Стронций титанат: свойства, применение и таусонит.

Strontium titanate is an oxide of strontium and titanium with the chemical formula SrTiO3. At room temperature, it is a centrosymmetric paraelectric material with a perovskite structure. At low temperatures it approaches a ferroelectric phase transition with a very large dielectric constant ~104 but remains paraelectric down to the lowest temperatures measured as a result of quantum fluctuations, making it a quantum paraelectric. It was long thought to be a wholly artificial material, until 1982 when its natural counterpart—discovered in Siberia and named tausonite—was recognised by the IMA. Tausonite remains an extremely rare mineral in nature, occurring as very tiny crystals. Its most important application has been in its synthesized form wherein it is occasionally encountered as a diamond simulant, in precision optics, in varistors, and in advanced ceramics. The name tausonite was given in honour of Lev Vladimirovich Tauson (1917–1989), a Russian geochemist. Disused trade names for the synthetic product include strontium mesotitanate, Diagem, and Marvelite. This product is currently being marketed for its use in jewelry under the name Fabulite. Other than its type locality of the Murun Massif in the Sakha Republic, natural tausonite is also found in Cerro Sarambi, Concepción department, Paraguay; and along the Kotaki River of Honshū, Japan.

SrTiO3 has an indirect band gap of 3.25 eV and a direct gap of 3.75 eV in the typical range of semiconductors. Synthetic strontium titanate has a very large dielectric constant (300) at room temperature and low electric field. It has a specific resistivity of over 109 Ω cm for very pure crystals. It is also used in high voltage capacitors. Introducing mobile charge carriers by doping leads to Fermi liquid metallic behavior already at very low charge carrier densities. At high electron densities strontium titanate becomes superconducting below 0.35 K and was the first insulator and oxide discovered to be superconductive. Strontium titanate is both much denser (specific gravity 4.88 for natural, 5.13 for synthetic) and much softer (Mohs hardness 5.5 for synthetic, 6–6.5 for natural) than diamond. Its crystal system is cubic and its refractive index (2.410—as measured by sodium light, 589.3 nm) is nearly identical to that of diamond (at 2.417), but the dispersion (the optical property responsible for the "fire" of the cut gemstones) of strontium titanate is 4.3x that of diamond, at 0.190 (B–G interval). This results in a shocking display of fire compared to diamond and diamond simulants such as YAG, GAG, GGG, Cubic Zirconia, and Moissanite. At temperatures lower than 105 K, its cubic structure transforms to tetragonal. Its monocrystals can be used as optical windows and high quality sputter deposition targets. SrTiO3 is an excellent substrate for epitaxial growth of high temperature superconductors and many oxide based thin films. It is particularly well known as the substrate for the growth of the lanthanum aluminate strontium titanate interface. Doping strontium titanate with niobium makes it electrically conductive, being one of the only conductive commercially available single crystal substrates for the growth of perovskite oxides. Its bulk lattice parameter of 3.905Å makes it suitable as the substrate for the growth of many other oxides, including the rare earth manganites, titanates, lanthanum aluminate (LaAlO3), strontium ruthenate (SrRuO3) and many others. Oxygen vacancies are fairly common in SrTiO3 crystals and thin films. Oxygen vacancies induce free electrons in the conduction band of the material, making it more conductive and opaque. These vacancies can be caused by exposure to reducing conditions, such as high vacuum at elevated temperatures. High quality, epitaxial SrTiO3 layers can also be grown on silicon without forming silicon dioxide, thereby making SrTiO3 an alternative gate dielectric material. This also enables the integration of other thin film perovskite oxides onto silicon. SrTiO3 can change its properties when it is exposed to light. These changes depend on the temperature and the defects in the material. At low temperatures, the main effects of light are electronic, meaning that they involve the creation, movement, and recombination of electrons and holes (positive charges) in the material.

Synthetic strontium titanate was one of several titanates patented during the late 1940s and early 1950s; other titanates included barium titanate and calcium titanate. Research was conducted primarily at the National Lead Company (later renamed NL Industries) in the United States, by Leon Merker and Langtry E. Lynd. Merker and Lynd first patented the growth process on February 10, 1953; a number of refinements were subsequently patented over the next four years, such as modifications to the feed powder and additions of colouring dopants. A modification to the basic Verneuil process (also known as flame fusion) is the favoured method of growth. An inverted oxy hydrogen blowpipe is used, with feed powder mixed with oxygen carefully fed through the blowpipe in the typical fashion, but with the addition of a third pipe to deliver oxygen—creating a tricone burner. The extra oxygen is required for successful formation of strontium titanate, which would otherwise fail to oxidize completely due to the titanium component. The ratio is ca. 1.5 volumes of hydrogen for each volume of oxygen. The highly purified feed powder is derived by first producing titanyl double oxalate salt (SrTiO(C2O4)2) by reacting strontium chloride (SrCl2) and oxalic acid ((COOH)2) with titanium tetrachloride (TiCl4). The salt is washed to eliminate chloride, heated to 1000 °C in order to produce a free flowing granular
powder of the required composition, and is then ground and sieved to ensure all particles are between 0.2 and 0.5 micrometres in size. Thin films of SrTiO3 can be grown epitaxially by various methods, including pulsed laser deposition, molecular beam epitaxy, RF sputtering and atomic layer deposition. As in most thin films, different growth methods can result in significantly different defect and impurity densities and crystalline quality, resulting in a large variation of the electronic and optical properties.

Its cubic structure and high dispersion once made synthetic strontium titanate a prime candidate for simulating diamond. Beginning c. 1955, large quantities of strontium titanate were manufactured for this sole purpose. Strontium titanate was in competition with synthetic rutile ("titania") at the time, and had the advantage of lacking the unfortunate yellow tinge and strong birefringence inherent to the latter material. While it was softer, it was significantly closer to diamond in likeness. Eventually, however, both would fall into disuse, being eclipsed by the creation of "better" simulants: first by yttrium aluminium garnet (YAG) and followed shortly after by gadolinium gallium garnet (GGG); and finally by the (to date) ultimate simulant in terms of diamond likeness and cost effectiveness, cubic zirconia. Despite being outmoded, strontium titanate is still manufactured and periodically encountered in jewellery. It is one of the most costly of diamond simulants, and due to its rarity collectors may pay a premium for large i. e. >2 carat (400 mg) specimens. As a diamond simulant, strontium titanate is most deceptive when mingled with melée i. e. <0.20 carat (40 mg) stones and when it is used as the base material for a composite or doublet stone (with, e. g., synthetic corundum as the crown or top of the stone). Under the microscope, gemmologists distinguish strontium titanate from diamond by the former's softness—manifested by surface abrasions—and excess dispersion (to the trained eye), and occasional gas bubbles which are remnants of synthesis. Doublets can be detected by a join line at the girdle ("waist" of the stone) and flattened air bubbles or glue visible within the stone at the point of bonding.

Due to its high melting point and insolubility in water, strontium titanate has been used as a strontium 90 containing material in radioisotope thermoelectric generators (RTGs), such as the US Sentinel and Soviet Beta M series. As strontium 90 has a high fission product yield and is easily extracted from spent nuclear fuel, Sr 90 based RTGs can in principle be produced cheaper than those based on plutonium 238 or other radionuclides which have to be produced in dedicated facilities. However, due to the lower power density (~0.45W thermal per gram of Strontium 90 Titanate) and half life, space based applications, which put a particular premium on low weight, high reliability and longevity prefer Plutonium 238. Terrestrial off grid applications of RTGs meanwhile have been largely phased out due to concern over orphan sources and the decreasing price and increasing availability of solar panels, small wind turbines, chemical battery storage and other off grid power solutions.