ZnO Films Research Articles

"Blue-free" orange ZnO-related light-emitting diode based on a natural interface layer of Ga2O3 and ZnGa2O4.

To fabricate a ZnO-related light-emitting diode (LED) with zero emission at blue wavelengths ("blue-free"), an ingenious strategy is employed. Specifically, for the first time to the best of our knowledge, a natural oxide interface layer, possessing remarkable visible emission potential, is introduced into the Au/i-ZnO/n-GaN metal-insulator-semiconductor (MIS) structure. The unique Au/i-ZnO/interface layer/n-GaN structure successfully eliminated the harmful blue emissions (400-500 nm) from the ZnO film, and the remarkable orange electroluminescence is mainly attributed to the impact ionization process of the natural interface layer at high electric field. It is worth mentioning that the device achieved ultra-low color temperature (2101 K) and excellent color rendering index (92.8) under electrical injection, indicating that the device could fulfill the requirements of electronic display systems and general illumination, and might even play unexpected roles in special lighting domains. The results obtained provide a novel and effective strategy for the design and preparation of ZnO-related LEDs.

Formation of ZnO films on SiC/porous Si/Si substrates

Reactive magnetron sputtering was used to obtain ZnO films on SiC/porous Si/Si substrates. The silicon carbide film on the surface of porous Si was obtained using chemical substitution of atoms. It has been shown that ZnO films grown at the partial oxygen pressure 0.6 Pa are characterized by a smoother and more uniform surface than coatings grown at the oxygen pressure 0.1 Pa. Being based on the analysis of Raman and photoluminescence spectra, it has been shown that the increase in partial pressure of oxygen leads to the increase in structural disorder of the ZnO crystal lattice, on the one hand, and at the same time to a decrease in the concentration of intrinsic defects, including ionized oxygen vacancies Oi, on the other hand.

The Progress on Magnetic Material Thin Films Prepared Using Polymer-Assisted Deposition.

Polymer-assisted deposition (PAD) has been widely used in the preparation of high-quality oxides and sulfides for basic research and applications. Specifically, diverse PAD-prepared magnetic material thin films such as ZnO, Ga2O3, SrRuO3, LaCoO3, LaMnO3, Y3Fe5O12, MoS2, MoSe2, and ReS2 thin films have been grown, in which thickness-dependent, strain-modulated, doping-mediated, and/or morphology-dependent room-temperature ferromagnetism (RTFM) have been explored. Inspired by the discovery of intrinsic low-temperature FM in two-dimensional (2D) systems prepared using mechanical exfoliation, the search for more convenient methods to prepare 2D ferromagnetic materials with high-temperature FM has seen explosive growth, but with little success. Fortunately, the very recent synthesis of 2D NiO by PAD has shed light on this challenge. Based on these abovementioned developments, the difficulties of PAD when preparing a-few-nanometer single-crystalline materials and the opportunities in PAD for novel materials such as chiral magnetic soliton material Cr1/3NbS2 are discussed.

Stable Superhydrophobic and Antimicrobial ZnO/Polytetrafluoroethylene Films via Radio Frequency (RF) Magnetron Sputtering.

In this study, superhydrophobic ZnO/Polytetrafluoroethylene (ZnO/PTFE) films with water droplet contact angles (CA) observed as high as 165° and water droplet sliding angles of (SA) <1° have been prepared on glass substrates by RF magnetron sputtering. The PTFE was wrapped on a nano-rod made of a ZnO film with superhydrophobic properties while providing excellent UV resistance compared to hexadecyltrimethoxysilane (HDTMS) hydrophobic agents. The upper surface of the rough ZnO film was coated with PTFE, and most of the underlying coating was bare ZnO, which could well make contact with bacteria. For the Gram-negative strain, E. coli, the cell viability count of the ZnO/PTFE sample (3.5 log reduction, 99.96%) was conspicuously lower than that of the ZnO/HDTMS sample (1.2 log reduction, 93.87%) under 1 h illumination of UV light, which showed that the ZnO/PTFE sample has a better photocatalytic property than the ZnO/ HDTMS films. The ZnO/PTFE films also showed good mechanical robustness, which is an important consideration in their widespread real-world adoption.

Comprehensive characterization of Al-doped ZnO thin films deposited in confocal radio frequency magnetron co-sputtering

Al-doped ZnO thin films with varying Aluminium (Al) content were deposited by radio frequency magnetron co-sputtering of two ZnO and Al targets in confocal configuration. A comprehensive study of the effect of Al content variation on the structural, optical and electrical properties were studied for as-deposited films and after an annealing step under controlled argon atmosphere. Chemical composition analyses, performed by both X-ray photoelectron spectroscopy and energy dispersive X-ray spectrometry, show an Al content variation in the deposited films in the 0-14 at.% range by varying the Al target power from 0 to 30 W, while the Zn target power was kept constant at 200 W. All deposited films exhibit a wurtzite crystalline structure and a decreasing crystalline quality for Al content above 5 at.% as shown by grazing incidence X-ray diffraction patterns. Atomic Force Microscopy analysis revealed films with homogeneous and dense surface morphology with roughness in the one nm range. Carrier concentration, resistivity and photoluminescence vary significantly with Al content in the ZnO films and appear optimized for an Al content window ranging from 1.5 to 5.5 at. %. Both optical and electrical properties are improved by a post-annealing at 300°C under argon. A high figure of merit of 43.6 × 10-4 sq.Ω-1 was obtained for the ZnO film with Al content of 3.6 at.% after annealing at 300°C. Optimized properties are obtained for a higher Al content than the standard value of 2 at. % widely used in published works.

Aluminum-doped zinc oxide (AZO) ultra-thin films deposited by radio frequency sputtering for flexible Cu(In,Ga)Se2 solar cells

Zinc oxide ultra-thin films doping with aluminum (AZO) were produced through radio frequency (rf) sputtering at a fixed pressure of 10 mTorr while varying the rf power between 80 and 140 W. The crystal structure of hexagonal Wurtzite was consistent throughout, with improved crystallinity observed at higher rf powers due to optimal diffusivity of the sputtered particles during nucleation and growth. The size of the crystallite was increased from 10.37 to 16.58 nm with increasing the rf power from 80 to 140 W. The Raman spectra provided evidence of the formation of ultra-thin AZO films, with discernable changes in morphology due to the influence of rf power. The value of optical band gap fluctuated between 3.49 and 3.58 eV as a function of rf power, a basis of the Burstein–Moss effect. The resistivity of the ultra-thin AZO films declined while augmenting rf power. A bilayer structure of intrinsic ZnO (i-ZnO) and AZO was fabricated and exhibited good transmittance, well-crystalline morphology, and excellent electrical conductivity. The optimized window layer (i-ZnO and AZO) was used to produce flexible Cu(In,Ga)Se2(CIGSe) solar cells with a photo conversion efficiency of 9.53%. Therefore, ultra-thin ZnO films exhibit potential as a favorable option for a window layer in the production of high-efficient flexible solar cells in cost effective way.

Enhanced solar-driven water splitting performance using oxygen vacancy rich ZnO photoanodes

This work reports a facile two-step method of producing highly efficient ZnO photoanodes for photoelectrochemical (PEC) water splitting under solar light conditions and describes the role of surface oxygen vacancies (VO) in their enhanced PEC performance. The photoanode fabrication involves post-growth oxidation of a metallic Zn layer, which produces a nanostructured ZnO film consisting of ∼50 nm diameter nanorods containing a high concentration of VO defects. The PEC activity of the ZnO films is investigated by studying water oxidation in an aqueous electrolyte under simulated solar illumination. The relationship of PEC and charge transfer characteristics of the ZnO photoanodes with ionized surface VO defects is established using cathodoluminescence, X-ray photoemission, voltammetry, electrochemical impedance spectroscopy and chronoamperometry. The combined results show that the photoanode fabricated in this work possesses a high surface density of ionized VO states that facilitate the effective transportation of holes for water oxidation. It is found that the photoanode exhibits an exceptional photocurrent density of 1.14 mA/cm2 at 1.23 VRHE, being one of the best performances reported in the literature for ZnO-based photoelectrodes so far. Our results demonstrate a simple, low-cost method for fabricating highly efficient VO rich ZnO-based PEC photoanodes that is suitable for large scale production.

Enabling high-quality transparent conductive oxide on 3D printed ZrO2 architectures through atomic layer deposition

The conformal atomic layer deposition of a transparent conductive oxide composed of Al-doped ZnO (AZO) over three-dimensional (3D) shaped ZrO2 microarchitectures produced using two-photon lithography (TPL) is reported here for the first time. The effect of ZrO2 morphology, surface roughness, and crystallographic phase (tetragonal and monoclinic) on the quality and properties of the deposited ZnO and AZO thin films is investigated. No discontinuities, domains, or areas differing from the desired chemical composition have been found in films grown over the 3D structures. Three different Al dopant concentrations (4.0 %, 4–5 %, and 5.0 % Al doping cycles) are examined and compared to undoped ZnO. AZO and ZnO optical and electrical properties are studied using cathodoluminescence (CL) and Hall effect measurements. The CL study confirms that the observed emissions from the ZnO and AZO films are associated with the near band emission of ZnO and defects, i.e., zinc and oxygen vacancies and interstitial oxygen. The AZO films exhibit n-type semiconductor behavior, and a minimum resistivity of 1.2 × 10-3 Ω cm is achieved. From a broad perspective, AZO deposition on 3D microarchitectures opens a new route towards dimensionally refined optoelectronic devices in which the ZrO2/AZO can serve as an enabling role for the production of electrodes.

Increase the current density and reduce the defects of ZnO by modification of the band gap edges with Cu ions implantation for efficient, flexible dye-sensitized solar cells (FDSSCs)

Flexible dye-sensitized solar cells (FDSSCs) have good potential in future photovoltaic technology. The spin coating method deposited the ZnO films on indium-tin-oxide-coated polyethylene terephthalate (ITO-PET) flexible plastic substrates. These films are implanted with Cu-ions with 1 × 1013 ions/cm2, 1 × 1014 ions/cm2, and 1 × 1015 ions/cm2. All the films have a hexagonal structure. The film irradiated with 1 × 1014 ions/cm2 showed high crystallinity and crystallite size. Important optical properties like bandgap energy (Eg), band edges, refractive index, extinction coefficient, and dielectric constants are measured by UV–Vis spectroscopy. Bandgap energy decreases, and the refractive index increases at the fluence of Cu ions. The maximum decrease in Eg is observed at the 1 × 1014 ions/cm2 dose. Photoluminescence spectra suggest that defects-related emission peaks are decreased at 1 × 1014 ions/cm2 Cu ions fluency. J-V measurements have significantly improved photovoltaic performance compared to pristine ZnO-based solar cells. The highest efficiency (2.30%) is observed at a 1 × 1014 ions/cm2 dose. The efficiency increase is related to improving the charge transfer ratio and shifting the fermi level toward the conduction band.

To improve device performance of self-driven heterojunction photodetectors by inserting a thin layer of silver nanoparticles into the electron-transporting layer

Lead selenide colloidal quantum dots (CQDs) are widely used in infrared photodetectors due to their size-dependent bandgap tunability, facile solution-processing techniques and low cost. Heterojunctions (HJs) are usually used to construct device to facilitate the separation of excitons and the transportation of photogenerated carriers. Based on the solution-processed HJ photodetector ITO/ZnO/PbSe/Ag, in which PbSe CQDs layer acts as the active layer and ZnO nanoparticles (NPs) layer as the electron-transporting layer, a greatly enhanced-performance was obtained after inserting 10 nm Ag NPs layer within the ZnO NPs layer close to the HJ ZnO/PbSe interface. By optimizing the concentration of Ag NPs solutions and the location of Ag NPs thin layer in ZnO film, the maximum responsivity of the self-driven HJ photodetector ITO/ZnO(50 nm):Ag-NPs(10 nm):ZnO(50 nm)/PbSe(300 nm)/Ag reaches to 6.25 mA/W with a specific detectivity D* of 5.17 ×1011 Jones under 8.5 μW/cm² 1550 nm illumination at zero bias. Further, the underlain physical mechanisms for the enhanced-performance were discussed in details. In this way, it provides a very efficient method for enhanced-performance self-driven HJ photodetectors by inserting a thin layer of metal NPs into the electron-transporting layer close to the heterojunction interface.

Investigation of carrier transport in ZnO and ZnO:Al thin films sputtered at different oxygen conditions

Undoped and doped zinc oxide in film form is used in a wide range of applications. Its electrical and optical properties depend on the oxide conditions during preparation, which are influenced by many deposition parameters. The aim of this work was to experimentally investigate the properties of films deposited under clearly defined oxygen-rich and oxygen-poor conditions. The observed property changes were then described based on theoretical assumptions about internal defects formed in ZnO under different oxygen conditions. To achieve the objective, the ZnO and ZnO:Al films were sputtered in a mixture of argon and oxygen to ensure oxygen-rich conditions. Oxygen-poor conditions were provided by co-sputtering from oxide and metal targets in argon. We have found that the growth in oxygen-rich conditions leads to approximately stoichiometric ZnO films and the films prepared under oxygen-poor conditions are strongly oxygen deficient. The resistivity of undoped ZnO films can be controlled from 108 to 10−2 Ωcm while maintaining high transparency in the visible spectrum. The high resistivity is caused by the formation of deep acceptors under oxygen-rich conditions. The high concentration of zinc interstitials is responsible for the low resistivity in oxygen poor conditions. Even in the case of ZnO:Al films, the carrier concentration is strongly reduced at oxygen-rich conditions by the deep acceptors. These defects tend to relax during vacuum annealing at 300 °C due to self-diffusion. The carrier mobility is mainly related to the crystallinity. The formation of a high number of basal edge dislocations has been identified as a reason for the reduction in transmittance.

The Influence of Surface Processing on the Surface Plasmonic Enhancement of an Al-Nanoparticles-Enhanced ZnO UV Photodectector.

Surface Plasmonic Resonance (SPR) induced by metallic nanoparticles can be exploited to enhance the response of photodetectors (PD) to a large degree. Since the interface between metallic nanoparticles and semiconductors plays an important role in SPR, the magnitude of the enhancement is highly dependent on the morphology and roughness of the surface where the nanoparticles are distributed. In this work, we used mechanical polishing to produce different surface roughnesses for the ZnO film. Then, we exploited sputtering to fabricate Al nanoparticles on the ZnO film. The size and spacing of the Al nanoparticles were adjusted by sputtering power and time. Finally, we made a comparison among the PD with surface processing only, the Al-nanoparticles-enhanced PD, and the Al-nanoparticles-enhanced PD with surface processing. The results showed that increasing the surface roughness could enhance the photo response due to the augmentation of light scattering. More interestingly, the SPR induced by the Al nanoparticles could be strengthened by increasing the roughness. The responsivity could be enlarged by three orders of magnitude after we introduced surface roughness to boost the SPR. This work revealed the mechanism behind how surface roughness influences SPR enhancement. This provides new means for improving the photo responses of SPR-enhanced photodetectors.

Kinetic and Thermodynamic Study of Methylene Blue Adsorption on TiO2 and ZnO Thin Films.

In this work, we fabricated and characterized ZnO and TiO2 thin films, determining their structural, optical, and morphological properties. Furthermore, we studied the thermodynamics and kinetics of methylene blue (MB) adsorption onto both semiconductors. Characterization techniques were used to verify thin film deposition. The semiconductor oxides reached different removal values, 6.5 mg/g (ZnO) and 10.5 mg/g (TiO2), after 50 min of contact. The pseudo-second-order model was suitable for fitting the adsorption data. ZnO had a greater rate constant (45.4 × 10-3) than that of TiO2 (16.8 × 10-3). The removal of MB by adsorption onto both semiconductors was an endothermic and spontaneous process. Finally, the stability of the thin films showed that both semiconductors maintained their adsorption capacity after five consecutive removal tests.

Study of the Influence of Doping on the Structural, Optical and Electrical Properties of zinc oxide thin Films Produced by by Spray Pyrolysis for Solar Cell Applications

In the present study, the effect of Al doping with 0.5 % Al (AZO-0.50), 1 % Al (AZO-1.00), and 1.5 % Al (AZO-1.50) have been successfully synthesized by Spray Pyrolysis method. The structural, optical and electrical properties of the obtained films was studied. The obtained films are characterized by different techniques such as X-ray diffraction (XRD), UV-visible and electrical Hall Effect measurements. The X-ray diffraction confirmed that the Al doping did not change the ZnO Hexagonal Wurtzite structure. Spectroscopic measurements in the UV-VIS-IR wavelength range were found to give good average transmittance values of about 73%, with a high transmittance of 75% with 0.5% Al doping. The optical gap value increases in the range of 3.23 to 3.26 eV with increasing aluminium content. The electrical analysis shows that the conductivity improved with doping compared to the pure ZnO film

Facile Synthesis of Multicolored Stacked Quantum Dot Films for Efficient White Light Emission

Quantum dot (QD)-based white light-emitting diodes (LEDs) or white QD-LEDs were successfully fabricated by stacking QD films of primary colors (i.e., red, green, and blue). An ultrathin ZnO film was deposited between each QD layer to facilitate the formation of a tricolor-stacked QD structure. Such stacked QD films effectively suppress the Förster resonance energy transfer between QDs and enable efficient blue light emission, unlike randomly mixed QD films of different colors. The photoluminescence (PL) spectra of various QD films were obtained to study the change in the corresponding color gamut with applied voltage. In addition, QD-LEDs were fabricated based on the PL behavior and electronic band diagrams of QDs of different colors. Maximum luminance and peak EQE of white QD-LED shows 5700 cd/m2 and 1.1% compared to 2200 cd/m2 and 0.3% of QD-LED with mixed QD layer. Finally, a smooth color transition and white light emission were achieved using a blue/green/red stacking sequence for the QDs, which successfully suppressed the energy transfer effect. The overall performance and brightness of the white QD-LEDs synthesized in this study can be further enhanced by developing high-performance blue QDs.

Tuning the texture and polarity of ZnO thin films deposited by spatial atomic layer deposition through the addition of a volatile shape-directing agent

Many functional devices are nowadays based on thin films deposited by physical or chemical vapour deposition methods. Being able to control the texture of the films is very important to tune their functional properties. Texture is commonly tuned by either using single crystalline substrates or seed layers, or by modifying the deposition parameters (gas flows, precursor concentration, temperature, etc.). In this study a volatile shape-directing agent (VSDA), namely 4-(5)-Methylimidazole (4-(5)-MeIM), is used during the deposition of ZnO thin films by Atmospheric-Pressure Spatial Atomic Layer Deposition (AP-SALD) to control the texture and growth rate of the films. In particular, ZnO thin films can be grown preferentially along [001], resulting in an enhanced piezoelectric coefficient. In addition, the polarity of the ZnO films also depends on the amount of VSDA used. An innovative industry-compatible approach to control texture and polarity of ZnO thin films is presented, having a clear potential for other functional materials and applications.

Room-temperature electrochemical deposition of nanostructured ZnO films on FTO substrate and their photoelectrochemical activity

The possibility of fabrication of nanostructured ZnO layers on conductive glass substrates via simple room-temperature electrodeposition was studied in detail. The process was carried out in zinc nitrate electrolyte at different potentials for various durations. The morphology, composition, and semiconducting properties of the deposits were examined by various techniques. As-synthesized materials were found to be amorphous and co-deposition of the metallic Zn at more negative potentials was confirmed. Nevertheless, thermal treatment in air results in the successful conversion of the as-deposited precipitate to the wurtzite ZnO. The potential of −1.5 V vs. SCE was identified as optimal to achieve both full coverage of the glass substrate, as well as uniform morphology of the deposits. In general, the photoelectrochemical performance of such kind of ZnO photoanodes was found to be significantly dependent on the electrodeposition duration since this parameter strongly affected the thickness, surface morphology, as well as semiconducting properties of the obtained material. In consequence, the photoanode deposited at −1.5 V vs. SCE for 40 min exhibited the most promising photoelectrochemical activity under studied conditions.

Characterization of ZnO, Ga-Doped ZnO, and Nd-Ga-Doped ZnO Thin Films Synthesized by Radiofrequency Magnetron Sputtering

Here is described the influence of deposition parameters of ZnO thin films doped with Ga and co-doped with (Ga + Nd) upon the structural, morphological, optical and electrical properties. The transparent conductive thin films were fabricated by radiofrequency (RF) magnetron sputtering using a power of 100 W and a deposition distance of 6 cm. The deposition was performed on glass substrates heated at 150 °C with a time deposition of 90 min. The influence of doping upon the structure of thin films was analyzed by x-ray diffraction (XRD). Optical transmission measurements showed an 85% transparency in the visible range for the undoped ZnO films and the transparency of these films decreased when the dopants were added. Micro-structural analysis obtained by atomic force microscopy (AFM) evidenced that the type of doping modify the microstructure of thin films. Raman and resistivity measurements emphasize the successful incorporation of dopants into the ZnO host material.

Efficient fluorescent vapour sensing induced by ZnO buffer

Fluorescent film sensors have been widely used in the detection and alarm of toxic and harmful gases such as explosives and drugs. However, its current development is limited by the complex design and synthesis of high-performance sensitive materials. Therefore, simple and effective methods that can improve the sensing performance of the existing fluorescent materials are severely demanded, which can further reduce the dependence on sensitive materials in fluorescent sensors. In this study, by simply growing or depositing ZnO film on the quartz substrate, enhanced sensing performance of the fluorescent sensor is realized. The sensing process between 4- (phenyl (4- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) phenyl) amino) benzaldehyde (OTB) probe molecules and H2O2 gas is effectively accelerated by utilizing the catalytic properties of ZnO buffer. Through mimicry, the reaction rate constant is increased 4.76 times, and the time required for 50% fluorescence quenching is reduced from 258 min to 80 min. In the film-based sensor, the time required for 50% fluorescence quenching is reduced from 531.7 s to 186.0 s. It is shown that zinc oxide buffers prepared by atomic layer deposition or hydrothermal method have similar effects for enhanced sensing capability. In addition, such a method is further verified to be effective for the detection of other two dangerous gas simulants, methamphetamine (MPEA) and diethyl chlorophosphate (DCP). Specifically, for MPEA and DCP sensing, the fluorescence enhancement ratio increases from 1.2 to 5 times to 2.7 and 18 times in the control group within 300 s and 20 s, respectively. Moreover, theoretical calculation and solution mimic experiments further reveal the mechanism of ZnO buffer for accelerated sensing is due to the catalytic activity of ZnO buffer for the reaction.

Preparation and evaluation of Zn(O,S) thin film layer by sulfurization method

In this paper, we propose a method of incorporating sulfur on the ZnO film surface, which can effectively alter the properties of the ZnO. Through sulfurization, a ZnS cubic crystal structure is formed in the ZnO film, with the ZnS peak increasing as the sulfur weight increases. This approach may pave the way for the successful production of Zn(O,S) film which may suit as an alternative buffer layer for CIGS solar cell structure.