Mesoporous Silicon

C, and one obtains nanowires of Sn02. If the same is done in a mesoporous template of silicon, the silicon acts as a reducing agent. Depending on temperature, the products are nanowires of SnSe or of tin (Fig. 20.4). 

For application of protein-immobilized porous materials to sensor fields, use of an electroactive substance as the framework material is important. DeLouise and Miller demonstrated the immobilization of glutathione-S-transferase in electrochemically etched porous silicon films [134], which are attractive materials for the construction of biosensors and may also have utility for the production of immobilized enzyme bioreactors. Not limited to this case, practical applications of nanohybrids from biomolecules and mesoporous materials have been paid much attention. Examples of the application of such hybrids are summarized in a later section of this chapter. 

Gao, T. Gao, J. Sailor, M. J., Tuning the response and stability of thin film mesoporous silicon vapor sensors by surface modification, Langmuir. 2002, 18, 9953 9957... 

If the wafer is not fixed in the cell, a mechanical wafer support is advisable. The ohmic contact can be an integral part of such a sample fixture, as shown in Fig. 1.5 a. During formation of mesoporous silicon on highly doped substrates at low bias (0-1.5 V), it was found that such a contact can even be immersed into the electrolyte without a significant degradation of its electrical properties. It is remarkable that mesoporous silicon formation takes place under the contact, too, without significant degradation of the contact properties. 

The etch rate is further increased if H202 is added to the solution, as shown in Fig. 2.5 b. At such low rates the reaction is controlled by the kinetics of the reaction at the interface and not by diffusion in the solution. This etching solution is therefore found to be perfect to remove micro- and mesoporous silicon selectively from a bulk silicon substrate or to increase the diameter of meso- or macropores in an well-controlled, isotropic manner [Sa3],... 

An electric field in the semiconductor may also produce passivation, as depicted in Fig. 6.1c. In semiconductors the concentration of free charge carriers is smaller by orders of magnitude than in metals. This permits the existence of extended space charges. The concept of pore formation due to an SCR as a passivating layer is supported by the fact that n-type, as well as p-type, silicon electrodes are under depletion in the pore formation regime [Ro3]. In addition a correlation between SCR width and pore density in the macroporous and the mesoporous regime is observed, as shown in Fig. 6.10 [Thl, Th2, Zh3, Le8]. 

The smallest pores that can be formed electrochemically in silicon have radii of < 1 nm and are therefore truly microporous. However, confinement effects proposed to be responsible for micropore formation extend well into the lower mesoporous regime and in addition are largely determined by skeleton size, not by pore size. Therefore the IUPAC convention of pore size will not be applied strictly and all PS properties that are dominated by quantum size effects, for example the optical properties, will be discussed in Chapter 7, independently of actual pore size. Furthermore, it is useful in some cases to compare the properties of different pore size regimes. Meso PS, for example, has roughly the same internal surface area as micro PS but shows only negligible confinement effects. It is therefore perfectly standard to decide whether observations at micro PS samples are surface-related or QC-related. As a result, a few properties of microporous silicon will be discussed in the section about mesoporous materials, and vice versa. Properties of PS common to all size regimes, e.g. growth rate, porosity or dissolution valence, will be discussed in this chapter. 

If the pore density is plotted versus the doping density of the silicon electrode, it can be seen that the micropore density is independent of doping, while the macropore and mesopore densities increase linearly with doping density, as shown in Fig. 6.10. This is a consequence of the QC formation mechanism being independent of doping, while the SCR-related mechanisms are not, as discussed in Section 6.2. 

Fig. 7.8 The below-bandgap transmission of free-standing mesoporous silicon compared to the bulk transmission of the corresponding n+ and p+ substrates. The strong increase in...

Microcrystallites of direct semiconductors usually show a simple exponential decay of the PL intensity P with time, with time constants r in the ps and ns range at RT. A similar simple exponential decay (r = 20ms at 2 K) is observed for PL from mesoporous silicon of high porosity, which shows a weak confinement effect... 

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