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.

Hydrogen sensors based on Pt-AlGaN/GaN back-to-back Schottky diode

In this paper, platinum (Pt) with a thickness of 45 nm was sputtered on the surface of AlGaN/GaN heterostructure to form the Schottky contact and the back-to-back Schottky diodes were characterized for H-2 sensing at room temperature. Both the forward and reverse current of the devices increased with exposure to H-2 gas, which was attributed to Schottky barrier height reduction caused by hydrogen absorption in the catalytic metals. A shift of 0.7 V at 297 K was obtained at a fixed forward current of 0.1 mA after switching from N-2 to 40% H-2 in N-2. The sensor's responses under different concentrations from 2500 ppm H-2 to 40% H-2 in N-2 at 297 K were investigated. Time response of the sensor at a fixed bias of 1 V was given. Finally, the decrease of the Schottky barrier height and the sensitivity of the sensor were calculated. (C) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen sensors based on Pt-AlGN/AIN/GaN Schottky diode - art. no. 68291R

Pt/AlGaN/AlN/GaN Schottky diodes have been fabricated and characterized for H-2 sensing. Platinum (Pt) with a thickness of 20nm was evaporated on the sample to form the Schottky contact. The ohmic contact, formed by evaporated Ti/Al/Ni/Au metals, was subsequently annealed by a rapid thermal treatment at 860 degrees C for 30 s in N-2 ambience. Both the forward and reverse current of the device increased greatly when exposed to H-2 gas. The sensor's responses under different hydrogen concentrations from 500ppm to 10% H-2 in N-2 at 300K were investigated. A shift of 0.45V at 297K is obtained at a fixed forward current for switching from N-2 to 10% H-2 in N-2. Time response of the sensor at a fixed bias of 0.5 V was also measured. The turn-on response of the device was rapid, while the recovery of the sensor at N-2 atmosphere was rather slow. But it recovered quickly when the device was exposed to the air. The decrease in the barrier height of the diode was calculated to be about 160meV upon introduction of 10% H-2 into the ambient. The sensitivity of the sensor is also calculated. Some thermodynamics analyses have been done according to the Langmuir isotherm equation.

Effect of CO on characteristics of AlGaN/GaN Schottky diode

Pt Schottky diode gas sensors for CO are fabricated using AlGaN/ GaN high electron mobility transistor ( HEMTs) structure. The diodes show a remarkable sensor signal (3 mA, in N-2; 2mA in air ambient) biased 2V after 1% CO is introduced at 50 degrees C. The Schottky barrier heights decrease for 36meV and 27meV in the two cases respectively. The devices exhibit a slow recovery characteristic in air ambient but almost none in the background of pure N2, which reveals that oxygen molecules could accelerate the desorption of CO and offer restrictions to CO detection.

A hydrogen gas sensor based on Pt/nanostructured WO3/SiC Schottky diode

Pt/nanostructured WO3/SiC Schottky diodes were fabricated and applied for hydrogen gas sensing applications. The nanostructured WO3 films were synthesized from tungsten coated SiC substrates via an acid-etching method using a 1.5 M HNO3 solution for 1 hr, 2 hrs and 3 hrs duration. Scanning electron microscopy of the developed films revealed platelet crystals with thicknesses in the order of 20-60 nm and lengths between 100-700 nm. X-ray diffraction analysis revealed that the rate of oxidation of tungsten increases as the duration of acid-etching increases. The devices were tested towards hydrogen gas balanced in air at different temperatures from 25°C to 200°C. At 200°C, voltage shifts of 0.45 V, 0.93 V and 2.37 V were recorded for devices acid-etched for 1 hr, 2 hrs and 3 hrs duration, respectively upon exposure to 1% hydrogen, under a constant forward bias current of 500 µA.

Reversed bias Pt/nanostructured ZnO Schottky diode with enhanced electric field for hydrogen sensing

In this paper, the effect of electric field enhancement on Pt/nanostructured ZnO Schottky diode based hydrogen sensors under reverse bias condition has been investigated. Current-voltage characteristics of these diodes have been studied at temperatures from 25 to 620 °C and their free carrier density concentration was estimated by exposing the sensors to hydrogen gas. The experimental results show a significantly lower breakdown voltage in reversed bias current-voltage characteristics than the conventional Schottky diodes and also greater lateral voltage shift in reverse bias operation than the forward bias. This can be ascribed to the increased localized electric fields emanating from the sharp edges and corners of the nanostructured morphologies. At 620 °C, voltage shifts of 114 and 325 mV for 0.06% and 1% hydrogen have been recorded from dynamic response under the reverse bias condition. © 2010 Elsevier B.V. All rights reserved.

Improving the hydrogen gas sensing performance of Pt/MoO3 nanoplatelets using a nano thick layer of La2O3

In this paper, we present how a thin RF sputtered layer of lanthanum oxide (La2O3) can alter electrical and improve hydrogen gas sensing characteristics of Pt/molybdenum oxide (MoO3) nanostructures Schottky diodes. We derived the barrier height, ideality factor and dielectric constant from the measured I–V characteristics at operating temperatures in the range of 25–300 ◦C. The dynamic response, response and recovery times were obtained upon exposure to hydrogen gas at different concentrations. Analysis of the results indicated a substantial improvement to the voltage shift sensitivity of the sensors incorporating the La2O3 layer. We associate this enhancement to the formation of numerous trap states due to the presence of the La2O3 thin film on the MoO3 nanoplatelets. These trap states increase the intensity of the dipolar charges at the metal–semiconductor interface, which induce greater bending of the energy bands. However, results also indicate that the presence of La2O3 trap states also increases response and recover times as electrons trapping and de-trapping processes occur before they can pass through this thin dielectric layer.

Reverse biased Schottky contact hydrogen sensors based on Pt∕nanostructured ZnO∕SiC

Pt/nanostructured ZnO/SiC Schottky contact devices were fabricated and characterized for hydrogen gas sensing. These devices were investigated in reverse bias due to greater sensitivity, which attributes to the application of nanostructured ZnO. The current-voltage (I-V) characteristics of these devices were measured in different hydrogen concentrations. Effective change in the barrier height for 1% hydrogen was calculated as 27.06 meV at 620°C. The dynamic response of the sensors was also investigated and a voltage shift of 325 mV was recorded at 620°C during exposure to 1% hydrogen in synthetic air.

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.

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.

Nanowires of metal oxides for gas sensing applications

Nanowires of different metal oxides (SnO2, ZnO) have been grown by evaporation-condensation process. Their chemical composition has been investigated by using XPS. The standard XPS quantification through main photoelectron peaks, modified Auger parameter and valence band spectra were examined for the accurate determination of oxidation state of metals in the nanowires. Morphological investigation has been conducted by acquiring and analyzing the SEM images. For the simulation of working conditions of sensor, the samples were annealed in ultra high vacuum (UHV) up to 500°C and XPS analysis repeated after this treatment. Finally, the nanowires of SnO 2 have were used to produce a novel gas sensor based on Pt/oxide/SiC structure and operating as Schottky diode. Copyright © 2008 John Wiley & Sons, Ltd.

Hydrogen sensing properties of Pt/Lanthanum oxide- molybdenum oxide nanoplatelet/SiC based Schottky diode

An investigation of the electrical and hydrogen sensing properties of a novel Schottky diode based on a nanostructured lanthanum oxide-molybdenum oxide compound is presented herein. Molybdenum oxide (MoO3) nanoplatelets were grown on SiC substrates via thermal evaporation which was then subsequently coated with lanthanum oxide (La2O3) by RF sputtering. The current-voltage characteristics and hydrogen sensing performance (change in barrier height and sensitivity as well as the dynamic response) were examined from 25 to 300°C. At 180°C, a voltage shift of 2.23V was measured from the sensor while exposed to 1% hydrogen gas under a 100 μA constant reverse bias current. The results indicate that the presence of a La2O3 thin layer substantially improves the hydrogen sensitivity of the MoO3 nanoplatelets.

Pt/ZnO/SiC thin film for hydrogen gas sensing

Zinc oxide (ZnO) is one of the most promising electronic and photonic materials to date. In this work, we present an enhanced ZnO Schottky gas sensor deposited on SiC substrates in comparison to those reported previously in literature. The performance of ZnO/SiC based Schottky thin film gas sensors produced a forward lateral voltage shift of 12.99mV and 111.87mV in response to concentrations of hydrogen gas at 0.06% and 1% in air at optimum temperature of 330 ºC. The maximum change in barrier height was calculated as 37.9 meV for 1% H2 sensing operation at the optimum temperature.

Pt/anodized TiO2/SiC-based MOS device for hydrocarbon sensing

Pt/anodized TiO2/SiC based metal-oxide-semiconductor (MOS) devices were fabricated and characterized for their sensitivity towards propene (C3H6). Titanium (Ti) thin films were deposited onto the SiC substrates using a filtered cathodic vacuum arc (FCVA) method. Fluoride ions containing neutral electrolyte (0.5 wt% NH4F in ethylene glycol)were used to anodize the Ti films. The anodized films were subsequently annealed at 600 °C for 4 hrs in an oxygen rich environment to obtain TiO2. The current-voltage(I-V) characteristics of the Pt/TiO2/SiC devices were measured in different concentrations of propene. Exposure to the analyte gas caused a change in the Schottky barrier height and hence a lateral shift in the I-V characteristics. The effective change in the barrier height for 1% propene was calculated as 32.8 meV at 620°C. The dynamic response of the sensors was also investigated and a voltage shift of 157 mV was measured at 620°C during exposure to 1% propene.

Anodized nanoporous WO3 Schottky contact structure for hydrogen and ethanol sensing

This paper reports the development of nanoporous tungsten trioxide (WO3) Schottky diode-based gas sensors. Nanoporous WO3 films were prepared by anodic oxidation of tungsten foil in ethylene glycol mixed with ammonium fluoride and a small amount of water. Anodization resulted in highly ordered WO3 films with a large surface-to-volume ratio. Utilizing these nanoporous structures, Schottky diode-based gas sensors were developed by depositing a platinum (Pt) catalytic contact and tested towards hydrogen gas and ethanol vapour. Analysis of the current–voltage characteristics and dynamic responses of the sensors indicated that these devices exhibited a larger voltage shift in the presence of hydrogen gas compared to ethanol vapour at an optimum operating temperature of 200 °C. The gas sensing mechanism was discussed, associating the response to the intercalating H+ species that are generated as a result of hydrogen and ethanol molecule breakdowns onto the Pt/WO3 contact and their spill over into nanoporous WO3.