Oxygen related defects excitation and photoconductivity dependence of SnO2 sol-gel films with several light sources

Since oxygen vacancies act as donors in SnO2, the electrical properties are related to deviation from stoichiometric composition. Depending on stoichiometry SnO2 can be highly insulating or may exhibit fairly high n-type conductivity. Since bandgap transitions are in the ultraviolet range, its photoconductivity is strongly dependent on the excitation source. We have measured variation of photoconductivity excitation with wavelength for tin dioxide grown by dip-coating sol-gel technique using several light sources: tungsten lamp, xenon, mercury and deuterium, and present selected results. The main band is obtained in the range 3-4eV according to light source spectrum in the ultraviolet range. The presence of oxygen in the cryostat also affects the spectrum since electron-hole pairs react with adsorbed oxygen specimens. © 1999 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

Far infrared photoconductivity in a silicon based material: vanadium supersaturated silicon

We have analyzed the spectral sub-bandgap photoresponse of silicon (Si) samples implanted with vanadium (V) at different doses and subsequently processed by pulsed-laser melting. Samples with V concentration clearly above the insulator-metal transition limit show an important increase of the photoresponse with respect to a Si reference sample. Their photoresponse extends into the far infrared region and presents a sharp photoconductivity edge that moves towards lower photon energies as the temperature decreases. The increase of the value of the photoresponse is contrary to the classic understanding of recombination centers action and supports the predictions of the insulator-metal transition theory.

Ruling out the impact of defects on the below band gap photoconductivity of Ti supersaturated Si

In this study, we present a structural and optoelectronic characterization of high dose Ti implanted Si subsequently pulsed-laser melted (Ti supersaturated Si). Time-of-flight secondary ion mass spectrometry analysis reveals that the theoretical Mott limit has been surpassed after the laser process and transmission electron microscopy images show a good lattice reconstruction. Optical characterization shows strong sub-band gap absorption related to the high Ti concentration. Photoconductivity measurements show that Ti supersaturated Si presents spectral response orders of magnitude higher than unimplanted Si at energies below the band gap. We conclude that the observed below band gap photoconductivity cannot be attributed to structural defects produced by the fabrication processes and suggest that both absorption coefficient of the new material and lifetime of photoexcited carriers have been enhanced due to the presence of a high Ti concentration. This remarkable result proves that Ti supersaturated Si is a promising material for both infrared detectors and high efficiency photovoltaic devices.

Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

Spin dependent photoconductivity in silicon-on-sapphire

Resonant and non resonant spin dependent photoconductivity is observed in(100) silicon films grown on sapphire by CVD and MBE techniques. The CVD films are either in their as-grown state or have undergone single or double solid phase epitaxial regrowth. For all samples, a resonant decrease in photoconductivity is observed at a field of about 0.34 T for a microwave frequency of about 9.7 GHz and at about 3.3 mT when the frequency is about 92 MHz. For all samples the maximum fractional change in photoconductivity is approximately 10-4 independent of magnetic field strength.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Photoconductivity and electrical properties of diamond films grown by MPCVD

The electrical and photoconductive features of as-grown microwave-plasma-assisted chemical-vapour deposition (MPCVD) diamond films are studied in correlation with magnetic results obtained from electron paramagnetic resonance (EPR). Also, the morphology is analysed by atomic force microscopy (AFM) showing [111] crystals with a good uniformity of the deposit. The photoresponse as well the current-voltage features observed show an efficient photogeneration of carriers while the optoelectronic characteristics of the metal-diamond junction have an ideality factor of 1.6 together with a rectification ratio of about 10(4) at +/-2.5 V. The nature of the mechanisms responsible for the conduction is discussed. (C) 1998 Elsevier Science S.A.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Photoconductivity and electrical properties of diamond films grown by MPCVD

The electrical and photoconductive features of as-grown microwave-plasma-assisted chemical-vapour deposition (MPCVD) diamond films are studied in correlation with magnetic results obtained from electron paramagnetic resonance (EPR). Also, the morphology is analysed by atomic force microscopy (AFM) showing [111] crystals with a good uniformity of the deposit. The photoresponse as well the current-voltage features observed show an efficient photogeneration of carriers while the optoelectronic characteristics of the metal-diamond junction have an ideality factor of 1.6 together with a rectification ratio of about 10(4) at +/-2.5 V. The nature of the mechanisms responsible for the conduction is discussed. (C) 1998 Elsevier Science S.A.

Optical and microscopic study of a polymer-nanotube mixture for organic photovoltaic applications

Organic solar cells based on bulk heterojunction between a conductive polymer and a carbon nanostructure offer potential advantages compared to conventional inorganic cells. Low cost, light weight, flexibility and high peak power per unit weight are all features that can be considered a reality for organic photovoltaics. Although polymer/carbon nanotubes solar cells have been proposed, only low power conversion efficiencies have been reached without addressing the mechanisms responsible for this poor performance. The purpose of this work is therefore to investigate the basic interaction between carbon nanotubes and poly(3-hexylthiophene) in order to demonstrate how this interaction affects the performance of photovoltaic devices. The outcomes of this study are the contributions made to the knowledge of the phenomena explaining the behaviour of electronic devices based on carbon nanotubes and poly(3-hexylthiophene). In this PhD, polymer thin films with the inclusion of uniformly distributed carbon nanotubes were deposited from solution and characterised. The bulk properties of the composites were studied with microscopy and spectroscopy techniques to provide evidence of higher degrees of polymer order when interacting with carbon nanotubes. Although bulk investigation techniques provided useful information about the interaction between the polymer and the nanotubes, clear evidence of the phenomena affecting the heterojunction formed between the two species was investigated at nanoscale. Identifying chirality-driven polymer assisted assembly on the carbon nanotube surface was one of the major achievements of this study. Moreover, the analysis of the electrical behaviour of the heterojunction between the polymer and the nanotube highlighted the charge transfer responsible for the low performance of photovoltaic devices. Polymer and carbon nanotube composite-based devices were fabricated and characterised in order to study their electronic properties. The carbon nanotube introduction in the polymer matrix evidenced a strong electrical conductivity enhancement but also a lower photoconductivity response. Moreover, the extension of pristine polymer device characterisation models to composites based devices evidenced the conduction mechanisms related to nanotubes. Finally, the introduction of carbon nanotubes in the polymer matrix was demonstrated to improve the pristine polymer solar cell performance and the spectral response even though the power conversion efficiency is still too low.

TlBr raw material purification, crystal growth, annealing, detector fabrication and characterisation for gamma-ray detector applications

The research reported in this thesis dealt with single crystals of thallium bromide grown for gamma-ray detector applications. The crystals were used to fabricate room temperature gamma-ray detectors. Routinely produced TlBr detectors often are poor quality. Therefore, this study concentrated on developing the manufacturing processes for TlBr detectors and methods of characterisation that can be used for optimisation of TlBr purity and crystal quality. The processes under concern were TlBr raw material purification, crystal growth, annealing and detector fabrication. The study focused on single crystals of TlBr grown from material purified by a hydrothermal recrystallisation method. In addition, hydrothermal conditions for synthesis, recrystallisation, crystal growth and annealing of TlBr crystals were examined. The final manufacturing process presented in this thesis deals with TlBr material purified by the Bridgman method. Then, material is hydrothermally recrystallised in pure water. A travelling molten zone (TMZ) method is used for additional purification of the recrystallised product and then for the final crystal growth. Subsequent processing is similar to that described in the literature. In this thesis, literature on improving quality of TlBr material/crystal and detector performance is reviewed. Aging aspects as well as the influence of different factors (temperature, time, electrode material and so on) on detector stability are considered and examined. The results of the process development are summarised and discussed. This thesis shows the considerable improvement in the charge carrier properties of a detector due to additional purification by hydrothermal recrystallisation. As an example, a thick (4 mm) TlBr detector produced by the process was fabricated and found to operate successfully in gamma-ray detection, confirming the validity of the proposed purification and technological steps. However, for the complete improvement of detector performance, further developments in crystal growth are required. The detector manufacturing process was optimized by characterisation of material and crystals using methods such as X-ray diffraction (XRD), polarisation microscopy, high-resolution inductively coupled plasma mass (HR-ICPM), Fourier transform infrared (FTIR), ultraviolet and visual (UV-Vis) spectroscopy, field emission scanning electron microscope (FESEM) and energy-dispersive X-ray spectroscopy (EDS), current-voltage (I-V) and capacity voltage (CV) characterisation, and photoconductivity, as well direct detector examination.

Effect of indium doping on the electrical switching behaviour of Ge-Te glasses

Bulk Ge15Te85-xInx (1 <= x <= 11) series of glasses have been found to exhibit a threshold switching behaviour for an input current of 2 mA. An initial decrease is seen in the switching voltages (V-T) with the addition of indium, which is due to the higher metallicity of indium. An increase is seen in V-T above 3 at.% of indium, which proceeds until 8 at.%, with a change in slope (lower to higher) seen around 7 at.%. Beyond x = 8, a reversal in trend is exhibited in the variation of V-T, with a well-defined minimum around x = 9 at.%. Based on the composition dependence of V-T, it is proposed that Ge15Te85-xInx glasses exhibit an extended rigidity percolation threshold. The composition, x = 3, at which the V-T starts to increase and the composition, x = 7, at which a slope change is exhibited correspond to the onset and completion, respectively, of the extended stiffness transition. Thermal studies and photoconductivity e85-xInx glasses. In addition, the minimum seen in V-T at x = 9 is associated with the chemical threshold (CT) of this glassy system.

Recombination and trapping in n-type cobalt-doped germanium

The role of cobalt centers in promoting the recombination and trapping processes in n-type germanium has been investigated. Data on lifetime measurements carried out by the steadystate photoconductivity and photo-magneto-electric methods in the temperature range 145 to 300°K on n-type germanium samples containing cobalt in the concentration range 1·1013 to 5.·014/cm3 are presented. The results are analysed on the basis of Sah-Shockley's multi-level formula to yield the capture cross-sections Sp= (hole capture cross-section at doubly negatively charged center) and Sn-(electron capture cross-section at singly negatively charged center) and temperature dependence. It is found that Sp= is (22 ± 6). 10-16 cm2 and Sn- is ∼ 0·1. 10-16 cm2 at 145°K. Sp= varies (n = 3·5 to 4·5) in the range 145-220°K; above 225°K the index 'n' tends to a smaller value. Sn- is practically temperature independent below 180°K and increases with increase of temperature above 180°K. The value of Sp= and its temperature variation lead one to the conclusion that during capture at attractive centers, the phonon cascade mechanism is responsible for the dissipation of the recombination energy.

Electron-hole recombination in cobalt-doped p-type germanium

The recombination properties of cobalt centers in p-type germanium containing cobalt in the concentration range 1014 to 1016 atoms/cm3 have been investigated. The measurement of lifetime has been carried out by steady-state photoconductivity and photo-magneto-electric methods in the temperature range 145 to 300°K. The cross-sections Sno (electron capture cross-section at neutral centers). Sn- (electron capture cross-section at singly negatively charged centers) and their temperature variations have been estimated by the analysis of the lifetime data on the basis of Sah-Shockley's multi-level formula. The value of Sno is (15±5).10-16 cm2 and is temperature independent. The value of Sn- is ≈4·10-16 cm2 around 225°K and it increases with increase of temperature. The possible mechanisms for capture at neutral and repulsive centers are discussed and a summary of the capture cross-sections for cobalt centers is given. A comparison of the cross-section values of cobalt and their temperature variations with those of the related impurities-manganese, iron and nickel-in germanium has been made.

Characterization of defects in gallium arsenide

It is well-known that the properties of semiconductor materials including gallium arsenide are controlled by defects and impurities. The characterization of these defects is important not only for better understanding of the solid state phenomena but also for improved reliability and performance of electronic devices. We have been investigating the defects in gallium arsenide for several years using deep level transient spectroscopy, photoconductivity, transient photoconductivity, photoluminescence etc. Results drawn from our recent studies are presented here to illustrate some of the problems concerning transition metal impurities, process-induced defects, occurrence of intracentre transitions and metastability of deep levels in gallium arsenide.