Measurements electrochemical photocurrent

Electrochemical Photocurrent Measurements (Optical/Electrical Method Class), Introduction of a New Model... 

Since photoelectrochemistry is not limited to photocurrent measurements, it may at this point be useful to think about some general new research possibilities to be expected from the combination of electrochemical and microwave measurements. Table 1 shows obvious combination possibilities between electrochemical and microwave measurements. 

The combination of photocurrent measurements with photoinduced microwave conductivity measurements yields, as we have seen [Eqs. (11), (12), and (13)], the interfacial rate constants for minority carrier reactions (kn sr) as well as the surface concentration of photoinduced minority carriers (Aps) (and a series of solid-state parameters of the electrode material). Since light intensity modulation spectroscopy measurements give information on kinetic constants of electrode processes, a combination of this technique with light intensity-modulated microwave measurements should lead to information on kinetic mechanisms, especially very fast ones, which would not be accessible with conventional electrochemical techniques owing to RC restraints. Also, more specific kinetic information may become accessible for example, a distinction between different recombination processes. Potential-modulation MC techniques may, in parallel with potential-modulation electrochemical impedance measurements, provide more detailed information relevant for the interpretation and measurement of interfacial capacitance (see later discus-... 

Another impedance-based imaging technique for laterally resolved characterization of thin films or electrochemical systems is Scanning Photo-induced Impedance Microscopy (SPIM) [44]. It is based on photocurrent measurements at field-effect structures. In their simplest arrangement, field-effect structures consist of a semiconductor substrate with a thin insulator, and a gate electrode. This gate electrode can be a metal film resulting in the structure Metal Insulator Semiconductor (MIS) or, alternatively. Electrolyte Insulator Semiconductor structures are used, in which the electrolyte is in direct contact with the insulator, and a reference electrode is required to fulfill the function of the gate electrode. 

As in all potentiostatic techniques, the double layer charging is a parallel process to the faradaic reaction that can substantially attenuate the photocurrent signal at short-time scale (see Section 5.3)" . This element introduces another important difference between fully spectroscopic and electrochemical techniques. Commercially available optical instrumentation can currently deliver time resolution of 50 fs or less for conventional techniques such as transient absorption. On the other hand, the resistance between the two reference electrodes commonly employed in electrochemical measurements at the liquid/liquid interfaces and the interfacial double layer capacitance provide time constants of the order of hundreds of microseconds. Consequently, direct information on the rate of heterogeneous electron injection from/to the excited state is not accessible from photocurrent measurements. These techniques do allow sensitive measurements of the ratio between electron injection and decay of the excited state under pho-tostationary conditions. Other approaches such as photopotential measurements, i.e. relative changes in the Fermi levels in both phases, can provide kinetic information in the nanosecond regime. 

The layer-by-layer structure of dithiol SAM and CdS monolayer was confirmed with X-ray photoelectron spectroscopy, Fourier transform infrared reflection-absorption spectroscopy, and inductively coupled plasma mass spectroscopy at each step of composite-film preparation. Photocurrent measurements revealed that the mono-layers of CdS nanoparticles were immobilized without mutual aggregation of particles [36]. Cadmium selenide nanoparticles were prepared electrochemically on gold substrates modified with alkanethio-lated -cyclodextrin SAMs [37]. 

The semiconducting properties of an electrochemically generated film of polybithiophene was studied by Fikus et al. [1008]. The value of the flat band potential for the p-type semiconducting polymer in its reduced state sCE = 0.6 V was confirmed by in situ photocurrent measurements. 

The boost in the photocurrent density mainly occurs due to the molecular complex formation between the diethyl oxalate and redox species in the electrolyte solution that promotes the electrochemical properties of electrolyte. Also, electrochemical impedance measurements indicate that adsorption of diethyl oxalate on the semiconductor surface leads to an incensement in the lifetime and the electron density in the conduction band of li02 that shifts the Fermi level, which leads to a small enhancement in the volatile organic compoimd (VOC). 

Stationary microwave electrochemical measurements can be performed like stationary photoelectrochemical measurements simultaneously with the dynamic plot of photocurrents as a function of the voltage. The reflected photoinduced microwave power is recorded. A simultaneous plot of both photocurrents and microwave conductivity makes sense because the technique allows, as we will see, the determination of interfacial rate constants, flatband potential measurements, and the determination of a variety of interfacial and solid-state parameters. The accuracy increases when the photocurrent and the microwave conductivity are simultaneously determined for the same system. As in ordinary photoelectrochemistry, many parameters (light intensity, concentration of redox systems, temperature, the rotation speed of an electrode, or the pretreatment of an electrode) may be changed to obtain additional information. 

McCann JE, Pezy J (1981) The measurement of the Hatband potentials of n-type and p-type semiconductors by rectified alternating photocurrent voltammetry. J Electrochem Soc 128 1735-1740... 

To compare quantitatively the current-voltage characteristic of an illuminated electrode, given by formula (31), with experimental data, Butler (1977) and Wilson (1977) measured the photocurrent, which arises in a cell with an n-type semiconductor photoanode ( 2, W03) when irradiated with monochromatic light at a frequency satisfying the condition ha>> Eg. In this case a light-stimulated electrochemical reaction of water oxidation with oxygen evolution... 

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