Defect study in ZnO related structures—A multi-spectroscopic approach

ZnO has attracted a great deal of attention in recent years because of its potential applications for fabricating optoelectronic devices. Using a multi-spectroscopic approach including positron annihilation spectroscopy (PAS), deep level transient spectroscopy (DLTS), photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS), we have studied the two observed phenomena from ZnO related structures. They namely included the H₂O₂ pre-treatment induced ohmic to rectifying contact conversion on Au/n-ZnO contact and the p-type doping by nitrogen ion implantation. The aim of the studies was to offering comprehensive views as to how the defects influenced the structures electrical and optical properties of the structures. It was also shown that PAS measurement using the monoenergetic positron beam could offer valuable information of vacancy type defects in the vertical ZnO nanorod array structure.     

Enhanced ethanol sensing properties of TiO2/ZnO core–shell nanorod sensors

TiO₂-core/ZnO-shell nanorods were synthesized using a two-step process: the synthesis of TiO₂ nanorods using a hydrothermal method followed by atomic layer deposition of ZnO. The mean diameter and length of the nanorods were ～300 nm and ～2.3 μm, respectively. The cores and shells of the nanorods were monoclinic-structured single-crystal TiO₂ and wurtzite-structured single-crystal ZnO, respectively. The multiple networked TiO₂-core/ZnO-shell nanorod sensors showed responses of 132–1054 % at ethanol (C₂H₅OH) concentrations ranging from 5 to 25 ppm at 150 ^°C. These responses were 1–5 times higher than those of the pristine TiO₂ nanorod sensors at the same C₂H₅OH concentration range. The substantial improvement in the response of the pristine TiO₂ nanorods to C₂H₅OH gas by their encapsulation with ZnO may be attributed to the enhanced absorption and dehydrogenation of ethanol. In addition, the enhanced sensor response of the core–shell nanorods can be attributed partly to changes in resistance due to both the surface depletion layer of each core–shell nanorod and the potential barriers built in the junctions caused by a combination of homointerfaces and heterointerfaces.     

Enhanced ethanol sensing properties of TeO2/In2O3 core–shell nanorod sensors

TeO₂/In₂O₃ core–shell nanorods were fabricated using thermal evaporation and sputtering methods. The multiple networked TeO₂/In₂O₃ core–shell nanorod sensor showed responses of 227–632%, response times of 50–160 s, and recovery times of 190–220 s at ethanol (C₂H₅OH) concentrations of 50–250 ppm at 300 °C. The response values are 1.6–2.9 times higher and the response and recovery times are also considerably shorter than those of the pristine TeO₂ nanorod sensor over the same C₂H₅OH concentration range. The origin of the enhanced ethanol sensing properties of the core–shell nanorod sensor is discussed.     

One‐Pot Synthesis of Algae‐Like MoS2/PPy Nanocomposite: A Synergistic Catalyst with Superior Peroxidase‐Like Catalytic Activity for H2O2 Detection

A facile one‐pot synthetic route is reported to prepare algae‐like molybdenum disulfide/polypyrrole (MoS₂/PPy) nanocomposite through a redox reaction between ammonium tetrathiomolybdate and pyrrole monomer under a hydrothermal condition without any other templates. The as‐prepared unique algae‐like MoS₂/PPy nanocomposites are composed of few layer MoS₂ nanosheets, which are covered with PPy. Structural and morphological characterizations of this unique nanocomposite are investigated by Fourier‐transform infrared spectra, Raman spectra, X‐ray diffraction pattern, X‐ray photoelectron spectra, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy. The as‐prepared MoS₂/PPy nanocomposites exhibit an excellent peroxidase‐like catalytic activity toward the oxidation of 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂) in acetate buffer solution (pH 4.0), which provides a facile strategy for the colorimetric detection of H₂O₂ with a high sensitivity.     

Hydrogen peroxide treatment on ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts

We utilize hydrogen peroxide (H₂O₂) treatment on (0 0 0 1) ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts (SCs). X-ray rocking curves show the mosaicity structure becomes larger after H₂O₂ treatment. Photoluminescence (PL) spectra show the yellow-orange emission peaking at ∼576-580 nm with respect to deep level of oxygen interstitials introduced by H₂O₂ treatment. The threshold formation of ZnO₂ resistive layer on H₂O₂-treated ZnO for 45 min is observed from grazing-incidence X-ray diffraction. The better electrical characteristic is performed by Pt oxide SC with the larger barrier height (1.09 eV) and the lower leakage current (9.52 × 10⁻¹¹ A/cm² at −2 V) than Pt SC on the H₂O₂-treated ZnO for 60 min. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometer (SIMS) examinations indicate the promoted interface oxide bonding and Zn outdiffusion for Pt oxide contact, different from Pt contact. Based on current-voltage, capacitance-voltage, X-ray diffraction, PL spectra, XPS, and SIMS results, the possible mechanism for effective rectifying characteristic and enhanced Schottky behavior is given.     

Temperature dependence and the effect of hydrogen peroxide on ITO/poly-ZnO Schottky diodes fabricated by laser evaporation

Transparent and efficient poly-ZnO ultraviolet Schottky diodes grown at different temperatures with indium-tin-oxide (ITO) as the metallic contact layer were fabricated with hydrogen peroxide (H₂O₂) applied as a surface treatment at 70 °C for 20 min. Analysis via field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) demonstrated that the ZnO films underwent gradual oxidation and that H₂O₂ treatment resulted in an interfacial ZnO₂ layer that covered the ZnO surface. I–V measurements indicated that the ideality factor and the Schottky barrier height improved with increasing shunt resistance, and the trade-off between film quality and the degree of oxidation revealed that films grown at 400 °C exhibited the best diode characteristics.     

Reduction of low‐frequency noise in multilayer MoS2 FETs using a Fermi‐level depinning layer

Two‐dimensional transition metal dichalcogenides (TMDCs) are potential candidate materials for future thin‐film field effect transistors (FETs). However, many aspects of this device must be optimized for practical applications. In addition, low‐frequency noise that limits the design window of electronic devices, in general, must be minimized for TMD‐based FETs. In this study, the low‐frequency noise characteristics of multilayer molybdenum disulphide (MoS₂) FETs were investigated in detail, with two different contact structures: titanium (Ti) metal–MoS₂ channel and Ti metal–TiO₂ interlayer–MoS₂ channel. The results showed that the noise level of the device with a TiO₂ interlayer reduced by one order of magnitude compared with the device without the TiO₂ interlayer. This substantial improvement in the noise characteristics could be explained using the carrier number of fluctuation model. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Adsorption of Cs and O2 on MoS2

Adsorption of Cs on basal planes of MoS₂ has been studied with LEED, Auger and work function measurements. LEED observations show that in the 200–300 K range Cs is adsorbed as amorphous layers on MoS₂. Correlation of Auger and work function measurements indicates that the work function, sticking coefficient and the maximum density of Cs that can be deposited on the MoS₂ surface depend strongly on substrate temperature. Cesium is deposited on MoS₂ in two adsorption states. Although MoS₂ is extremely inert to O₂ adsorption, the presence of Cs causes a drastic increase in the adsorption of oxygen which in turn increases the amount of Cs that can be deposited on the surface. Lastly, it has been found that part of the Cs adatoms are diffused into the bulk of MoS₂.     

Low-temperature growth of ZnO nanorods on PET fabrics with two-step hydrothermal method

An effective low-temperature growth method to fabricate hexagonally oriented ZnO nanorod arrays onto PET fabrics is reported. The effect of substrate pre-treatment and C₆H₁₂N₄ concentration on the structure of ZnO nanorod arrays were investigated in details by X-ray diffraction (XRD), FE-SEM and ultraviolet protection factor (UPF). The results show that substrate pre-treatment, C₆H₁₂N₄ concentration indeed have great influence on the growth of ZnO nanorod arrays. It is indispensable to introduce a ZnO seed layer on the substrate and under growth condition of n(C₆H₁₂N₄):n[Zn(NO₃)₂] = 1:1, T = 90 °C, t = 3 h, the well-aligned ZnO nanorod arrays with 40-50 nm in diameter and 300-400 nm in length were achieved on the pre-treated PET fabrics. The ZnO nanorods grown on PET fabrics possessed an ultrahigh ultraviolet protection factor of 480.52 in this study, indicating an excellent protection against ultraviolet radiation in comparison with the untreated PET fabrics.     

水热法合成纳米花状二硫化钼及其微观结构表征

本文以钼酸钠、硫代乙酰胺为前驱体, 硅钨酸为添加剂, 成功用水热法合成高纯度纳米花状二硫化钼. 产物特性用X射线衍射(XRD)、能量色散谱(EDS)、扫描电子显微镜(SEM)进行表征. XRD和EDS图显示实验产物为二硫化钼, 且其结晶度和层状堆垛良好. SEM图谱则表明二硫化钼为纳米花状结构, 颗粒直径300 nm左右, 由几十上百片花瓣组成, 每片花瓣厚度十个纳米左右. 通过以硅钨酸为变量的梯度实验, 研究发现, 硅钨酸对于纳米花状MoS₂的形成具有重要作用, 不添加硅钨酸, 无法形成纳米花状MoS₂, 此外, 硅钨酸的剂量会影响合成MoS₂的大小和形貌. 本文还对纳米花状二硫化钼的形成机理做了初步的讨论.     

Variability of electrical contact properties in multilayer MoS2 thin-film transistors

We report the variability of electrical properties of Ti contacts in back-gated multilayer MoS₂ thin-film transistors based on mechanically exfoliated flakes. By measuring current–voltage characteristics from room temperature to 240 °C, we demonstrate the formation of both ohmic and Schottky contacts at the Ti–MoS₂ junctions of MoS₂ transistors fabricated using identical electrode materials under the same conditions. While MoS₂ transistors with ohmic contacts exhibit a typical signature of band transport, those with Schottky contacts indicate thermally activated transport behavior for the given temperature range. These results provide the experimental evidence of the variability of Ti metal contacts on MoS₂, highlighting the importance of understanding the variability of electronic properties of naturally occurring MoS₂ for further investigation.     

Spectroscopic ellipsometry modeling of ZnO thin films with various O2 partial pressures

ZnO films were deposited on thermally oxidized SiO₂/p-type Si (100) substrates and glass substrates by DC magnetron sputtering using a metal Zn target. Three types of samples were prepared with various O₂/(Ar + O₂) ratios (O₂ partial pressure) of 20%, 50%, and 80%. The properties of these ZnO thin films were investigated using X-ray diffraction (XRD), optical transmittance, atomic force microscopy (AFM), and spectroscopic ellipsometry in the spectral region of 1.7–3.1 eV. The structural and optical properties of ZnO thin films were affected by O₂ partial pressure. Relationships between crystallinity, the ZnO surface roughness layer, and the refractive index (n) were investigated with varying O₂ partial pressure. It was shown that the spectroscopic ellipsometry extracted parameters well represented the ZnO thin film characteristics for different O₂ partial pressures.     

Controlled synthesis of oriented ZnO nanorod arrays by seed-layer-free electrochemical deposition

Oriented ZnO nanorod arrays were successfully prepared on transparent conductive substrates by seed-layer-free electrochemical deposition in solution of Zn(NO₃)₂ at a low temperature of 70 °C without using any catalysts, additives, and additional seed crystals. The effects of the Zn(NO₃)₂ concentration, deposition time and applied current on the localized nanorod arrays are investigated. X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) were used to characterize the structures and the morphologies of ZnO nanorod arrays. The heights and diameters of ZnO nanorods can be tuned by controlling the electrodeposition parameters.     

Sonochemical synthesis and anchoring of zinc oxide on hemin-mediated multiwalled carbon nanotubes-cellulose nanocomposite for ultra-sensitive biosensing of H2O2

In this work, the metal oxide and biopolymer nanocomposites on multiwalled carbon nanotubes (MWCNT) were prepared using a simple sonochemical method. The hexagonal nanorods of zinc oxide (ZnO NR) were synthesized by probe sonication (frequency = 20 kHz, amplitude = 50) method and were integrated on ultrasonically functionalized MWCNT-cellulose nanocrystals (MWCNT-CNC) for the first time. The stable hemin bio-composites also were prepared using the bath sonication (37 kHz of frequency, 150 W of power) method, and was used for the selective and ultrasensitive electrochemical detection of H₂O₂. The UV–Vis spectroscopy studies confirmed the presence of native hemin on MWCNT-CNC/ZnO NR nanocomposite. Cyclic voltammetry studies revealed that an enhanced redox electrochemical behaviour of hemin was observed on hemin immobilised MWCNT-CNC/ZnO NR nanocomposite than that of other hemin modified electrodes. Also, the MWCNT-CNC/ZnO NR/hemin modified SPCE showed 2.3 folds higher electrocatalytic activity with a lower reduction potential (−0.2 V) towards H₂O₂ than that of other investigated hemin modified electrodes including hemin/MWCNT and hemin/CNC-ZnO. The fabricated biosensor displayed a stable amperometric response (-0.2 V vs Ag/AgCl) in the linear concentration of H₂O₂ ranging up to 4183.3 µM with a lower detection limit of 4.0 nM.     

The CO coadsorption and reactions of sulfur,hydrogen and oxygen on clean and sulfided Mo(100) and on MoS2(0001) crystal faces

The chemisorption and reactivity of O₂ and H₂ with the sulfided Mo(100) surface and the basal (0001) plane of MoS₂ have been studied by means of Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). These studies have been carried out at both low (10^?8–10^?5Torr) and high (1 atm) pressures of O₂ and H₂. Sulfur desorbs from Mo(100) both as an atom and as a diatomic molecule. Sulfur adsorbed on Mo(100) blocks sites of hydrogen adsorption without noticeably changing the hydrogen desorption energies. TDS of ¹⁸O coadsorbed with sulfur on the Mo(100) surface produced the desorption of SO at 1150 K, and of S, S₂ and O, but not SO₂. A pressure of 1 × 10^?7 Torr of O₂ was sufficient to remove sulfur from Mo(100) at temperatures over 1100 K. The basal plane of MoS₂ was unreactive in the presence of 1 atm of O₂ at temperatures of 520 K. Sputtering of the MoS₂ produced a marked uptake of oxygen and the removal of sulfur under the same conditions.     

Effect of bi-layer ratio in ZnO/Al2O3 multilayers on microstructure and functional properties of ZnO nanocrystals embedded in Al2O3 matrix

Zinc oxide (ZnO) nanocrystals (NCs) embedded in alumina (Al₂O₃) matrix were produced via rapid thermal annealing (RTA) of pulsed laser deposited ZnO/Al₂O₃ multilayered nanostructures. The effect of the thickness ratio (R) between Al₂O₃ and ZnO in one bi-layer on the microstructure and functional properties of NCs has been investigated. Grazing incidence small angle X-ray scattering confirmed the formation of nanocrystals after RTA. Grazing incidence wide angle X-ray scattering studies revealed that ZnO NCs have a high crystalline quality with (100) as preferred orientation. Tensile strain of NCs decreases with increasing R and is correlated to the distribution of NCs. From Raman analysis, it is noticed that the phonon frequency of the E₂ mode, related to the ZnO wurtzite phase, in NCs is shifted towards that of bulk ZnO with increasing R. Photoluminescence studies revealed that the near edge peak position shifts from 382 nm to 371 nm as the ratio R changes from 1.5 to 4 and is attributed to the strain effect. The intensity of emission in the yellow–green region due to defects decreases significantly with increasing R. Current–voltage (I–V) characteristics of Al/ZnO NCs embedded in Al₂O₃/n-Si (100)/Al have shown a hysteresis behavior. The increasing width of the hysteresis with increasing R revealed that the origin of the hysteresis might be due to the existence of polar surface charges on well-separated NCs. The high-resistance and low-resistance states in I–V hysteresis curves seem to be governed by Fowler–Nordheim tunneling and Schottky emission mechanisms, respectively.     

Silicon surface passivation by atomic‐layer‐deposited Al2O3 facilitated in situ by the combination of H2O and O3 as reactants

We investigate the effect of O₃ and H₂O oxidant pre‐pulse prior to Al₂O₃ atomic layer deposition for Si surface passivation. Interfacial oxide SiO_x formed by the O₃ pre‐pulse is more beneficial than that by H₂O to a high level of surface passivation. The passivation of thinner H₂O–Al₂O₃ films is more improved by this O₃ pre‐pulse. O₃ pre‐pulse for 10 nm H₂O–Al₂O₃ reduces saturation current density in boron emitter to 18 fA cm^–2 by a factor of 1.7. Capacitance–voltage measurements reveal this interfacial oxide plays a role of decreasing interface trap density without detrimental effect to negative charge density of Al₂O₃. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Swift ion irradiation effect on high-k ZrO2- and Al2O3-based MOS devices

This paper describes the heavy ion-induced effects on the electrical characteristics of reactively sputtered ZrO₂ and Al₂O₃ high-k gate oxides deposited in argon plus nitrogen containing plasma. Radiation-induced degradation of sputtered high-k dielectric ZrO₂/Si and Al₂O₃/Si interface was studied using 45?MeV Li³⁺ ions. The devices were irradiated with Li³⁺ ions at various fluences ranging from 5?×?10⁹ to 5?×?10¹²?ions/cm². Capacitance–voltage and current–voltage characteristics were used for electrical characterization. Shift in flat band voltage towards negative value was observed in devices after exposure to ion radiation. Post-deposition annealing effect on the electrical behavior of high-k/Si interface was also investigated. The annealed devices showed better electrical and reliability characteristics. Different device parameters such as flat band voltage, leakage current, interface defect density and oxide-trapped charge have been extracted.The surface morphology and roughness values for films deposited in nitrogen containing plasma before and after ion radiation are extracted from Atomic Force Microscopy.     

Room temperature hydrogen sensing of multiple networked ZnO/WO3 core–shell nanowire sensors under UV illumination

ZnO/WO₃ core–shell nanowires were synthesized by thermal evaporation of a mixture of ZnO and graphite powders (ZnO:C = 1:1) followed by sputter-deposition of WO₃. The sensing properties of multiple networked ZnO-core/WO₃-shell nanorod sensors toward H₂ gas was examined. The responses of pristine ZnO and ZnO-core/WO₃-shell nanorods to 1000 ppm H₂ at room temperature under UV illumination were ∼236% and ∼645%, respectively. The responses of the core–shell nanowires increased from ∼118 to ∼645% with increasing the UV illumination intensity from 0 mW/cm² to 1.2 mW/cm². The enhanced sensing performance of the ZnO-core/WO₃-shell nanowires induced by encapsulation with WO₃ was explained based on a combination of surface depletion and potential barrier-controlled carrier transport models. The origin of the enhanced sensing properties of ZnO-core/WO₃-shell nanorods toward H₂ under UV illumination was also discussed.     

Generation of MoS<Subscript>2</Subscript> quantum dots by laser ablation of MoS<Subscript>2</Subscript> particles in suspension and their photocatalytic activity for H<Subscript>2</Subscript> generation

MoS₂ quantum dots (QDs) have been obtained in colloidal suspensions by 532 nm laser ablation (7 ns fwhp/pulse, 50 mJ/pulse) of commercial MoS₂ particles in acetonitrile. High-resolution transmission electron microscopy images show a lateral size distribution from 5 to 20 nm, but a more homogeneous particle size of 20 nm can be obtained by silica gel chromatography purification in acetonitrile. MoS₂ QDs obtained by laser ablation are constituted by 3–6 MoS₂ layers (1.8–4 nm thickness) and exhibit photoluminescence whose λ_PL varies from 430 to 530 nm depending on the excitation wavelength. As predicted by theory, the confinement effect and the larger periphery in MoS₂ QDs increasing the bandgap and having catalytically active edges are reflected in an enhancement of the photocatalytic activity for H₂ generation upon UV–Vis irradiation using CH₃OH as sacrificial electron donor due to the increase in the reduction potential of conduction band electrons and the electron transfer kinetics.