Polysilanes, linear properties

In addition to photoconductivity, polysilanes have been found to exhibit marked nonlinear optical properties,95-97 suggesting that they may eventually be useful in laser and other optical technology. The third-order non-linear susceptibility, X3, is a measure of the strength of this effect. The non-linear properties of polysilanes, like the absorption spectra, seem to be dependent on chain conformation and are enhanced for polymers having an extended, near anti conformation (Table 5.5). The value of 11 x 10 12 esu observed for (n-Hex2Si) below its transition temperature is the largest ever observed for a polymer which is transparent in the visible region. 

The history and development of polysilane chemistry is described. The polysilanes (polysilylenes) are linear polymers based on chains of silicon atoms, which show unique properties resulting from easy delocalization of sigma electrons in the silicon-silicon bonds. Polysilanes may be useful as precursors to silicon carbide ceramics, as photoresists in microelectronics, as photoinitiators for radical reactions, and as photoconductors. 

In any event, between 1951 and 1975, no papers appeared on polysilane high polymers. However, linear permethylpolysilanes of the type MelSiMezhiMe were prepared and studied, especially by Kumada and his students,(5) and cyclic polysilanes were being investigated in several laboratories.(6,7) Studies of the permethyl-cyclosilanes, (Me2Si)n where n = 4 to 7, showed that these compounds exhibit remarkable delocalization of the ring sigma electrons, and so have electronic properties somewhat like those of aromatic hydrocarbons.(6)... 

Physical properties of the polysilanes depend greatly upon the nature of the organic groups bound to silicon. A few of the many polysilanes are listed in Table I. Typically the linear polysilanes are thermoplastics, soluble in organic solvents like toluene, ethers,... 

The second approach to linear polysilanes is based on the modification of polysilanes prepared by the reductive coupling method. The severe conditions of this reaction allow only alkyl or aryl substituents at the silicon atom in the starting dichlorosilane. Therefore only alkyl or aryl substituted polysilanes are known. We have successfully prepared new polysilanes with pendant alkoxy and amino side groups. This approach allows fine tuning of the properties of... 

Such a structure would be more rigid than a polysilane and contain a range of structural elements, accounting for the observed spectroscopic properties, but would still be soluble due to its semi-linear nature. 

The proton NMR spectral data of organopolysilanes have often been published incidental to preparative studies (51, 54, 62, 74, 108, 119, 177, 187, 190). Only recently has a systematic investigation to determine the chemical shifts and coupling constants in linear and cyclic permethylated polysilanes, and to study the effects of substituents on the NMR properties of methyl derivatives of disilane and trisilane been reported (see Table V-VII) (206). 

The ct-ct conjugation along Si-Si bonds in linear and reticulated polysilanes results in valuable optical and charge transport properties, with broad... 

In phenyl-substituted polysilanes, the problems become more complicated because the benzene n electron system is mixed with the a (Si-Si) orbitals and the highest occupied molecular orbital is assigned to a linear combination of 7r (C6H5) and a (Si—Si) orbitals452. Similar properties are found in mixed-substituted methyl-phenylpolysilanes, where the effect of extension of the 3 d molecular orbitals of the polysilane-chain is found to be minimal453. ... 

The decisive question whether linear or branched silanes are formed preferentially is thus answered the properties of the final polysilane depend on this difference. Tetrasilanes 3 and 4 can continue reacting with TCDMS to give a rapidly increasing variety of products. 

The situation is somewhat more complicated in two-dimensional polysilanes, which have intermediate properties between the one-dimensional chain-like polysilanes and three-dimensional bulk silicon. The gap is of a quasi-direct nature as the indirect gap is only slightly smaller than the direct one [11]. However, the excitons strongly bind to the lattice which results in a large Stokes shift of the PL [26]. The observed blue shift of the absorption and photoluminescence with decreasing size of the polysilanes is considered to be due to confinement effects of the excitons [12,26]. The strong coupling of the exciton to the lattice decreases somewhat the blue shifts as compared with the linear chains, and it results in a stronger localization of the exciton over a smaller number of Si atoms [12,26]. 

By the way, although a dominant majority of papers concerning the formation of amorphous SiC layers describes appUcations of CVD or PVD techniques, there have also been some attempts to use the polymer route for preparing SiC films. Starting from solutions of various polysilanes or polycarbosilanes, frequently films are formed by spin-coating and pyrolyzed under inert atmosphere [215-218]. Of course, such a procedure does not form a part of this section SiC layers via gas phase reactions . However, in this connection it should be mentioned that polysilanes are also applied to form films via evaporation, not only with the aim to build amorphous and/or crystalline SiC films, but also to use special properties of the polysilane films themselves, i.e. without a subsequent pyrolysis of these films. Such amorphous films are characterized by non-linear optical effects [219, 220] and their properties may be controlled by the uniformity of the orientation of polysilane chains which is susceptible to epitaxial influences [221-223]. 

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