Thermal conductivity semiconductors

Thermal conductivity detector. The most important of the bulk physical property detectors is the thermal conductivity detector (TCD) which is a universal, non-destructive, concentration-sensitive detector. The TCD was one of the earliest routine detectors and thermal conductivity cells or katharometers are still widely used in gas chromatography. These detectors employ a heated metal filament or a thermistor (a semiconductor of fused metal oxides) to sense changes in the thermal conductivity of the carrier gas stream. Helium and hydrogen are the best carrier gases to use in conjunction with this type of detector since their thermal conductivities are much higher than any other gases on safety grounds helium is preferred because of its inertness. 

The compact structure of diamond accounts for its outstanding properties. It is the hardest of all materials with the highest thermal conductivity. It is the most perfectly transparent material and has one of the highest electrical resistivities and, when suitably doped, is an outstanding semiconductor material. The properties of CVD and single-crystal diamonds are summarized in Table 7 2.[1][18]-[20]... 

The Keyes figure of merit, based on thermal conductivity as an additional factor, (see following section) predicts the suitability of a semiconductor for dense logic circuit applications. Again, diamond is far superior to other materials. 

Calvet and Guillaud (S3) noted in 1965 that in order to increase the sensitivity of a heat-flow microcalorimeter, thermoelectric elements with a high factor of merit must be used. (The factor of merit / is defined by the relation / = e2/pc, where e is the thermoelectric power of the element, p its electrical resistivity, and c its thermal conductivity.) They remarked that the factor of merit of thermoelements constructed with semiconductors (doped bismuth tellurides usually) is approximately 19 times greater than the factor of merit of chromel-to-constantan thermocouples. They described a Calvet-type microcalorimeter in which 195 semiconducting thermoelements were used instead of the usual thermoelectric pile. 

The resistance thermometry is based on the temperature dependence of the electric resistance of metals, semiconductors and other resistive materials. This is the most diffused type of low-temperature thermometry sensors are usually commercial low-cost components. At very low temperatures, however, several drawbacks take place such as the low thermal conductivity in the bulk of the resistance and at the contact surface, the heating due to RF pick up and overheating (see Section 9.6.3)... 

The HEM is a thermal model which represents a doped semiconductor thermistor (e.g. Ge NTD) as made up of two subsystems carriers (electrons or holes) and phonons. Each subsystem has its own heat capacity and is thermally linked to the other one through a thermal conductance which takes into account for the electron-phonon decoupling (see Fig. 15.2). 

The energy densities of laser beams which are conventionally used in the production of thin films is about 103 — 104Jcm 2s, and a typical substrate in the semiconductor industry is a material having a low thermal conductivity, and therefore the radiation which is absorbed by the substrate is retained near to the surface. Table 2.8 shows the relevant physical properties of some typical substrate materials, which can be used in the solution of Fourier s equation given above as a first approximation to the real situation. 

Unlike a geometrical factor, the value of the factor

with composition in a predictable way. To illustrate this, suppose that stoichiometric MO2 is heated in a vacuum so that it loses oxygen. Initially, all cations are in the M4+ state, and we expect the material to be an insulator. Removal of O2- to the gas phase as oxygen causes electrons to be left in the crystal, which will be localized on cation sites to produce some M3+ cations. The oxide now has a few M3+ cations in the M4+ matrix, and thermal energy should allow electrons to hop from M3+ to M4+. Thus, the oxide should be an n-type semiconductor. The conductivity increases until

reduction continues, eventually almost all the ions will be in the M3+ state and only a few M4+ cations will remain. In this condition it is convenient to imagine holes hopping from site to site and the material will be a p-typc semiconductor. Eventually at x = 1.5, all cations will be in the M3+ state and M2C>3 is an insulator (Fig. 7.3). 

Thermally activated chemical vapor deposition, 24 744-745 Thermally activated conductivity, in organic semiconductors, 22 202 Thermally conductive path, 14 863... 

We shall briefly discuss the electrical properties of the metal oxides. Thermal conductivity, electrical conductivity, the Seebeck effect, and the Hall effect are some of the electron transport properties of solids that characterize the nature of the charge carriers. On the basis of electrical properties, the solid materials may be classified into metals, semiconductors, and insulators as shown in Figure 2.1. The range of electronic structures of oxides is very wide and hence they can be classified into two categories, nontransition metal oxides and transition metal oxides. In nontransition metal oxides, the cation valence orbitals are of s or p type, whereas the cation valence orbitals are of d type in transition metal oxides. A useful starting point in describing the structures of the metal oxides is the ionic model.5 Ionic crystals are formed between highly electropositive... 

Returning now to thermal conductivity, Eq. (4.40) tells us that any functional dependence of heat capacity on temperature should be implicit in the thermal conductivity, since thermal conductivity is proportional to heat capacity. For example, at low temperatures, we would expect thermal conductivity to follow Eq. (4.43). This is indeed the case, as illustrated in Figure 4.25. In copper, a pure metal, electrons are the primary heat carriers, and we would expect the electronic contribution to heat capacity to dominate the thermal conductivity. This is the case, with the thermal conductivity varying proportionally with temperature, as given by Eq. (4.42). For a semiconductor such as germanium, there are less free electrons to conduct heat, and lattice conduction dominates—hence the dependence on thermal conductivity as suggested by Eq. (4.41). 

This competition between electrons and the heat carriers in the lattice (phonons) is the key factor in determining not only whether a material is a good heat conductor or not, but also the temperature dependence of thermal conductivity. In fact, Eq. (4.40) can be written for either thermal conduction via electrons, k, or thermal conduction via phonons, kp, where the mean free path corresponds to either electrons or phonons, respectively. For pure metals, kg/kp 30, so that electronic conduction dominates. This is because the mean free path for electrons is 10 to 100 times higher than that of phonons, which more than compensates for the fact that C <, is only 10% of the total heat capacity at normal temperatures. In disordered metallic mixtures, such as alloys, the disorder limits the mean free path of both the electrons and the phonons, such that the two modes of thermal conductivity are more similar, and kg/kp 3. Similarly, in semiconductors, the density of free electrons is so low that heat transport by phonon conduction dominates. 

A photoconductive detector is a semiconductor whose conductivity increases when infrared radiation excites electrons from the valence band to the conduction band. Photovoltaic detectors contain pn junctions, across which an electric field exists. Absorption of infrared radiation creates electrons and holes, which are attracted to opposite sides of the junction and which change the voltage across the junction. Mercury cadmium telluride (Hg,. Cd/Te, 0 < x < 1) is a detector material whose sensitivity to different wavelengths is affected by the stoichiome-try coefficient, x. Photoconductive and photovoltaic devices can be cooled to 77 K (liquid nitrogen temperature) to reduce thermal electric noise by more than an order of magnitude. 

Thermistor bead element. A thermal conductivity detection device in which a small glass-coated semiconductor sphere is used as the variable resistive element in the cell chamber. 

The thermal conductivity of diamond at 300 K is higher than that of any other material, and its thermal expansion coefficient at 300 K is 0.8 x 10". lower than that of Invar (an Fe-Ni alloy). Diamond is a very widc-band gap semiconductor Eg = 5.5 eV), has a high breakdown voltage (I07V cm-1), and its saturation velocity of 2.7 x I01 cm s-1 is considerably greater than that of silicon, gallium arsenide, or indium phosphide. 

Diamond Hints, although not approaching bulk diamond, are harder than most refractory nitride and carbide thin films, which makes them attractive for tribological coatings. Transparency in the visible and infrared regions of the optical spectrum can be maintained and index-of-refraction values approaching that of bulk diamond have been measured. Electrical resistivities of diamond films have been produced within the full range of bulk diamond, and thermal conductivities equivalent to those of bulk diamond also have been achieved. As substrates for semiconductor electronic devices, diamond films can be produced by both the PACVD and IBRD techniques. 

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