Gallium compounds forthe design of (nano)radiophamarceuticals

Tese de doutoramento, Química (Química Inorgânica), Universidade de Lisboa, Faculdade de Ciências, 2014

Electrical properties of undoped In0.53Ga0.47As grown on InP substrates by molecular beam epitaxy

A series of 1-mu m-thick undoped In0.53Ga0.47As with different substrate growth temperature (T-g) or different beam flux pressure (BFP) of As were grown on lattice-matched semi-insulating InP (001) substrates by molecular beam epitaxy (MBE). Van der Pauw Hall measurements were carried out for these In0.53Ga0.47As samples. The residual electron concentration decreased with increasing temperature from 77 to 140 K, but increased with increasing temperature from 140 to 300 K. Rapid thermal annealing (RTA) can reduce the residual electron concentration. The residual electron mobility increased with increasing temperature from 77 to 300 K. All these electrical properties are associated with As antisite defects. (c) 2006 Elsevier B.V. All rights reserved.

Realization of GaAs/AlGaAs quantum-cascade lasers with high average optical power

Quasi-continuous-wave operation of GaAs/AlGaAs quantum-cascade lasers with high average optical power is demonstrated. Double X-ray diffraction has been used to investigate the quality of the epitaxial material. The compositional gradients and the interface quality are controlled effectively. The corrected average power of per facet about 17 mW and temperature tuning coefficient of the gain peak about 0.91 nm/K from 83 K to 140 K is achieved in pulse operation. Best value of threshold current density is less than 3.0 kA/cm(2) at 83 K. (C) 2005 Elsevier Ltd. All rights reserved.

Current-induced migration of surface adatoms during GaN growth by molecular beam epitaxy

The influence of electric fields on surface migration of Gallium (Ga) and Nitrogen (N) adatoms is studied during GaN growth by molecular beam epitaxy (MBE). When a direct current (DC) is used to heat the sample, long distance migration of Ga adatoms and diffusion asymmetry of N adatoms at steps are observed. On the other hand, if an alternating current (AC) is used, no such preferential adatom migration is found. This effect is attributed to the effective positive charges of surface adatoms. representing an effect of electro-migration. The implications of such current-induced surface migration to GaN epitaxy are subsequently investigated. It is seen to firstly change the distribution of Ga adatoms on a growing surface, and thus make the growth to be Ga-limited at one side of the sample but N-limited at the other side. This leads to different optical qualities of the film and different morphologies of the surface. (C) 2001 Elsevier Science B.V. All rights reserved.

High-quality GaN grown by gas-source MBE

High-quality GaN epilayers were consistently obtained using a home-made gas-sourer MBE system on sapphire substrates. Room-temperature electron mobility of the grown GaN film is 300 cm(2)/V s with a background electron concentration as low as 2 x 10(17) cm(-3) The full-width at half-maximum of the GaN (0 0 0 2) double-crystal X-ray rocking curve is 6 arcmin. At low temperature (3.5 K), the FWHM of the: near-band-edge photoluminescence emission line is 10 meV. Furthermore, using piezoelectric effect alone with the high-quality films, two-dimensional electron gas was formed in a GaN/AlN/GaN/sapphire structure. Its room-temperature and low-temperature (77 K) electron mobility is 680 cm(2)/V s and 1700 cm(2)/V s, and the corresponding sheet electron density is 3.2 x 10(13) and 2.6 x 10(13) cm(-2), respectively. (C) 2001 Published by Elsevier Science.

Study of infrared luminescence from Er-implanted GaN films

In this study, we report the dependences of infrared luminescence properties of Er-implanted GaN thin films (GaN:Er) on the kinds of substrates used to grow GaN, the growth techniques of GaN, the implantation parameters and annealing procedures. The experimental results showed that the photoluminescence (PL) intensity at 1.54 mum was severely influenced by different kinds of substrates. The integrated PL peak intensity from GaN:Er /Al2O3 (00001) was three and five times stronger than that from GaN:Er /Si (111) grown by molecular beam epitaxy (MBE) and by metalorganic chemical vapor deposition (MOCVD), respectively. The PL spectra observed from GaN:Er/Al2O3 (0001) grown by MOCVD and by MBE displayed a similar feature, but those samples grown by MOCVD exhibited a stronger 1.54 mum PL. It was also found that there was a strong correlation between the PL intensity with ion implantation parameters and annealing procedures. Ion implantation induced damage in host material could be only partly recovered by an appropriate annealing temperature procedure. The thermal quenching of PL from 15 to 300 K was also estimated. In comparison with the integrated PL intensity at 15 K, it is reduced by only about 30 % when going up to 300 K for GaN:Er/Al2O3 sample grown by MOCVD. Our results also show that the strongest PL intensity comes from GaN:Er grown on Al2O3 substrate by MOCVD. (C) 2004 Elsevier B.V. All rights reserved.

Current-induced migration of surface adatoms during GaN growth by molecular beam epitaxy

The influence of electric fields on surface migration of Gallium (Ga) and Nitrogen (N) adatoms is studied during GaN growth by molecular beam epitaxy (MBE). When a direct current (DC) is used to heat the sample, long distance migration of Ga adatoms and diffusion asymmetry of N adatoms at steps are observed. On the other hand, if an alternating current (AC) is used, no such preferential adatom migration is found. This effect is attributed to the effective positive charges of surface adatoms. representing an effect of electro-migration. The implications of such current-induced surface migration to GaN epitaxy are subsequently investigated. It is seen to firstly change the distribution of Ga adatoms on a growing surface, and thus make the growth to be Ga-limited at one side of the sample but N-limited at the other side. This leads to different optical qualities of the film and different morphologies of the surface. (C) 2001 Elsevier Science B.V. All rights reserved.

High-quality GaN grown by gas-source MBE

High-quality GaN epilayers were consistently obtained using a home-made gas-sourer MBE system on sapphire substrates. Room-temperature electron mobility of the grown GaN film is 300 cm(2)/V s with a background electron concentration as low as 2 x 10(17) cm(-3) The full-width at half-maximum of the GaN (0 0 0 2) double-crystal X-ray rocking curve is 6 arcmin. At low temperature (3.5 K), the FWHM of the: near-band-edge photoluminescence emission line is 10 meV. Furthermore, using piezoelectric effect alone with the high-quality films, two-dimensional electron gas was formed in a GaN/AlN/GaN/sapphire structure. Its room-temperature and low-temperature (77 K) electron mobility is 680 cm(2)/V s and 1700 cm(2)/V s, and the corresponding sheet electron density is 3.2 x 10(13) and 2.6 x 10(13) cm(-2), respectively. (C) 2001 Published by Elsevier Science.

Urbach energy parameter of flash evaporated amorphous gallium arsenide films

The dependence of the optical absorption edge on the deposition crucible temperature is used to investigate the electronic states in As-rich a-GaAs flash evaporated films. The Urbach energy parameter, determined from photothermal deflection spectroscopy (PDS), presents large correlated variations with crucible temperature. The optical and electrical results are consistent with the As under coordinated sites being the more important defect in the material. © 2002 Elsevier Science B.V. All rights reserved.

Structure and properties of intermetallic ternary rare earth compounds

The so called material science is an always growing field in modern research. For the development of new materials not only the experimental characterization but also theoretical calculation of the electronic structure plays an important role. A class of compounds that has attracted a great deal of attention in recent years is known as REME compounds. These compounds are often referred to with RE designating rare earth, actinide or an element from group 1 - 4, M representing a late transition metal from groups 8 - 12, and E belonging to groups 13 - 15. There are more than 2000 compounds with 1:1:1 stoichiometry belonging to this class of compounds and they offer a broad variety of different structure types. Although many REME compounds are know to exist, mainly only structure and magnetism has been determined for these compounds. In particular, in the field of electronic and transport properties relatively few efforts have been made. The main focus in this study is on compounds crystallizing in MgAgAs and LiGaGe structure. Both structures can only be found among 18 valence electron compounds. The f electrons are localized and therefor not count as valence electrons. A special focus here was also on the magnetoresistance effects and spintronic properties found among the REME compounds. An examination of the following compounds was made: GdAuE (E = In, Cd, Mg), GdPdSb, GdNiSb, REAuSn (RE = Gd, Er, Tm) and RENiBi (RE = Pr, Sm, Gd - Tm, Lu). The experimental results were compared with theoretic band structure calculations. The first half metallic ferromagnet with LiGaGe structure (GdPdSb) was found. All semiconducting REME compounds with MgAgAs structure show giant magnetoresistance (GMR) at low temperatures. The GMR is related to a metal-insulator transition, and the value of the GMR depends on the value of the spin-orbit coupling. Inhomogeneous DyNiBi samples show a small positive MR at low temperature that depends on the amount of metallic impurities. At higher fields the samples show a negative GMR. Inhomogeneous nonmagnetic LuNiBi samples show no negative GMR, but a large positive MR of 27.5% at room temperature, which is interesting for application.

Field-effect transistors based on self-organized molecular nanostripes

Charge transport properties in organic semiconductors depend strongly on molecular order. Here we demonstrate field-effect transistors where drain current flows through a precisely defined array of nanostripes made of crystalline and highly ordered molecules. The molecular stripes are fabricated across the channel of the transistor by a stamp-assisted deposition of the molecular semiconductors from a solution. As the solvent evaporates, the capillary forces drive the solution to form menisci under the stamp protrusions. The solute precipitates only in the regions where the solution is confined by the menisci once the critical concentration is reached and self-organizes into molecularly ordered stripes 100-200 nm wide and a few monolayers high. The charge mobility measured along the stripes is 2 orders of magnitude larger than the values measured for spin-coated thin films.

Characteristics of high-performance ambipolar organic field-effect transistors based on a diketopyrrolopyrrole-benzothiadiazole copolymer

In this paper, we report the device characteristics of ambipolar thin-film transistors (TFTs) based on a diketopyrrolopyrrole-benzothiadiazole copolymer. This polymer semiconductor exhibits the largest comparable electron and hole mobility values in a single organic semiconductor. The key to realizing such high mobility values, which are $0.5&cm}{2}/\hbox{V}̇\hbox{s, is molecular design, i.e., the use of suitable surface treatments of the source/drain contact electrodes and device architectures, particularly top-gate configurations. The subthreshold characteristics of the TFT devices are greatly improved by the use of dual-gate device geometry. We also report the first measurement of the velocity distribution of electron and hole velocities in an ambipolar organic semiconductor.

High mobility diketopyrrolopyrrole (DPP)-based organic semiconductor materials for organic thin film transistors and photovoltaics

In recent years, the electron-accepting diketopyrrolopyrrole (DPP) moiety has been receiving considerable attention for constructing donor-acceptor (D-A) type organic semiconductors for a variety of applications, particularly for organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Through association of the DPP unit with appropriate electron donating building blocks, the resulting D-A molecules interact strongly in the solid state through intermolecular D-A and π-π interactions, leading to highly ordered structures at the molecular and microscopic levels. The closely packed molecules and crystalline domains are beneficial for intermolecular and interdomain (or intergranular) charge transport. Furthermore, the energy levels can be readily adjusted, affording p-type, n-type, or ambipolar organic semiconductors with highly efficient charge transport properties in OTFTs. In the past few years, a number of DPP-based small molecular and polymeric semiconductors have been reported to show mobility close to or greater than 1 cm2 V -1 s-1. DPP-based polymer semiconductors have achieved record high mobility values for p-type (hole mobility: 10.5 cm2 V-1 s-1), n-type (electron mobility: 3 cm2 V-1 s-1), and ambipolar (hole/electron mobilities: 1.18/1.86 cm2 V-1 s-1) OTFTs among the known polymer semiconductors. Many DPP-based organic semiconductors have favourable energy levels and band gaps along with high hole mobility, which enable them as promising donor materials for OPVs. Power conversion efficiencies (PCE) of up to 6.05% were achieved for OPVs using DPP-based polymers, demonstrating their potential usefulness for the organic solar cell technology. This article provides an overview of the recent exciting progress made in DPP-containing polymers and small molecules that have shown high charge carrier mobility, around 0.1 cm2 V-1 s-1 or greater. It focuses on the structural design, optoelectronic properties, molecular organization, morphology, as well as performances in OTFTs and OPVs of these high mobility DPP-based materials.

Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives : novel acceptors for organic solar cells

Novel low bandgap solution processable diketopyrrolopyrrole (DPP) based derivatives functionalized with electron withdrawing end capping groups (trifluoromethylphenyl and trifluorophenyl) were synthesized, and their photophysical, electrochemical and photovoltaic properties were investigated. These compounds showed optical bandgaps ranging from 1.81 to 1.94 eV and intense absorption bands that cover a wide range from 300 to 700 nm, attributed to charge transfer transition between electron rich phenylene-thienylene moieties and the electron withdrawing diketopyrrolopyrrole core. All of the compounds were found to be fluorescent in solution with an emission wavelength ranging from 600 to 800 nm. Cyclic voltammetry indicated reversible oxidation and reduction processes with tuning of HOMO-LUMO energy levels. Bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor with these new acceptors were used for fabrication. The best power conversion efficiencies (PCE) using 1:2 donor-acceptor by weight mixture were 1% under simulated AM 1.5 solar irradiation of 100 mW cm-2. These findings suggested that a DPP core functionalized with electron accepting end-capping groups were a promising new class of solution processable low bandgap n-type organic semiconductors for organic solar cell applications.

Numerical Simulation of the Flow Field and Concentration Distribution in the Bulk Growth of Silicon Carbide Crystals

The physical vapor transport (PVT) method is being widely used to grow large-size single SiC crystals. The growth process is associated with heat and mass transport in the growth chamber, chemical reactions among multiple species as well as phase change at the crystal/gas interface. The current paper aims at studying and verifying the transport mechanism and growth kinetics model by demonstrating the flow field and species concentration distribution in the growth system. We have developed a coupled model, which takes into account the mass transport and growth kinetics. Numerical simulation is carried out by employing an in-house developed software based on finite volume method. The results calculated are in good agreement with the experimental observation.