Band Engineering in Thermoelectric Materials Using Optical, Electronic, and Ab-Initio Computed Properties

Thermoelectric materials have demanded a significant amount of attention for their ability to convert waste heat directly to electricity with no moving parts. A resurgence in thermoelectrics research has led to significant enhancements in the thermoelectric figure of merit, zT, even for materials that were already well studied. This thesis approaches thermoelectric zT optimization by developing a detailed understanding of the electronic structure using a combination of electronic/thermoelectric properties, optical properties, and ab-initio computed electronic band structures. This is accomplished by applying these techniques to three important classes of thermoelectric materials: IV-VI materials (the lead chalcogenides), Half-Heusler’s (XNiSn where X=Zr, Ti, Hf), and CoSb₃ skutterudites.

In the IV-VI materials (PbTe, PbSe, PbS) I present a shifting temperature-dependent optical absorption edge which correlates well to the computed ab-initio molecular dynamics result. Contrary to prior literature that suggests convergence of the primary and secondary bands at 400 K, I suggest a higher convergence temperature of 700, 900, and 1000 K for PbTe, PbSe, and PbS, respectively. This finding can help guide electronic properties modelling by providing a concrete value for the band gap and valence band offset as a function of temperature.

Another important thermoelectric material, ZrNiSn (half-Heusler), is analyzed for both its optical and electronic properties; transport properties indicate a largely different band gap depending on whether the material is doped n-type or p-type. By measuring and reporting the optical band gap value of 0.13 eV, I resolve the discrepancy in the gap calculated from electronic properties (maximum Seebeck and resistivity) by correlating these estimates to the electron-to-hole weighted mobility ratio, A, in narrow gap materials (A is found to be approximately 5.0 in ZrNiSn).

I also show that CoSb₃ contains multiple conduction bands that contribute to the thermoelectric properties. These bands are also observed to shift towards each other with temperature, eventually reaching effective convergence for T>500 K. This implies that the electronic structure in CoSb₃ is critically important (and possibly engineerable) with regards to its high thermoelectric figure of merit.

A new method of modeling cladding band structure of air-guiding photonic crystal fibers

Cladding band structure of air-guiding photonic crystal fibers with high air-filling fraction is calculated in terms of fiber shape variation. The fundamental photonic band gap dependence on structure parameters, air-filling fraction and spacing, is also investigated. The numerical results show that the band gap edges shift toward longer wavelength as the air-filling fraction is increased, whereas the relative band gap width increases linearly. For a fixed air-filling fraction, the band gap edges with respect to spacing keep constant. With this method, the simulation results agree well with the reported data. © 2007 Elsevier B.V. All rights reserved.

Band structure of photonic crystal fibers with silica rings in triangular lattice

The characteristics of the cladding band structure of air-core photonic crystal fibers with silica rings in triangular lattice are investigated by using a standard plane wave method. The numerical results show that light can be localized in the air core by the photonic band gaps of the fiber. By increasing the air-filling fraction, the band gap edges of the low frequency photonic band gaps shift to shorter wavelength.. whereas the band gap width decreases linearly. In order to make a specified light fall in the low frequency band gaps of the fiber, the interplay of the silica ring spacing and the air-filling fraction is also analyzed. It shows that the silica ring spacing increases monotonously when the air-filling fraction is increased, and the spacing range increases exponentially. This type fiber might have potential in infrared light transmission. (c) 2006 Elsevier B.V. All rights reserved.

Smooth thin film C/diamond membranes with controllable optical band gaps

Mixed phase carbon-diamond films which consist of small grain diamond in an a:C matrix were deposited on polished Si using a radio frequency CH4 Ar plasma CVD deposition process. Ellipsometry, surface profilometry, scanning electron microscopy (SEM) and spectrophotometry were used to analyse these films. Film thicknesses were typically 50-100 nm with a surface roughness of ± 30 A ̊ over centimetre length scans. SEM analysis showed the films were smooth and pinhole free. The Si substrate was etched using backside masking and a directional etch to give taut carbon-diamond membranes on a Si grid. Spectrophotometry was used to analyse the optical properties of these membranes. Band gap control was achieved by varying the dc bias of the deposition process. Band gaps of 1.2 eV to 4.0 eV were achieved in these membranes. A technique for controlling the compressive stress in the films, which can range from 0.02 to 7.5 GPa has been employed. This has allowed the fabrication of thin, low stress, high band gap membranes that are extremely tough and chemically inert. Such carbon-diamond membranes seem promising for applications as windows in analytical instruments. © 1992.

Electro-optic modulation of 1.5μm light in an active InGaAsP/InP quantum well waveguide

We report an InGaAsP/InP phase modulator operating in the 1.5μm wavelength band. Phase modulation of 7.5°/mA and 1.7°/mA of injected current have been measured for TE and TM polarised light respectively at a signal wavelength of 1.52 μm.

Optical gap in carbon nitride films

In this paper we study the effect of introducing nitrogen into different carbon networks. Two kinds of carbon nitride films were deposited: (a) Using a DC-magnetron sputtering system sp2 bonded carbon nitride (a-CN) films were deposited and (b) Using a combination of filtered cathodic vacuum arc and a low-pressure N2 plasma source, N was introduced into sp3 carbon networks (ta-C), leading to the formation of a more dense CN film named ta-CN. For ta-CN films we found that the optical gap initially decreases as the N content and the sp2 fraction rises, but above a certain N quantity there is a level-off of the value, and the gap then remains constant despite further increases in the fraction and clustering of the sp2 phase. However, for a-CN films the optical gap increases with the nitrogen content. These two different trends are not easily explained using the same framework as that for carbon films, in which any decrease in the band gap is associated to an increase in the sp2 fraction or its clustering. Here we discuss the conditions that lead to high optical gap in sp2-bonded carbon nitride samples, which are clearly not associated to the presence of any crystalline super-hard phase. We also compared other differences in properties observed between the two films, such as deposition rate, infrared and Raman spectra. © 2003 Elsevier Science B.V. All rights reserved.

Valence band offset of MgO/InN heterojunction measured by x-ray photoelectron spectroscopy

MgO may be a promising gate dielectric and surface passivation film for InN based devices and the valence band offset of MgO/InN heterojunction has been measured by x-ray photoelectron spectroscopy. The valence band offset is determined to be 1.59 +/- 0.23 eV. Given the experimental band gap of 7.83 for the MgO, a type-I heterojunction with a conduction band offset of 5.54 +/- 0.23 eV is found. The accurate determination of the valence and conduction band offsets is important for use of MgO/InN electronic devices. (c) 2008 American Institute of Physics.

Measurement of polar C-plane and nonpolar A-plane InN/ZnO heterojunctions band offsets by x-ray photoelectron spectroscopy

The valence band offsets of the wurtzite polar C-plane and nonpolar A-plane InN/ZnO heterojunctions are directly determined by x-ray photoelectron spectroscopy to be 1.76 +/- 0.2 eV and 2.20 +/- 0.2 eV. The heterojunctions form in the type-I straddling configuration with a conduction band offsets of 0.84 +/- 0.2 eV and 0.40 +/- 0.2 eV. The difference of valence band offsets of them mainly attributes to the spontaneous polarization effect. Our results show important face dependence for InN/ZnO heterojunctions, and the valence band offset of A-plane heterojunction is more close to the "intrinsic" valence band offset.

Determination of MgO/AlN heterojunction band offsets by x-ray photoelectron spectroscopy

MgO is a promising gate dielectric and surface passivation film for GaN/AlGaN transistors, but little is known of the band offsets in the MgO/AlN system. X-ray photoelectron spectroscopy was used to measure the energy discontinuity in the valence band (Delta E-v) of MgO/AlN heterostructures. A value of Delta E-v=0.22 +/- 0.08 eV was obtained. Given the experimental band gap of 7.83 eV for MgO, a type-I heterojunction with a conduction band offset of similar to 1.45 eV is found. The accurate determination of the valence and conduction band offsets is important for use of III-N alloys based electronic devices.

Design of Narrow-Gap TiO2: A Passivated Codoping Approach for Enhanced Photoelectrochemical Activity

To improve the photoelectrochemical activity of TiO2 for hydrogen production through water splitting, the band edges of TiO2 should be tailored to match with visible light absorption and the hydrogen or oxygen production levels. By analyzing the band structure of TiO2 and the chemical potentials of the dopants, we propose that the band edges of TiO2 can be modified by passivated codopants such as (Mo+C) to shift the valence band edge up significantly, while leaving the conduction band edge almost unchanged, thus satisfying the stringent requirements. The design principle for the band-edge modification should be applicable to other wide-band-gap semiconductors.

Valence band offset of InN/4H-SiC heterojunction measured by x-ray photoelectron spectroscopy

The valence band offset (VBO) of InN/4H-SiC heterojunction has been directly measured by x-ray photoelectron spectroscopy. The VBO is determined to be 0.55 +/- 0.23 eV and the conduction band offset is deduced to be -2.01 +/- 0.23 eV, indicating that the heterojunction has a type-I band alignment. The accurate determination of the valence and conduction band offsets is important for applications of InN/SiC optoelectronic devices.

Photonic band structures of two-dimensional photonic crystals with deformed lattices

Using the plane-wave expansion method, we have calculated and analysed the changes of photonic band structures arising from two kinds of deformed lattices, including the stretching and shrinking of lattices. The square lattice with square air holes and the triangular lattice with circular air holes are both studied. Calculated results show that the change of lattice size in some special ranges can enlarge the band gap, which depends strongly on the filling factor of air holes in photonic crystals; and besides, the asymmetric band edges will appear with the broken symmetry of lattices.

A 10-GHz bandwidth electroabsorption modulated laser by ultra-low-pressure selective area growth

A novel integration technique has been developed using band-gap energy control of InGaAsP/InGaAsP multi-quantum-well (MQW) structures during simultaneous ultra-low-pressure (22 mbar) selective-area-growth (SAG) process in metal-organic chemical vapour deposition. A fundamental study of the controllability of band gap energy by the SAG method is performed. A large band-gap photoluminescence wavelength shift of 83nm is obtained with a small mask width variation (0-30 mu m). The method is then applied to fabricate an MQW distributed-feedback laser monolithically integrated with an electroabsorption modulator. The experimental results exhibit superior device characteristics with low threshold of 19 mA, over 24 dB extinction ratio when coupled into a single mode fibre. More than 10GHz modulation bandwidth is also achieved, which demonstrates that the ultra-low-pressure SAG technique is a promising approach for high-speed transmission photonic integrated circuits.

Electronic structure and g factors of narrow-gap zinc-blende nanowires and nanorods

The Hamiltonian in the framework of eight-band effective-mass approximation of the zinc-blende nanowires and nanorods in the presence of external homogeneous magnetic field is given in the cylindrical coordinate. The electronic structure, optical properties, magnetic energy levels, and g factors of the nanowires and nanorods are calculated. It is found that the electron states consist of many hole-state components, due to the coupling of the conduction band and valence band. For the normal bands which are monotone functions of |k(z)|, long nanorods can be modeled by the nanowires, the energy levels of the nanorods approximately equal the values of the energy band E(k(z)) of the nanowires with the same radius at a special k(z), where k(z) is the wave vector in the wire direction. Due to the coupling of the states, some of the hole energy bands of the nanowires have their highest points at k(z)=0. Especially, the highest hole state of the InSb nanowires is not at the k(z)=0 point. It is an indirect band gap. For these abnormal bands, nanorods can not be modeled by the nanowires. The energy levels of the nanorods show an interesting plait-like pattern. The linear polarization factor is zero, when the aspect ratio L/2R is smaller than 1, and increases as the length increases. The g(z) and g(x) factors as functions of the k(z), radius R and length L are calculated for the wires and rods, respectively. For the wires, the g(z) of the electron ground state increases, and the g(z) of the hole ground state decreases first, then increases with the k(z) increasing. For the rods, the g(z) and g(x) of the electron ground state decrease as the R or the L increases. The g(x) of the hole ground state decreases, the g(z) of the hole ground state increases with the L increasing. The variation of the g(z) of the wires with the k(z) is in agreement with the variation of the g(z) of the rods with the L.

Synthesis and temperature-dependent near-band-edge emission of chain-like Mg-doped ZnO nanoparticles

Chain-like Mg-doped ZnO nanoparticles were prepared using a wet chemical method combined with subsequent heat treatment. The blueshifted near-band-edge emission of the doped ZnO sample with respect to the undoped one was investigated by temperature-dependent photoluminescence. Based on the energy shift of the free-exciton transition, a band gap enlargement of similar to 83 meV was estimated, which seems to result in the equivalent shift of the bound-exciton transition. At 50 K, the transformation from the donor-acceptor-pair to free-to-acceptor emissions was observed for both the undoped and doped samples. The results show that Mg doping leads to the decrease of the acceptor binding energy. (c) 2006 American Institute of Physics.