Titanium semiconductor

For the visible and near-ultraviolet portions of the spectmm, tunable dye lasers have commonly been used as the light source, although they are being replaced in many appHcation by tunable soHd-state lasers, eg, titanium-doped sapphire. Optical parametric oscillators are also developing as useful spectroscopic sources. In the infrared, tunable laser semiconductor diodes have been employed. The tunable diode lasers which contain lead salts have been employed for remote monitoring of poUutant species. Needs for infrared spectroscopy provide an impetus for continued development of tunable infrared lasers (see Infrared technology and RAMAN spectroscopy). 

Naphthaleneamine. 1-Naphthylamine or a-naphth5iamine/7i5 -i2- can be made from 1-nitronaphthalene by reduction with iron—dilute HCl, or by catalytic hydrogenation it is purified by distillation and the content of 2-naphthylamine can be reduced as low as 8—10 ppm. Electroreduction of 1-nitronaphthalene to 1-naphthylamine using titania—titanium composite electrode has been described (43). Photoinduced reduction of 1-nitronaphthalene on semiconductor (eg, anatase) particles produces 1-naphthylamine in 77% yield (44). 1-Naphthylamine/7J4-J2-. can also be prepared by treating 1-naphthol with NH in the presence of a catalyst at elevated temperature. The sanitary working conditions are improved by gas-phase reaction at... 

Heterogeneous Photocatalysis. Heterogeneous photocatalysis is a technology based on the irradiation of a semiconductor (SC) photocatalyst, for example, titanium dioxide [13463-67-7] Ti02, zinc oxide [1314-13-2] ZnO, or cadmium sulfide [1306-23-6] CdS. Semiconductor materials have electrical conductivity properties between those of metals and insulators, and have narrow energy gaps (band gap) between the filled valence band and the conduction band (see Electronic materials Semiconductors). 

The most common Schottky contacts for compound semiconductors are gold-based metallizations deposited by thermal or electron beam evaporation. The metal may include a thin titanium layer in direct contact with the semiconductor which acts as an adhesion layer. AdditionaHy, a thin layer... 

Titanium Sesc uioxide. Ti202 has the comndum stmcture. At room temperature it behaves as a semiconductor having a small (0.2 eV) band gap. At higher temperatures, however, it becomes metallic. This is associated with marked change in the mean Ti—Ti distance. As with TiO, titanium sesquioxide, Ti202, may be made by heating a stoichiometric mixture of titanium metal and titanium dioxide powders at 1600°C under vacuum in an aluminum or molybdenum capsule. 

Both anatase and mtile are broad band gap semiconductors iu which a fiUed valence band, derived from the O 2p orbitals, is separated from an empty conduction band, derived from the Ti >d orbitals, by a band gap of ca 3 eV. Consequendy the electrical conductivity depends critically on the presence of impurities and defects such as oxygen vacancies (7). For very pure thin films, prepared by vacuum evaporation of titanium metal and then oxidation, conductivities of 10 S/cm have been reported. For both siugle-crystal and ceramic samples, the electrical conductivity depends on both the state of reduction of the and on dopant levels. At 300 K, a maximum conductivity of 1 S/cm has been reported at an oxygen deficiency of... 

Berylha ceramic parts ate frequendy used in electronic and microelectronic apphcations requiting thermal dissipation (see Ceramics as ELECTRICAL materials). Berylha substrates are commonly metallized using refractory metallizations such as molybdenum—manganese or using evaporated films of chromium, titanium, and nickel—chromium alloys. Semiconductor devices and integrated circuits (qv) can be bonded by such metallization for removal of heat. 

The most common oxidation state of titanium is +4, in which the atom has lost both its 4s-electrons and its two 3d-electrons. Its most important compound is tita-nium(IV) oxide, Ti02, which is almost universally known as titanium dioxide. This oxide is a brilliantly white (when finely powdered), nontoxic, stable solid used as the white pigment in paints and paper. It acts as a semiconductor in the presence of light, and so it is used to convert solar radiation into electrical energy in solar cells. 

Many CVD reactions are being investigated for the deposition of carbides and nitrides, particularly for titanium nitride for semiconductor applications, such as diffusion barrier. The following is a summary of the metallo-organic precursors and deposition condition presently used in development or production of these materials. 

Titanium i s a light metal with high strength and excellent corrosion resi stance. It i s readily produced by CVD and has important applications, particularly in semiconductors. Its properties are summarized in Table 6.12... 

CVD titanium nitride (TiN) is the most important interstitial-nitride coating from an application standpoint. It is used extensively to provide wear resistance and as a diffusion barrier and antireflection coating in semiconductor devices. 1 °]... 

Interconnect. Three-dimensional structures require interconnections between the various levels. This is achieved by small, high aspect-ratio holes that provide electrical contact. These holes include the contact fills which connect the semiconductor silicon area of the device to the first-level metal, and the via holes which connect the first level metal to the second and subsequent metal levels (see Fig. 13.1). The interconnect presents a major fabrication challenge since these high-aspect holes, which may be as small as 0.25 im across, must be completely filled with a diffusion barrier material (such as CVD titanium nitride) and a conductor metal such as CVD tungsten. The ability to fill the interconnects is a major factor in selecting a thin-film deposition process. 

Copper is intrinsically a better metal than aluminum for the metallization of IC s. Latest developments in MOCVD show that it can be readily deposited without major changes in existing processing equipment. Diffusion problems are minimized and it appears that present barrier materials, such as titanium nitride or titanium-tungsten alloys, should provide adequate diffusion barriers for the copper-silicon couple, certainly up to the highest temperatures presently used in IC s processing (see Ch. 6). The development of CVD copper for semiconductor metallization is on a considerable scale at this time.Clt ]... 

A typical semiconductor device (found in the back-end of the line or the interconnects) consists of a layer of glass followed by a sputtered layer of titanium, which is thermally treated to form a titanium silicide. Next, a layer of titanium nitride is deposited on top of the silicide and on the sidewall of the contacts by sputtering or by MOCVD (see Fig. 13.3 in Ch. 13).P ]P ] This layer of TiN acts as a diffusion barrier and an adhesion promoter. It is followed by the main interconnect, which is an aluminum-copper alloy, in turn followed by another layer of TiN, which acts as adhesion and antireflecting layer. 

Somasundaram S, Chenthamarakshan CR, Tacconi NR, Ming Y, Rajeshwar K (2004) Photoassisted deposition of chalcogenide semiconductors on the titanium dioxide surface Mechanistic and other aspects. Chem Mater 16 3846-3852... 

If the semiconductor is doped, the excitation transition may be a MMCT transition. An example is Cr in Ti02 or SrTiOj where irradiation promotes an electron from the Cr ion to the conduction band which is essentially titanium 3d. This type of transition was discussed in the first part of this section. 

Fig. 3.8. Experimental set-up to examine interaction of atom particles with the surface of a solid body by means of atom beam reflection. I - Chamber with atom particles source installed II, III - Intermediate and main chambers / -Pyrolysis filament 2 - Collimation channel 3 - Beam chopper 4 - Titanium atomizer 5 - Collimation slot 6 - Target 7 - Deflector 8 - To vacuum pump pipe 9 - Filament 10 - ZnO semiconductor sensor...

Fig.4.12. The sample construction 1 - polished quartz plate 2 — semiconductor sensor (ZnO) i - a strip of marblyte glass 4 - a layer of titanium (palladium) X = 0.027 cm ( the length of surface migration of H atoms h = 0.0025 cm ( the air gap between the quartz plate and the glass strip).

The above results on detection of trace concentrations of oxygen by sine oxide films (and titanium oxide films, to a lesser degree), as well as the results on detection of alkyl radicals, which are acceptors of semiconductor electrons, show that the behaviour and electric properties of... 

All of these uses are based on the behavior of titanium dioxide as a semiconductor. Photons having energies greater than v 3.2 eV (wavelengths shorter than 400 nm) produce electron/hole separation and initiate the photoreactions. Electron spin resonance (esr) studies have demonstrated electron capture by adsorbed oxygen to produce the superoxide radical ion (Scheme 1) (11). Superoxide and the positive hole are key factors in photoreactions involving titanium dioxide reported here are the results of attempts to alter the course of these photoreactions by use of metal ions and to understand better the mechanisms of these photoreactions. 

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