Semiconductor interfaces

Contacts between semiconductors on one side, and metals, electrolyte solutions, and other semiconductors are pervasive in today s technology. Contacts between semiconductors and various types of molecular environments are increasingly found in advanced application such as organic light-emitting diodes. Understanding the electrical properties of semiconductor interfaces starts again with the relatively simple 

A detailed answer to this question can be found in many texts on semiconductors and semiconductor interfaces. Here we just outline the main points of this theory and make a few observations that will be referred to elsewhere in this text  

As in Section 4,5.2, the solution to this problem is obtained from the Poisson equation (1.219), which is again needed in one dimension 

In turn, the excess charge density Spq(x) depends on the local potential. To see 

This case is completely analogous to the case of ionic solution that was treated in Section 1.6.3. Indeed, Eq. (4.151) is identical to (1.247). For e 5 t kpT we can proceed along the same lines as in that treatment to obtain (cf. Eq. (1.253)) 

In turn, the excess charge density Spq x) depends on the local potential. To see this consider Eqs (4.127) and (4.129) for the densities of electrons in the conduction band and holes in the valence bands. These equations where written for a system where the potential is uniform everywhere (and can therefore be taken zero). The presence of an additional potential 54 (r ) at positions has the effect of shifting the local electron energy by —ei54 (x). Under the approximation that yields (4.132) the corresponding local electron and hole densities become 

Transparent conducting oxides are widely used as electrodes in thin film optoelectronic devices as solar cells and light emitting diodes because of their transparency for visible light and their high electrical conductivity. Highest optical transparency and electrical conductivity are thus key aspects for such applications. Most work on TCO electrodes is, therefore, dedicated to find deposition parameters, which improve these material parameters. In addition, contact properties are essential for the application of TCOs as electrodes. 

The issue of Schottky barrier formation to ZnO is not treated in this chapter as such contacts are not of big importance in thin-film solar cells. This is related to the fact that in thin film solar cells metals are only used to contact highly-doped films. For degenerately doped semiconductors, the barrier heights become very small because of the large space charge associated with depletion layers in such materials. 

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Figure Bl.22.4. Differential IR absorption spectra from a metal-oxide silicon field-effect transistor (MOSFET) as a fiinction of gate voltage (or inversion layer density, n, which is the parameter reported in the figure). Clear peaks are seen in these spectra for the 0-1, 0-2 and 0-3 inter-electric-field subband transitions that develop for charge carriers when confined to a narrow (<100 A) region near the oxide-semiconductor interface. The inset shows a schematic representation of the attenuated total reflection (ATR) arrangement used in these experiments. These data provide an example of the use of ATR IR spectroscopy for the probing of electronic states in semiconductor surfaces [44]-...

Katzenellenbogen N and Grischkowsky D 1991 Efficient generation of 380 fs pulses of THz radiation by ultrafast laser pulse excitation of a biased metal-semiconductor interface Appl. Phys. Lett. 58 222-4... 

Metals for Schottl Contacts. Good Schottky contacts on semiconductor surfaces should not have any interaction with the semiconductor as is common in ohmic contacts. Schottky contacts have clean, abmpt metal—semiconductor interfaces that present rectifying contacts to electron or hole conduction. Schottky contacts are usuaHy not intentionaHy annealed, although in some circumstances the contacts need to be able to withstand high temperature processing and maintain good Schottky behavior. 

Applications of CL to the analysis of electron beam-sensitive materials and to depth-resolved analysis of metal-semiconductor interfaces by using low electron-beam energies (on the order of 1 keV) will be extended to other materials and structures. 

To obtain a relationship between the voltage VK applied to the metal and the surface potential Vv, we assume a continuity of the electric field at the insulator-semiconductor interface that implies... 

In the case of negative bias, the Fermi level moves closer to the valence band edge. Consequently, the concentration of the majority of carriers (holes) at die insulator-semiconductor interface becomes laiger than in the bulk. This corresponds to the accumulation regime. When a positive bias is applied to die metal, the... 

In Eq. (14.16), the sign of the right hand side equals that of the applied bias. The total charge in the semiconductor, Qt, is related to the electric field at the insula-tor-semiconductor interface, F according to Gauss s law ... 

Figure 7. Example of space-resolved photoinduced microwave conductivity mapping of semiconductor interface distribution of photoconductivity in natural pyrite (from Murgul, Turkey, surface etched in acid solution). The overflow was adjusted to show patterns of low photoactivity. For color version please see color plates opposite p. 452.

These three equations (11), (12), and (13) contain three unknown variables, ApJt kn and sr The rest are known quantities, provided the potential-dependent photocurrent (/ph) and the potential-dependent photoinduced microwave conductivity are measured simultaneously. The problem, which these equations describe, is therefore fully determined. This means that the interfacial rate constants kr and sr are accessible to combined photocurrent-photoinduced microwave conductivity measurements. The precondition, however is that an analytical function for the potential-dependent microwave conductivity (12) can be found. This is a challenge since the mathematical solution of the differential equations dominating charge carrier behavior in semiconductor interfaces is quite complex, but it could be obtained,9 17 as will be outlined below. In this way an important expectation with respect to microwave (photo)electro-chemistry, obtaining more insight into photoelectrochemical processes... 

In the following section the mathematical derivation of the stationary, potential-dependent, photoinduced microwave conductivity signal, which integrates over all photogenerated charge carriers in the semiconductor interface, is explained. This is a necessary requirement for the interpretation of the PMC-potential curves. 

Experimental evidence with very different semiconductors has shown that at semiconductor interfaces where limited surface recombination and a modest interfacial charge-transfer rate for charge carriers generate a peak... 

Figure 28. Semiconductor interfaces with increasing electric fields in the space charge layer (from top to bottom) compared with tubes of different diameters through which an equivalent amount of water is pressed per unit time (equivalent to limiting current).

Surface recombination processes of charge carriers are mechanisms that cannot easily be separated from real semiconductor interfaces. Only a few semiconductor surfaces can be passivated to such an extent as to permit suppression of surface recombination (e.g., Si with optimized oxide or nitride layers). A pronounced dip is typically seen between the potential-dependent PMC curve in the accumulation region and the photocurrent potential curve (e.g., Fig. 29). This dip may be partially caused by a surface... 

Similar results have recently been reported by Aspnes and Heller. They proposed an autocatalytic model for photoactive systems involving metal/compound semiconductor interfaces. To explain induction times in CdS systems (.9), they suggest that hydrogen incorporated in the solid lowers the barrier to charge transfer across the interface and thereby accelerates H2 production rates. 

A number of solid compounds have been examined with this time-domain method since the first report of coherent phonons in GaAs [10]. Coherent phonons were created at the metal/semiconductor interface of a GaP photodiode [29] and stacked GaInP/GaAs/GalnP layers [30]. Cesium-deposited [31-33] and potassium-deposited [34] Pt surfaces were extensively studied. Manipulation of vibrational coherence was further demonstrated on Cs/Pt using pump pulse trains [35-37]. Magnetic properties were studied on Gd films [38, 39]. 

The term photovoltaic effect is further used to denote non-electrochemical photoprocesses in solid-state metal/semiconductor interfaces (Schottky barrier contacts) and semiconductor/semiconductor pin) junctions. Analogously, the term photogalvanic effect is used more generally to denote any photoexcitation of the d.c. current in a material (e.g. in solid ferroelectrics). Although confusion is not usual, electrochemical reactions initiated by light absorption in electrolyte solutions should be termed electrochemical photogalvanic effect , and reactions at photoexcited semiconductor electodes electrochemical photovoltaic effect . 

The sensitizers display a crucial role in harvesting of sunlight. To trap solar radiation efficiently in the visible and the near IR region of the solar spectrum requires engineering of sensitizers at a molecular level (see Section 9.16.3).26 The electrochemical and photophysical properties of the ground and the excited states of the sensitizer have a significant influence on the charge transfer (CT) dynamics at the semiconductor interface (see Section 9.16.4). The open-circuit potential of the cell depends on the redox couple, which shuttles between the sensitizer and the counter electrode (for details see Section 9.16.5). 

The adsorbed sensitizers in the excited state inject an electron into the conduction band of the semiconductor substrate, provided that the excited state oxidation potential is above that of the conduction band. The excitation of the sensitizer involves transfer of an electron from the metal t2g orbital to the 7r orbital of the ligand, and the photo-excited sensitizer can inject an electron from a singlet or a triplet electronically excited state, or from a vibrationally hot excited state. The electrochemical and photophysical properties of both the ground and the excited states of the dye play an important role in the CT dynamics at the semiconductor interface. 

A constant bias potential is applied across the sensor in order to form a depletion layer at the insulator-semiconductor interface. The depth and capacitance of the depletion layer changes with the surface potential, which is a function of the ion concentration in the electrolytic solution. The variation of the capacitance is read out when the semiconductor substrate is illuminated with a modulated light and the generated photocurrent is measured by means of an external circuit. 

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