Capacitance transient techniques

Capacitance transient spectroscopy encompasses a powerful set of techniques to detect and characterise deep levels in semiconductors. The list of techniques applied for III-V nitrides includes deep level transient spectroscopy (DLTS) [1,2], double correlation DLTS (DDLTS) [3], isothermal capacitance transient spectroscopy (ICTS) [2], photoemission capacitance transient spectroscopy (ODLTS) [4] and optical ICTS (OICTS) [5], This Datareview presents the current status of deep level studies by capacitance transient techniques for III-V nitrides. A brief introduction to the techniques is given, followed by an example that demonstrates the application of DLTS and DDLTS for Si-doped... 

The measurements utilise one-sided pn junction (p+n or pn ) and Schottky diodes, which possess a voltage modulated space charge region near the p/n and metal/semiconductor interface, respectively [8], The common feature of capacitance transient techniques is that the electronic properties of deep levels are determined by monitoring the transient high-frequency differential capacitance response of the diode as the electron occupancy of metastably charged deep levels located within the space charge... 

As the field of electrochemical kinetics may be relatively unfamiliar to some readers, it is important to realize that the rate of an electrochemical process is the current. In transient techniques such as cyclic and pulse voltammetry, the current typically consists of a nonfaradaic component derived from capacitive charging of the ionic medium near the electrode and a faradaic component that corresponds to electron transfer between the electrode and the reactant. In a steady-state technique such as rotating-disk voltammetry the current is purely faradaic. The faradaic current is often limited by the rate of diffusion of the reactant to the electrode, but it is also possible that electron transfer between the electrode and the molecules at the surface is the slow step. In this latter case one can define the rate constant as ... 

The simplest and most commonly used method for determination of a double layer s capacitance is the galvanostatic (constant-current) transient technique. 

The plot V = f(t), in the microseconds range, is a straight line with slope dVIdt. Thus, the double-layer capacitance Qj may be calculated by means of Eq. (4.17) using the slope (dV/dt) provided by the experimental data. One example of such calculations is presented in Problem 4.2. Galvanostatic transient technique is discussed in detail in Section 6.9. 

Galvanostatic Transient Technique Double-Layer Capacitance Measurements. The value of the fractional surface coverage 9 may be inferred by means of doublelayer capacitance data. As discussed in Section 6.9, the double-layer capacitance C may, in turn, be determined by means of a transient technique. In the galvanostatic transient technique (as in Fig. 6.18), the duration of the constant-current (density) pulse is on the order of microseconds. In the microsecond time range the only process taking place at the electrode is charging of the double layer. Flence, in this case, Eq. (6.96) reduces to... 

In Table IV we present Eai and Ei0 data on two important deep centers in GaAs, Cr, and O (EL2). The results from three different laboratories are included, but no attempt was made to show everything available in the literature. It is clear that neither the Eai results nor the Ei0 results agree well for Cr, but are not too bad for O. In contrast, the TDH measurements of El0, shown in Table II, are much more consistent. It should be noted that the TDH samples (Table II) were semi-insulating, whereas the emission-spectroscopy samples (Table IV) were conducting in order that capacitance transient (DLTS) experiments could be performed. The PITS and OTCS techniques applied to these samples would have been unable to clearly distinguish between hole and electron traps. 

When transient techniques are employed for fundamental research on these and other subjects, the effect of double-layer charging has to be accounted for in the analysis procedures. It has been observed frequently that at solid—solution interfaces, this process does not obey the capacitive behaviour predicted by double-layer theories. For example, the doublelayer admittance, Fc, cannot be represented by Yc = jciCd, but rather follows the relation [118]... 

The most widely used of these methods in the study of a-Si H have been field-effect, capacitance, and deep level transient spectroscopy (DLTS) measurements. Capacitance measurements actually include quite a number of variations such as capacitance versus applied voltage (C- V), frequency (C- w), or temperature (C-T), and also several kinds of distinct capacitance profiling techniques. The technique referred to as DLTS normally includes both capacitance-transient as well as current-transient measurements and will also be used as a generic term for such recent variations as isothermal capacitance transient spectroscopy (ICTS), constant capacitance methods, and the like. 

Photoluminescence (PL) and EL spectroscopy can be used to determine the presence of traps. Other techniques include current voltage measurements, capacitance voltage measurements, capacitance transient spectroscopy, and admittance spectroscopy. Under favorite conditions, the identification of the nature of the trap is possible. 

This last point, which has been ignored until now, in fact imposes limitations on all transient techniques. Essentially, in addition to the faradaic current flowing in response to a potential perturbation, there is also a current due to the charging of the electrochemical double-layer capacitance (for more details see Chapter 5). In chronoamperometry this manifests itself as a sharp spike in the current at short times, which totally masks the faradaic current. The duration of the double layer charging spike depends upon the cell configuration, but might typically by a few hundred microseconds. Since It=o cannot be measured directly it is necessary to resort to an extrapolation procedure to obtain its value, and whilst direct extrapolation of an /Vs t transient is occasionally possible, a linear extrapolation is always preferable. In order to see how this should be done we must first solve Pick s 2nd Law for a potential step experiment under the conditions of mixed control. The differential equations to be solved are... 

This relationship is used in the capacitance-voltage technique for profiling carrier concentrations near diode junctions and is usable for any type of diode in which one side of the junction is much more heavily doped than the other. It can also be used in a transient mode to detect and analyze point defects as they charge and discharge with bias voltage changes. 

The differential capacitance method cannot be used for reactive metals, such as transition metals in aqueous solutions, on which the formation of a surface oxide occurs over a wide potential re ion. An immersion method was thus developed by Jakuszewski et al. 3 With this technique the current transient during the first contact of a freshly prepared electrode surface with the electrolyte is measured for various immersion potentials. The electrode surface must be absolutely clean and discharged prior to immersion.182-18 A modification of this method has been described by Sokolowski et al. The values of obtained by this method have been found to be in reasonable agreement with those obtained by other methods, although for reactive metals this may not be a sufficient condition for reliability. 

For capacity measurements, several techniques are applicable. Impedance spectroscopy, lock-in technique or pulse measurements can be used, and the advantages and disadvantages of the various techniques are the same as for room temperature measurements. An important factor is the temperature dependent time constant of the system which shifts e.g. the capacitive branch in an impedance-frequency diagram with decreasing temperature to lower frequencies. Comparable changes with temperature are also observed in the potential transients due to galvanostatic pulses. 

Finally, we quote some recent results of Pons (1980), who also used transient capacitance techniques to determine the temperature dependences of the (EL2) and Cr energy levels. In the room-temperature range, his results, designated by a superscript P are... 

The only transient-spectroscopic techniques capable of determining concentration are those involving capacitance, such as the original DLTS. Even for DLTS this measurement is not always possible, and, in any case, it is not feasible to use the capacitive techniques with SI material. Thus, none of the various methods discussed here are, by themselves, very useful for determining impurity or defect concentrations in SI GaAs. That is, they are more qualitative than quantitative. 

Volume 21, Part C, is concerned with electronic and transport properties, including investigative techniques employing field effect, capacitance and deep level transient spectroscopy, nuclear and optically detected magnetic resonance, and electron spin resonance. Parameters and phenomena considered include electron densities, carrier mobilities and diffusion lengths, densities of states, surface effects, and the Staebler-Wronski effect. 

Figure 5 represents an ideal reversible one-electron transfer process in the absence of drop or capacitative charging current, although in real experiments contributions to the response from both these terms are unavoidable. Figure 6 shows the effect of uncompensated resistance for both transient and steady-state voltammograms, whilst Fig. 7 shows the influence of double layer capacitance on a cyclic voltammetric wave. Note that for steady-state voltammetric techniques only very low capacitative charging... 

The first of these approaches is used in the technique of deep level transient spectroscopy (DLTS), which is perhaps the most common experiment for measuring deep levels in crystalline semiconductors (Lang 1974). The DLTS experiment is the measurement of the transient capacitance of a Schottky contact to the sample and is... 

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