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Lecture 15 Current-Potential Curves at Semiconductor Electrodes - Part II - Reference. 1.R. Memming, Semiconductor Electrochemistry, Wiley-VCH, 2000 (e-book) 2.A.J. Bard and L.R. Faulkner, Electrochemical Methods: Fundamentals and Applications, Wiley, 2001 3.J. O’M. Bockris, A.K.N. Reddy, and M. Gamboa-Aldeco, Modern Electrochemistry, Kluwer Academic/Plenum Publishers, 2000 Lecture note http://les.kaist.ac.kr/B_Lecture
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Light-induced Process
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Majority Carrier Reaction - Dark I-V Examples - 1.ln(j) vs. U E (is the 60 mV/dec.?) 2.Rate constant or charge transfer kinetics
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ZnO in Water n-ZnO in water with various redox systems 1. pH dependence 2. Slope = 60 mV/dec. 3. Reaction rate constants k c,max - U 0 redox = 0.2 V and E s c = -0.2V for [Fe(CN) 6 ] 3-/4- - k - c from log j- vs. sc 1.3 10 -17 cm 4 s -1 k - c,max ~ 10 -17 cm 4 s -1 k + c,max ~ 10 -24 cm 4 s -1
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n-InP in Methanol with Methyl Ferrocene 1. SC in non-aqueous solution No interference associated with corrosion and H 2 evolution 2. Standard redox system Ferrocene (F c 0/1+ ) and cobaltocene (CoC p2 0/1+ ) Non-adsorbing outer sphere redox systems 3. k - c,max ~ 10 -16 cm 4 s -1 for ferrocene k - c,max ~ 10 -15 cm 4 s -1 for cobaltocene
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n-GaAs in Acetonitrile with Cobaltocene 1. Reduction of cobaltocene at GaAs electrode Ultrafast charge transfer kinetics 2. I-V curve model by the thermionic model What does it mean? 3. Charge transfer velocity S et (cm/s) S et = k - c N ad,ox ~ 5 10 6 cm/s
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n-GaAs in Water (H 2 Formation) Hydrogen evolving reaction (HER) 1. 2H + + 2e - = H 2 U 0 redox = 0 V vs. NHE 2. 2H 2 O + 2e - = H 2 + 2OH - U 0 redox = - 0.828 V vs. NHE
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Minority Carrier Reactions - Photo-effect -
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n-WSe 2 in Water
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p-GaAs in Water
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Next Meeting Electrochemical Decomposition of Seminconductors
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