Engineering electrodeposited ZnO films and their memristive switching performance

We report the influence of zinc oxide (ZnO) seed layers on the performance of ZnO-based memristive devices fabricated using an electrodeposition approach. The memristive element is based on a sandwich structure using Ag and Pt electrodes. The ZnO seed layer is employed to tune the morphology of the electrodeposited ZnO films in order to increase the grain boundary density as well as construct highly ordered arrangements of grain boundaries. Additionally, the seed layer also assists in optimizing the concentration of oxygen vacancies in the films. The fabricated devices exhibit memristive switching behaviour with symmetrical and asymmetrical hysteresis loops in the absence and presence of ZnO seed layers, respectively. A modest concentration of oxygen vacancy in electrodeposited ZnO films as well as an increase in the ordered arrangement of grain boundaries leads to higher switching ratios in Ag/ZnO/Pt devices.

Hexagon platinum Schottky contact with ZnO thin film for hydrogen sensing

This paper reports on the study of the effect on adding total peripheries and sharp edges to the Schottky contact as a hydrogen sensor. Schottky contact was successfully designed and fabricated as hexagon-shape. The contact was integrated together with zinc oxide thin film and tested towards 1% hydrogen gas. Simulations of the design were conducted using COMSOL Multiphysics to observe the electric field characteristic at the contact layer. The simulation results show higher electric field induced at sharp edges with 4.18×104 V/m. Current-voltage characteristic shows 0.27 V voltage shift at 40 μA biased current.

ZnO nanocones with high-index {101̅1} facets for enhanced energy conversion efficiency of dye-sensitized solar cells

ZnO is a promising photoanode material for dye-sensitized solar cells (DSCs) due to its high bulk electron mobility and because different geometrical structures can easily be tailored. Although various strategies have been taken to improve ZnO-based DSC efficiencies, their performances are still far lower than TiO2 counterparts, mainly because low conductivity Zn2+–dye complexes form on the ZnO surfaces. Here, cone-shaped ZnO nanocrystals with exposed reactive O-terminated {101̅1} facets were synthesized and applied in DSC devices. The devices were compared with DSCs made from more commonly used rod-shaped ZnO nanocrystals where {101̅0} facets are predominantly exposed. When cone-shaped ZnO nanocrystals were used, DSCs sensitized with C218, N719, and D205 dyes universally displayed better power conversion efficiency, with the highest photoconversion efficiency of 4.36% observed with the C218 dye. First-principles calculations indicated that the enhanced DSCs performance with ZnO nanocone photoanodes could be attributed to the strength of binding between the dye molecules and reactive O-terminated {101̅1} ZnO facets and that more effective use of dye molecules occurred due to a significantly less dye aggregation on these ZnO surfaces compared to other ZnO facets.

Using pulse transit delay in Z-scan to discriminate between excited-state absorption and other nonlinear processes in ZnO nanocones

We report a new approach that uses the single beam Z-scan technique, to discriminate between excited state absorption (ESA) and two and three photon nonlinear absorption. By measuring the apparent delay or advance of the pulse in reaching the detector, the nonlinear absorption can be unambiguously identified as either instantaneous or transient. The simple method does not require a large range of input fluences or sophisticated pulse-probe experimental apparatus. The technique is easily extended to any absorption process dependent on pulse width and to nonlinear refraction measurements. We demonstrate in particular, that the large nonlinear absorption in ZnO nanocones when exposed to nanosecond 532 nm pulses, is due mostly to ESA, not pure two-photon absorption.

Encapsulation of nanoparticles into single-crystal ZnO nanorods and microrods

One-dimensional single crystal incorporating functional nanoparticles of other materials could be an interesting platform for various applications. We studied the encapsulation of nanoparticles into single-crystal ZnO nanorods by exploiting the crystal growth of ZnO in aqueous solution. Two types of nanodiamonds with mean diameters of 10 nm and 40 nm, respectively, and polymer nanobeads with size of 200 nm have been used to study the encapsulation process. It was found that by regrowing these ZnO nanorods with nanoparticles attached to their surfaces, a full encapsulation of nanoparticles into nanorods can be achieved. We demonstrate that our low-temperature aqueous solution growth of ZnO nanorods do not affect or cause degradation of the nanoparticles of either inorganic or organic materials. This new growth method opens the way to a plethora of applications combining the properties of single crystal host and encapsulated nanoparticles. We perform micro-photoluminescence measurement on a single ZnO nanorod containing luminescent nanodiamonds and the spectrum has a different shape from that of naked nanodiamonds, revealing the cavity effect of ZnO nanorod.

Property-performance control of multidimensional, hierarchical, single-crystalline ZnO nanoarchitectures

Diverse morphologies of multidimensional hierarchical single-crystalline ZnO nanoarchitectures including nanoflowers, nanobelts, and nanowires are obtained by use of a simple thermal evaporation and vapour-phase transport deposition technique by placing Au-coated silicon substrates in different positions inside a furnace at process temperatures as low as 550 °C. The nucleation and growth of ZnO nanostructures are governed by the vapour–solid mechanism, as opposed to the commonly reported vapour–liquid–solid mechanism, when gold is used in the process. The morphological, structural, compositional and optical properties of the synthesized ZnO nanostructures can be effectively tailored by means of the experimental parameters, and these properties are closely related to the local growth temperature and gas-phase supersaturation at the sample position. In particular, room-temperature photoluminescence measurements reveal an intense near-band-edge ultraviolet emission at about 386 nm for nanobelts and nanoflowers, which suggests that these nanostructures are of sufficient quality for applications in, for example, optoelectronic devices.

Plasma-aided hydrogenation and Al-doping : increasing the conductivity and optical transparency of ZnO transparent conducting oxide

Plasma-assisted magnetron sputtering with varying ambient conditions has been utilised to deposit Al-doped ZnO (AZO) transparent conductive thin films directly onto a glass substrate at a low substrate temperature of 400 °C. The effects of hydrogen addition on electrical, optical and structural properties of the deposited AZO films have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), Hall effect measurements and UV–vis optical transmission spectroscopy. The results indicate that hydrogen addition has a remarkable effect on the film transparency and conductivity with the greatest effects observed with a hydrogen flux of approximately 3 sccm. It has been demonstrated that the conductivity and the average transmittance in the visible range can increase simultaneously contrary to the effects observed by other authors. In addition, hydrogen incorporation further leads to the absorption edge shifting to a shorter wavelength due to the Burstein–Moss effect. These results are of particular relevance to the development of the next generation of optoelectronic and photovoltaic devices based on highly transparent conducting oxides with controllable electronic and optical properties.

Structural, optical and electrical properties of Al-doped ZnO transparent conducting oxide for solar cell applications

Al-doped zinc oxide (AZO) thin films are deposited onto glass substrates using radio-frequency reactive magnetron sputtering and the improvements in their physical properties by post-synthesis thermal treatment are reported. X-ray diffraction spectra show that the structure of films can be controlled by adjusting the annealing temperatures, with the best crystallinity obtained at 400°C under a nitrogen atmosphere. These films exhibit improved quality and better optical transmittance as indicated by the UV-Vis spectra. Furthermore, the sheet resistivity is found to decrease from 1.87 × 10-3 to 5.63 × 10-4Ω⋅cm and the carrier mobility increases from 6.47 to 13.43 cm2 ⋅ V-1 ⋅ s-1 at the optimal annealing temperature. Our results demonstrate a simple yet effective way in controlling the structural, optical and electrical properties of AZO thin films, which is important for solar cell applications.

Temperature-dependent growth mechanisms of low-dimensional ZnO nanostructures

One-dimensional ZnO nanostructures were successfully synthesized on single-crystal silicon substrates via a simple thermal evaporation and vapour-phase transport method under different process temperatures from 500 to 1000 °C. The detailed and in-depth analysis of the experimental results shows that the growth of ZnO nanostructures at process temperatures of 500, 800, and 1000 °C is governed by different growth mechanisms. At a low process temperature of 500 °C, the ZnO nanostructures feature flat and smooth tips, and their growth is primarily governed by the vapour-solid mechanism. At an intermediate process temperature of 800 °C, the ZnO nanostructures feature cone-shape tips, and their growth is primarily governed by the self-catalyzed and saturated vapour–liquid–solid mechanism. At a high process temperature of 1000 °C, the alloy tip appears on the front side of the ZnO nanostructures, and their growth is primarily governed by the common catalyst-assisted vapour–liquid–solid mechanism. It is also shown that the morphological, structural, optical, and compositional properties of the synthesized ZnO nanostructures are closely related to the process temperature. These results are highly relevant to the development of light-emitting diodes, chemical sensors, energy conversion devices, and other advanced applications.

Effect of doping with Co and/or Cu on electronic structure and optical properties of ZnO

This paper reports on ab initio numerical simulations of the effect of Co and Cu dopings on the electronic structure and optical properties of ZnO, pursued to develop diluted magnetic semiconductors vitally needed for spintronic applications. The simulations are based upon the Perdew-Burke-Enzerh generalized gradient approximation on the density functional theory. It is revealed that the electrons with energies close to the Fermi level effectively transfer only between Cu and Co ions which substitute Zn atoms, and are located in the neighbor sites connected by an O ion. The simulation results are consistent with the experimental observations that addition of Cu helps achieve stable ferromagnetism of Co-doped ZnO. It is shown that simultaneous insertion of Co and Cu atoms leads to smaller energy band gap, redshift of the optical absorption edge, as well as significant changes in the reflectivity, dielectric function, refractive index, and electron energy loss function of ZnO as compared to the doping with either Co or Cu atoms. These highly unusual optical properties are explained in terms of the computed electronic structure and are promising for the development of the next-generation room-temperature ferromagnetic semiconductors for future spintronic devices on the existing semiconductor micromanufacturing platform.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Self-organized ZnO nanodot arrays : effective control using SiNx interlayers and low-temperature plasmas

An advanced inductively coupled plasma (ICP)-assisted rf magnetron sputtering deposition method is developed to synthesize regular arrays of pear-shaped ZnO nanodots on a thin SiNx buffer layer pre-deposited onto a silicon substrate. It is shown that the growth of ZnO nanodots obey the cubic root-law behavior. It is also shown that the synthesized ZnO nanodots are highly-uniform, controllable by the experimental parameters, and also feature good structural and photoluminescent properties. These results suggest that this custom-designed ICP-based technique is very effective and highly-promising for the synthesis of property- and size-controllable highly-uniform ZnO nanodots suitable for next-generation light emitting diodes, energy storage, UV nanolasers, and other applications.

Raman-active wurtzite CdO nanophase and phonon signatures in CdO/ZnO heterostructures fabricated by nonequilibrium laser plasma ablation and stress control

A combination of laser plasma ablation and strain control in CdO/ZnO heterostructures is used to produce and stabilize a metastable wurtzite CdO nanophase. According to the Raman selection rules, this nanophase is Raman-active whereas the thermodynamically preferred rocksalt phase is inactive. The wurtzite-specific and thickness/strain-dependent Raman fingerprints and phonon modes are identified and can be used for reliable and inexpensive nanophase detection. The wurtzite nanophase formation is also confirmed by x-ray diffractometry. The demonstrated ability of the metastable phase and phonon mode control in CdO/ZnO heterostructures is promising for the development of next-generation light emitting sources and exciton-based laser diodes.

ZnO layers for opto-electronic applications from solution-based and low-temperature processing of an organometallic precursor

As printed and flexible plastic electronic gadgets become increasingly viable today, there is a need to develop materials that suit the fabrication processes involved. Two desirable requirements are solution-processable active materials or precursors and low-temperature processability. In this article, we describe a straightforward method of depositing ZnO films by simple spin coating of an organometallic diethylzinc precursor solution and annealing the resulting film at low temperatures (≤200 °C) without involving any synthetic steps. By controlling the humidity in which annealing is conducted, we are able to adjust the intrinsic doping level and carrier concentration in diethylzinc-derived ZnO. Doped or conducting transport layers are greatly preferable to undoped layers as they enable low-resistance contacts and minimize the potential drops. This ability to controllably realize doped ZnO is a key feature of the fabrication process that we describe in this article. We employ field-effect measurements as a diagnostic tool to measure doping levels and mobilities in ZnO and demonstrate that doped ZnO with high charge carrier concentration is ideal for solar cell applications. Respectable power conversion efficiencies (up to 4.5%) are achieved in inverted solar cells that incorporate diethylzinc-derived ZnO films as the electron transport layer and organic blends as the active material. Extensions of this approach to grow ternary and quaternary films with organometallic precursor chemicals will enable solution based growth of a number of semiconductor films as well as a method to dope them.