds. 2014;606:189-195.
33. Bott AW. Electrochemistry of semiconductors. Current Separations. 1998;17:87-92.
34. Chang W-S, Wu C-C, Jeng M-S, Cheng K-W, Huang C-M, Lee T-C. Ternary Ag–In–S polycrystalline films deposited using chemical bath deposition for photoelectrochemical applications. Materials Chemistry and Physics. 2010;120(2–3):307-312.
35. Tseng C-J, Wang C-H, Cheng K-W. Photoelectrochemical performance of gallium-doped AgInS2 photoelectrodes prepared by electrodeposition process. Solar Energy Materials and Solar Cells. 2012;96(0):33-42.
36. 謝叢憶. IMPS/IMVS於半導體電極之分析與應用. 中正大學. 2011.