Silicon discovery

Generally speaking, there is every ground to classify silicon as an element of antiquity. Its compounds were known and used from time immemorial (suffice it to mention silicon tools of primitive man). We classified carbon as an element of antiquity since it was known in a free state from very remote times. However, that carbon is a chemical element became clear only two hundred years ago. Glass, in the long run, is also a silicon material. However, the date of silicon discovery is the date of its preparation in a free state since such is the established practice in the history of science. 

In 1824 Berzelius, generally credited with the discovery, prepared amorphous silicon by the same general method and purified the product by removing the fluosilicates by repeated washings. Deville in 1854 first prepared crystalline silicon, the second allotropic form of the element. 

Raman spectrometry is another variant which has become important. To quote one expert (Purcell 1993), In 1928, the Indian physicist C.V. Raman (later the first Indian Nobel prizewinner) reported the discovery of frequency-shifted lines in the scattered light of transparent substances. The shifted lines, Raman announced, were independent of the exciting radiation and characteristic of the sample itself. It appears that Raman was motivated by a passion to understand the deep blue colour of the Mediterranean. The many uses of this technique include examination of polymers and of silicon for microcircuits (using an exciting wavelength to which silicon is transparent). 

Silicon in the elemental state has important electronic applications as a semiconductor that were developed only during the last decade. The discovery of these uses was possible only after methods were developed for preparing silicon of extremely high purity. Reduction of Si02 with... 

And Maher goes on explicitly to underline the conclusions about confirmatory weight that he sees as illustrated by this episode. He claims that Mendeleev s prediction of the existence of the third of the new elements, eka-silicon (aka germanium), was initially regarded as quite unlikely to be true but then later, with the discovery of the first two new elements (gallium and scandium), confidence in the prediction of the existence of the third new element became so high that its eventual empirical confirmation was widely regarded as a matter of course. Maher writes ... 

This fundamental discovery dramatically affected the whole chemistry of main-group elements. Subsequently, a series of new compounds with silicon element multiple bonds has been introduced. Within only a few years, stable silenes (silaethenes with a Si = C double bond) [8-11], silaimines Si = N [12-14], and silaphosphenes Si = P [15] were synthesized. As a pacemaker, silicon chemistry has exerted a strong influence on further areas of main-group chemistry a variety of stable molecules with Ge = Ge [16], P = P [17], As = As [18], P = C and P = C [19-22] bonds were subsequently isolated, and systems with cumulated double bonds P = C = P [23-25] are also known today. 

Very recently, the coordination chemistry of low valent silicon ligands has been established as an independent, rapidly expanding research area. With the discovery of stable coordination compounds of silylenes [35-38], a major breakthrough was achieved. Within a short time a variety of stable complexes with a surprising diversity of structural elements was realized. Besides neutral coordination compounds (A, B) [35, 36, 38], and cationic compounds (C) [37], also cyclic bissilylene complexes (D) [39,40] exist. A common feature of the above-mentioned compounds is the coordination of an additional stabilizing base (solvent) to the silicon. However, base-free silylene complexes (A) are also accessible as reactive intermediates at low temperatures. 

The radical-based functionalization of silicon surfaces is a growing area because of the potential practical applications. Although further knowledge is needed, the scope, limitations, and mechanism of these reachons are sufficiently well understood that they can be used predictably and reliably in the modification of hydrogen-terminated silicon surfaces. The radical chemistry of (TMSlsSiH has frequently served as a model in reactions of both hydrogen-terminated porous and flat silicon surfaces. We trust that the survey presented here will serve as a platform to expand silicon radical chemistry with new and exciting discoveries. 

The flexibility of the synthesis method provides for opportunities to incorporate other elements besides silicon. One of the first elements added was Al (11). Soon after the discovery of the silicon based TUD-1, it was found that adding suitable aluminum sources to the above procedure yielded very similar Al-Si-TUD-1 stractures. Since then, many other TUD-1 variants have been prepared. Most TUD-1 variants are either Si-TUD-1 or an M-Si version, where M is another element (e.g.,... 

Ever since their discovery in 1967, there has been interest in the kinds of rearrangements that silenes might undergo and curiosity about the behavior of the silicon-carbon double bond as compared to that of the carbon-carbon double bond. 

The classic problem of the silicon-silicon double bond dates back at least to the early part of this century, when F. S. Kipping and his students attempted unsuccessfully to synthesize disilenes. Evidence for the probable transient existence of disilenes began to appear in the 1970s, but it was the isolation of the stable disilene 1 in 19811 that opened up modem disilene chemistry. The early history of this discovery has been recounted in a review2 several other reviews covering Si=Si double bonds have been published.2 5... 

Professor Mailer and I have enjoyed cordial relations for over thirty years, but this is the first time he and I have been honored together for our separate and almost simultaneous discovery of what has become known as the Mttller-Rochow Process. It is a great pleasure, and a source of much personal satisfaction to us, that we have both been awarded the "Wacker Silicon-Preis" during the stimulating and enjoyable "Munich Silicon Days 92". 

Transition-metal chemistry is currently one of the most rapidly developing research areas. The record of investigation for compounds with metal silicon bonds is closely comparable to that for silicones it was in 1941 when Hein discovered the first metal silicon complex, followed by Wilkinson in 1956. A milestone in the development of this chemistry was Speier s discovery of the catalytic activity of nobel metal complexes in hydrosilylation reactions in 1977. Hydrosilylation is widely used in modem organic syntheses as well as in the preparation of organo functionalized silicones. Detailed investigations of the reaction mechanisms of various catalysts continue to be subject of intense research efforts. 

A turning point in the study of amorphous semiconductors was reached with the discovery that the addition of hydrogen to amorphous silicon could dramatically improve the material s optical and electrical properties. Unlike pure amorphous silicon, which is not photoconductive and cannot be readily doped, hydrogenated amorphous silicon (a-Si H) displays a photoconductive gain of over six orders of magnitude and its dark conductivity can be changed by over ten orders of magnitude by n-type or p-type... 

Accidently, using hexafluoro-p-xylene with the contaminated copper wire obtained from the precursor method experiments, a polymer film was deposited on the silicon substrates. Obviously, some dibromotetrafluoro-p-xylene from the precursor method that adhered to, or reacted with, the metal could somehow initiate this VDP process. However, a complete explanation of these results is not yet available. As an extension of this discovery, commercially available 1,4-bis(trifluoromethyl)benzene in conjunction with a catalyst/initiator has proved to be a potential alternative by which to deposit poly(tetrafluoro-p-xylylene) film successfully.23... 

More than 60 years after its simultaneous discovery by Rochow and Muller, the direct reaction of copper-activated silicon with alkyl chlorides is arguably still the most important industrial process for the preparation of basic organosilanes. An inspiring historic account highlighting the significance of this seminal work has been given by Seyferth.12 A comprehensive review on the subject has been written by Jung and Yoo.13 The most recent work associated with the direct process is concerned with the role of metallic promoters, such as Zn and Cd, as well as mechanistic aspects.14... 

Figure 1. Progress in the discovery of morphological phenomena and in the development of theories on formation mechanisms of porous silicon.

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