Electroreflection

Lee C H, Chang R K and Bloembergen N 1967 Nonlinear electroreflectance in silicon and silver Phys. Rev. Lett. 18 167-70... 

Aktsipetrov O A and Mishina E D 1984 Nonlinear optical electroreflection in germanium and silicon Dokl. Akad. Nauk SSSR 274 62-5... 

Dadap J I, Hu X F, Anderson M H, Downer M C, Lowell J Kand Aktsiperov O A 1996 Optical second-harmonic electroreflectance spectroscopy of a Si(OOOI) metal-oxide-semiconductor structure Phys. Rev. B 53 R7607-9... 

Commercial versions of PR are available. Other contactless methods of electro-modulation are Electron-Beam Electro-reflectance (EBER) and Contacdess Electroreflectance (CER). In EBER the pump beam of Figure 2 is replaced by a modulated low-energy electron beam (- 200 eV) chopped at about 1 kHz. However, the sample and electron gun must be placed in an ultrahigh vacuum chamber. Contactless electroreflectance uses a capacitor-like arrangement. 

Kolb and Franke have demonstrated how surface reconstruction phenomena can be studied in situ with the help of potential-induced surface states using electroreflectance (ER) spectroscopy.449,488,543,544 The optical properties of reconstructed and unreconstructed Au(100) have been found to be remarkably different. In recent model calculations it was shown that the accumulation of negative charges at a metal surface favors surface reconstruction because the increased sp-electron density at the surface gives rise to an increased compressive stress between surface atoms, forcing them into a densely packed structure.532... 

Electroreflectance data for pc-Cu579 confirm that the capacity minimum at E- -0.2 to -0.3 V (SCE) is due to the oxidation of the electrode surface. According to impedance data,564,565 as for pc-Ag and pc-Au,63 67 74 roughness factor for a pc-Cu electrode is approximately 2, which has been explained by the high surface inhomogeneity of the electrode surface. 

Electrochemical techniques have been developed into very powerful tools for research and technology. However, decades ago, researchers started to understand that even more insight could be obtained if electrochemical techniques were combined with additional spectroscopic tools. Among these it is sufficient to mention infrared spectroscopy, Raman spectroscopy, luminescence techniques, electroreflection or ellipsometry. 

Frequently, electrochemical information can be interpreted better in the presence of additional nonelectrochemical information. Typically, however, there is one significant restriction electrochemical and spectroscopic techniques often do not detect exactly the same mechanisms. With spectroscopic measurements (e.g., infrared spectroscopy), products that are formed by electrochemical processes may be detected. In other cases (luminescence techniques) mechanisms may be found by which charge carriers are trapped and recombine. Other techniques (electroreflection studies) allow the nature of electronic transitions to be determined and provide information on the presence or absence of an electric field in the surface of an electrode. With no traditional technique, however, is it... 

Electrolyte contacts have been used to characterize as-deposited and annealed CdS/CdTe solar cell structures by photocurrent spectroscopy and electrolyte elec-troabsorbance/electroreflectance measurements (EEA/EER) [267-269]. 

Duffy NW, Peter LM, Wang RL, Lane DW, Rogers KD (2000) Electrodeposition and characterisation of CdTe films for solar ceU applications. Electrochim Acta 45 3355-3365 Duffy NW, Peter LM, Wang RL (2002) Characterisation of CdS/CdTe heterojunctions by photocurrent spectroscopy and electrolyte electroreflectance/absorbance spectroscopy (EEA/EER). J Electroanal Chem 532 207-214 (see also references therein). 

Chaparro AM, Salvador P, Mir A (1996) The scanning microscope for semiconductor characterization (SMSC) Study of the influence of surface morphology on the photoelectrochemical behavior of an n-MoSe2 single crystal electrode by photocurrent and electrolyte electroreflectance imaging. J Electroanal Chem 418 175-183... 

A relatively new arrangement for the study of the interfacial region is achieved by so-called emersed electrodes. This experimental technique developed by Hansen et al. consists of fully or partially removing the electrode from the solution at a constant electrical potential. This ex situ experiment (Fig. 9), usually called an emersion process, makes possible an analysis of an electrode in an ambient atmosphere or an ultrahigh vacuum (UHV). Research using modem surface analysis such as electron spectroscopy for chemical analysis (ESCA), electroreflectance, as well as surface resistance, electrical current, and in particular Volta potential measurements, have shown that the essential features (e.g., the charge on... 

Cuesta A, Lopez N, Gutierrez C. 2003. Electrolyte electroreflectance study of carbon monoxide adsorption on polycrystalline silver and gold electrodes. Electrochim Acta 48 2949-2956. Date M, Hamta M. 2001. Moisture effect on CO oxidation over Au/Ti02 catalyst. J Catal 201 221-224. 

Reflectance spectroscopy in the infrared and visible ultraviolet regions provides information on electronic states in the interphase. The external reflectance spectroscopy of the pure metal electrode at a variable potential (in the region of the minimal faradaic current) is also termed electroreflectance . Its importance at present is decreased by the fact that no satisfactory theory has so far been developed. The application of reflectance spectroscopy in the ultraviolet and visible regions is based on a study of the electronic spectra of adsorbed substances and oxide films on electrodes. 

The XPS results obtained by Kolb and Hansen are reproduced in Fig. 6 and they clearly demonstrate not only that cations as well as anions stay on the surface but also that the amount of ions exhibits the expected potential dependence even in the case of specific adsorption. The preservation of the double layer charge after emersion was also shown by other techniques like charge monitoring [28] and electroreflectance measurements [29],... 

In order to explain the changing optical properties of AIROFs several models were proposed. The UPS investigations of the valence band of the emersed film support band theory models by Gottesfeld [94] and by Mozota and Conway [79, 88]. The assumption of nonstoichiometry and electron hopping in the model proposed by Burke et al. [87] is not necessary. Recent electroreflectance measurements on anodic iridium oxide films performed by Gutierrez et al. [95] showed a shift of optical absorption bands to lower photon energies with increasing anodic electrode potentials, which is probably due to a shift of the Fermi level with respect to the t2g band [67]. 

Valence Band Spectroscopy. Optical and electronic properties of UPD metal flms on metal electrodes have been studied in situ by means of differential- and electroreflectance spectroscopy [98], Optical absorption bands, however, reflect a combined density of electronic states at a photon energy which is the energetic difference of... 

Electroreflectance effects arising from changing electron densities at the electrode surface as a result of the applied potential. 

This section is primarily concerned with in situ UV-visible spectroscopy and, for the various reasons discussed in the section on electroreflectance, we shall confine the discussion to transmittance techniques. 

Z.Q. Feng, S. Imabayashi, T. Kakiuchi, and K. Niki, Electroreflectance spectroscopic study of the electron transfer rate of cytochrome c electrostatically immobilized on the w-carboxyl alkanethiol monolayer modified gold electrode. J. Electroanal. Chem. 394, 149-154 (1995). 

The initial stages, notably the formation of a monolayer on a foreign substrate at underpotentials, were mainly studied by classical electrochemical techniques, such as cyclic voltammetry [8, 9], potential-step experiments or impedance spectroscopy [10], and by optical spectroscopies, e.g., by differential reflectance [11-13] or electroreflectance [14] spectroscopy, in an attempt to evaluate the optical and electronic properties of thin metal overlayers as function of their thickness. Competently written reviews on the classic approach to metal deposition, which laid the basis of our present understanding and which still is indispensable for a thorough investigation of plating processes, are found in the literature [15-17]. 

The reflectivity of bulk materials can be expressed through their complex dielectric functions e(w) (i.e., the dielectric constant as a function of frequency), the imaginary part of which signifies absorption. In the early days of electroreflectance spectroscopy the spectra were often interpreted in terms of the dielectric functions of the participating media. However, dielectric functions are macroscopic concepts, ill suited to the description of surfaces, interfaces, or thin layers. It is therefore preferable to interpret the data in terms of the electronic transitions involved wherever possible. 

Electronic transitions from occupied bulk states to surface states decrease the reflectivity at the associated energy and show up as positive or negative peaks - remember these are difference spectra - in the electroreflectance spectra. Figure 15.10 shows the spectra of a Ag(100) electrode at normal incidence for various values of the electrode potential. Two sets of peaks are prominent one near 1 eV and the other near 3 eV. The first set is caused by electronic transitions into the lower surface state B] the other set corresponds to state A. As expected, both peaks shift toward higher energies as the electrode... 

Electroreflectance spectroscopy has been successfully applied to numerous other systems such as oxide films or adsorbed dyes. It is most useful when the observed features can be related to specific electronic transitions. As an example we mention the reactions of a film of Prussian Blue adsorbed on gold or platinum. Prussian Blue can be oxidized to Berlin Green, or reduced to Prussian White. The appearance of the products gives rise to characteristic features in the electroreflectance spectra [11]. 

Figure 15.10 Normal-incidence electroreflectance spectrum of Ag(100) in 0.5 M NaF solutions for various bias potentials. Reprinted from Ref. 10 with...

---