Modifying the band gap and optical properties of Germanium nanowires by surface termination

Semiconductor nanowires, based on silicon (Si) or germanium (Ge) are leading candidates for many ICT applications, including next generation transistors, optoelectronics, gas and biosensing and photovoltaics. Key to these applications is the possibility to tune the band gap by changing the diameter of the nanowire. Ge nanowires of different diameter have been studied with H termination, but, using ideas from chemistry, changing the surface terminating group can be used to modulate the band gap. In this paper we apply the generalised gradient approximation of density functional theory (GGA-DFT) and hybrid DFT to study the effect of diameter and surface termination using –H, –NH2 and –OH groups on the band gap of (001), (110) and (111) oriented germanium nanowires. We show that the surface terminating group allows both the magnitude and the nature of the band gap to be changed. We further show that the absorption edge shifts to longer wavelength with the –NH2 and –OH terminations compared to the –H termination and we trace the origin of this effect to valence band modifications upon modifying the nanowire with –NH2 or –OH. These results show that it is possible to tune the band gap of small diameter Ge nanowires over a range of ca. 1.1 eV by simple surface chemistry.

Effects of GaN Capping on the Structural and the Optical Properties of InN Nanostructures Grown by Using MOCVD

InN nanostructures with and without GaN capping layers were grown by using metal-organic chemical vapor deposition. Morphological, structural, and optical properties were systematically studied by using atomic force microscopy, X-ray diffraction (XRD) and temperature-dependent photoluminescence (PL). XRD results show that an InGaN structure is formed for the sample with a GaN capping layer, which will reduce the quality and the IR PL emission of the InN. The lower emission peak at similar to 0.7 eV was theoretically fitted and assigned as the band edge emission of InN. Temperature-dependent PL shows a good quantum efficiency for the sample without a GaN capping layers; this corresponds to a lower density of dislocations and a small activation energy.

High-gain subwavelength resonant cavity antennas based on metamaterial ground planes

Planar metarnaterial Surfaces with negative reflection phase values are proposed as ground planes in a high-gain resonant cavity antenna configuration. The antenna is formed by the metarnaterial ground plane (MGP) and a superimposed metallodielectric electromagnetic band gap (MEBG) array that acts as a partially reflective surface (PRS). A single dipole positioned between the PRS and the ground IS utilised as the excitation. Ray analysis is employed to describe the functioning of the antennas and to qualitatively predict the effect of the MGP oil the antenna performance. By employing MGPs with negative reflection phase values, the planar antenna profile is reduced to subwavelength values (less than lambda/6) whilst maintaining high directivity. Full-wave simulations have been carried out with commercially available software (Microstripes (TM)). The effect of the finite PRS size on the antenna radiation performance (directivity and sidelobe level) is studied. A prototype has been fabricated and tested experimentally in order to validate the predictions.

Perturbed frequency selective surfaces for multiband high impedance surfaces

Multiresonant high impedance surfaces (HIS) without grounding vias that perform as artificial magnetic conductors (AMC) in multiple frequency bands and furthermore exhibit electromagnetic band gaps (EBG) in the same bands are presented. This is achieved by introducing perturbed frequency selective surface (FSS) arrays printed on grounded dielectric substrates. Arrays of linear dipoles are employed as an example. Perturbations are introduced by means of reducing the length of every other array element. Starting from the characteristics of a perturbed free-standing FSS, the authors present the effect of the perturbation on the excited currents and on the reflection properties of a corresponding AMC. Conclusions about the performance limitations are derived. Subsequently, a parametric study on practical HIS is presented and an optimised design with dual-band AMC and EBG response is demonstrated. Method of moments-based software has been developed and utilised for the fast and accurate analysis of such arrays. Experimental results validate the performance of the optimised structure.

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.

Conduction band offset and electron effective mass in GaInNAs/GaAs quantum-well structures with low nitrogen concentration

We have investigated the optical transitions in Ga1-yInyNxAs1-x/GaAs single and multiple quantum wells using photovoltaic measurements at room temperature. From a theoretical fit to the experimental data, the conduction band offset Q(c), electron effective mass m(e)*, and band gap energy E-g were estimated. It was found that the Q(c) is dependent on the indium concentration, but independent on the nitrogen concentration over the range x=(0-1)%. The m(e)* of GaInNAs is much greater than that of InGaAs with the same concentration of indium, and increases as the nitrogen concentration increases up to 1%. Our experimental results for the m(e)* and E-g of GaInNAs are quantitatively explained by the two-band model based on the strong interaction of the conduction band minimum with the localized N states. (C) 2001 American Institute of Physics.

Energy band engineering of complex metal oxides

This doctoral studies focused on the development of new materials for efficient use of solar energy for environmental applications. The research investigated the engineering of the band gap of semiconductor materials to design and optimise visible-light-sensitive photocatalysts. Experimental studies have been combined with computational simulation in order to develop predictive tools for a systematic understanding and design on the crystal and energy band structures of multi-component metal oxides.

Photocatalytic properties of KBiO(3) and LiBiO(3) with tunnel structures

In the present study, KBiO(3) is synthesized by a standard oxidation technique while LiBiO(3) is prepared by hydrothermal method. The synthesized catalysts are characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), BET surface area analysis and Diffuse Reflectance Spectroscopy (DRS). The XRD patterns suggest that KBiO(3) crystallizes in the cubic structure while LiBiO(3) crystallizes in orthorhombic structure and both of these adopt the tunnel structure. The SEM images reveal micron size polyhedral shaped KBiO(3) particles and rod-like or prismatic shape particles for LiBiO(3). The band gap is calculated from the diffuse reflectance spectrum and is found to be 2.1 eV and 1.8 eV for KBiO(3) and LiBiO(3), respectively. The band gap and the crystal structure data suggest that these materials can be used as photocatalysts. The photocatalytic activity of KBiO(3) and LiBiO(3) are evaluated for the degradation of anionic and cationic dyes, respectively, under UV and solar radiations.

Photovoltaic structures using thermally evaporated SnS and CdS thin films

Polycrystalline tin sulfide thin films were prepared by thermal evaporation technique. The films grown at substrate temperature of 300 degrees C had an orthorhombic crystal structure with strong preferred orientation along (111) plane. Electrical resistivity of the deposited films was about 32.5 Omega cm with a direct optical band gap of 1.33 eV. Carrier concentration and mobility of charge carriers estimated from the Hall measurement were found to be 6.24 x 10(15) cm(-3) and 30.7 cm(2)V(-1) s(-1) respectively. Heterojunction solar cells were fabricated in superstrate configuration using thermally evaporated SnS as an absorber layer and CdS, In: CdS as window layer. The resistivity of pure CdS thin film of a thickness of 320 nm was about 1-2 Omega cm and was reduced to 40 x 10(-3) Omega cm upon indium doping. The fabricated solar cells were characterized using solar simulator. The solar cells with indium doped CdS window layer showed improved performance as compared to pure CdS window layer. The best device had a conversion efficiency of 0.4% and a fill factor of 33.5%. (C) 2013 Elsevier B.V. All rights reserved.

First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

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.

Photovoltaic effects in InGaN structures with p-n junctions

InGaN photovoltaic structures with p-n junctions have been fabricated by metal organic chemical vapour deposition. Using double-crystal X-ray diffraction measurements, it was found that the room temperature band gaps of p-InGaN and n-InGaN films were 2.7 and 2.8 eV, respectively. Values of 3.4 x 10(-2) mA cm(-2) short-circuit current, 0.43 V open-circuit voltage and 0.57 fill factor have been achieved under ultraviolet illumination (360 nm), which were related to p-n junction connected back-to-back with a Schottky barrier and many defects of the p-InGaN film. 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray double-crystal characterization of the strain relaxation in GaAs/GaNxAs1-x/GaAs(001) sandwiched structures

An X-ray diffraction method, estimating the strain relaxation in an ultrathin layer, has been discussed by using kinematic and dynamical X-ray diffraction (XRD) theory. The characteristic parameter Delta Omega, used as the criterion of the strain relaxation in ultrathin layers, is deduced theoretically. It reveals that Delta Omega should be independent of the layer thickness in a coherently strained layer. By this method, we characterized our ultrathin GaNxAs1-x samples with N contents up to 5%. XRD measurements show that our GaNxAs1-x layers are coherently strained on GaAs even for such a large amount of N. Furthermore, a series of GaNxAs1-x samples with same N contents but different layer thicknesses were also characterized. It was found that the critical thickness (L-c) of GaNAs in the GaAs/GaNAs/GaAs structures determined by XRD measurement was 10 times smaller than the theoretical predictions based on the Matthews and Blakeslee model. This result was also confirmed by in situ observation of reflection high-energy electron diffraction (RHEED) and photoluminescence (PL) measurements. RHEED observation showed that the growth mode of GaNAs layer changed from 2D- to 3D-mode as the layer thickness exceeded L-c. PL measurements showed that the optical properties of GaNAs layers deteriorated rapidly as the layer thickness exceeded L-c. (C) 2000 Elsevier Science B.V. All rights reserved.

High energy ion implantation enhanced intermixed quantum well structures and their absorption characteristics in passive optical waveguides

We have shown that high energy ion implantation enhanced intermixing (HE-IIEI) technology for quantum well (QW) structures is a powerful technique which can be used to blue shift the band gap energy of a QW structure and therefore decrease its band gap absorption. Room temperature (RT) photoluminescence (PL) and guided-wave transmission measurements have been employed to investigate the amount of blue shift of the band gap energy of an intermixed QW structure and the reduction of band gap absorption, Record large blue shifts in PL peaks of 132 nm for a 4-QW InGaAs/InGaAsP/InP structure have been demonstrated in the intermixed regions of the QW wafers, on whose non-intermixed regions, a shift as small as 5 nm is observed. This feature makes this technology very attractive for selective intermixing in selected areas of an MQW structure. The dramatical reduction in band gap absorption for the InP based MQW structure has been investigated experimentally. It is found that the intensity attenuation for the blue shifted structure is decreased by 242.8 dB/cm for the TE mode and 119 dB/cm for the TM mode with respect to the control samples. Electro-absorption characteristics have also been clearly observed in the intermixed structure. Current-Voltage characteristics were employed to investigate the degradation of the p-n junction in the intermixed region. We have achieved a successful fabrication and operation of Y-junction optical switches (JOS) based on MQW semiconductor optical amplifiers using HE-IIEI technology to fabricate the low loss passive waveguide. (C) 1997 Published by Elsevier Science B.V.

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.