Sol–gel derived undoped and boron-doped ZnO semiconductor thin films: Preparation and characterization

We report the influence of boron doping concentration on the microstructure, electrical and optical properties of solution-processed zinc oxide (ZnO) thin films. The B doping concentration in the resultant solutions was varied from 0 to 5 at%, and the pH value of each synthetic solution was adjusted to 7.0. XRD measurements, SEM observations, and SPM examinations revealed that boron doping produced ZnO thin films consisting of a fine grain structure with a flat surface morphology. Moreover, ZnO thin films doped with B raised the texture coefficient along the (002) plane. All B-doped ZnO (ZnO:B) thin films exhibited higher transparency than that of the undoped ZnO thin film in the wavelengths between 350 and 650 nm. The optical band gap and Urbach energy of the ZnO:B thin films were higher than those of the undoped thin film. According to electrical transport characteristics, the 1% B-doped ZnO thin film exhibited the highest Hall mobility of 17.9 cm²/V s, the highest electron concentration of 1.2×10¹⁵ cm⁻³, and the lowest electrical resistivity of 2.2×10² Ω cm among all of the ZnO:B thin films.     

Concentration dependence of physical properties of low temperature processed ZnO quantum dots thin films on polyethylene terephthalate as potential electron transport material for perovskite solar cell

Colloidal Zinc oxide quantum dots (ZnO QDs) prepared with varying concentrations through precipitation method were deposited on flexible ITO/PET substrates using spin-coating technique. Various characterization tools were utilized to investigate the morphological, structural, electrical and optical properties of the films. The crystallinity of the films was found to improve with increasing ZnO QD concentration (ZQ_C) as evident from the X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) studies. Crystallographic and optical parameters were evaluated and explained in depth. The average nanograin size and bandgap were increased and decreased respectively, from ～5 nm to ～8 nm and 3.29 eV–3.24 eV with an increase in ZQ_C from 10 mg/mL to 70 mg/mL. Columnar structure growth of the films is revealed by AFM results. The films showed decent optical transparency up to 81%. All the ZnO films exhibited n-type semiconducting property as indicated by the electrical measurements with carrier mobility and low resistivity of 12.21–26.63 cm²/Vs and 11.84 × 10^?3 to 13.16 × 10^?3 Ω cm respectively. Based on the experimental findings, ZnO QD nanostructure film grown at 50 mg/mL is envisaged to be a potential candidate for flexible perovskite photovoltaic application.     

Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors

This work presents a novel method to prepare graphene quantum dots (GQDs) directly from graphite. A composite film of GQDs and ZnO was first prepared using the composite target of graphite and ZnO via magnetron sputtering, followed with hydrochloric acid treatment and dialysis. Morphology and optical properties of the GQDs were investigated using a number of techniques. The as-prepared GQDs are 4–12 nm in size and 1–2 nm in thickness. They also exhibited typical excitation-dependent properties as expected in carbon-based quantum dots. To demonstrate the potential applications of GQDs in electronic devices, pure ZnO and GQD–ZnO thin-film transistors (TFTs) using ZrO_x dielectric were fabricated and examined. The ZnO TFT incorporating the GQDs exhibited enhanced performance: an on/off current ratio of 1.7 × 10⁷, a field-effect mobility of 17.7 cm²/Vs, a subthreshold swing voltage of 90 mV/decade. This paper provides an efficient, reproducible and eco-friendly approach for the preparation of monodisperse GQDs directly from graphite. Our results suggest that GQDs fabricated using magnetron sputtering method may envision promising applications in electronic devices.     

p-type doping by B ion implantation into diamond at elevated temperatures

We have studied B ion implantation at 400 °C into undoped homoepitaxial chemical vapor deposition diamond films and high-pressure and high-temperature (HPHT) synthetic IIa substrates. The highest Hall mobility at room temperature is 268 cm²/Vs among B implanted homoepitaxial films, while it is 38 cm²/Vs for the B implanted HPHT synthetic IIa substrate. The present result reveals that the quality of a doped layer is strongly dependent upon that of a diamond substrate employed for ion implantation.     

Effect of Au ion beam on structural,surface, optical and electrical properties of ZnO thin films prepared by RF sputtering

In the present work, ZnO thin films were irradiated with 700?keV Au⁺ ions at different fluence (1?× 10¹³, 1?× 10¹⁴, 2?× 10¹⁴ and 5?× 10¹⁴ ions/cm²). The structural, morphological, optical and electrical properties of pristine and irradiated ZnO thin films were characterized by X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR), scanning electron microscope (SEM), spectroscopy ellipsometry (SE) and four point probe technique respectively. XRD results showed that the crystallite size decreased from pristine value at the fluence 1?×?10¹³ ions/cm², with further increase of ion fluence the crystallite size also increased due to which the crystallinity of thin films improved. SEM micrographs showed acicular structures appeared on the ZnO thin film surface at high fluence of 5?×?10¹⁴ ions/cm². FTIR showed absorption band splitting due to the growth of ZnO nanostructures. The optical study revealed that the optical band gap of ZnO thin films changed from 3.08?eV (pristine) to 2.94?eV at the high fluence (5?× 10¹⁴ ions/cm²). The electrical resistivity of ZnO thin film decreases with increasing ion fluence. All the results can be attributed to localized heating effect by ions irradiation of thin films and well correlated with each other.     

Extremely Thin Al2O3 Surface‐Passivated Nanocrystalline ZnO Thin‐Film Transistors Designed for Low Process Temperature

Nanocrystalline ZnO (nc‐ZnO) thin‐film transistors (TFTs) exhibit inherent instability under bias/photo stresses, which originates from the oxygen molecules adsorbed on the surface of the crystal grains. The space charge region at nanocrystal surfaces that is induced by adsorbed oxygen molecules produces a high electrical potential barrier and significantly interrupts charge transport between the source and drain in nc‐ZnO TFTs. In this article, we developed high‐performance TFTs via the continuous deposition of an extremely thin Al₂O₃ layer on a nc‐ZnO channel. These devices were fabricated by atomic layer deposition at an extremely low process temperature of 150°C, including both the deposition and postannealing temperatures. The nc‐ZnO TFT with an extremely thin Al₂O₃ layer (1.8 nm) showed a significantly higher mobility (25 cm²/Vs) compared to devices without an Al₂O₃ layer (3.6 cm²/Vs). This dramatic difference was ascribed to the suppression of the chemisorption of oxygen molecules at the nanocrystal surface during thermal annealing (reducing the potential barrier width/height between adjacent nanocrystals). Furthermore, ultrathin Al₂O₃‐covered nc‐ZnO TFTs exhibited considerably enhanced electrical/photo stability due to the reduction in adsorption/desorption events of oxygen molecules on the nanocrystal surfaces (with no change in the depletion width after illumination) under gate bias or illumination stress.     

Sol–Gel‐Derived High‐Performance Stacked Transparent Conductive Oxide Thin Films

Single‐ and multi‐layer transparent conductive oxide (TCO) thin films exhibiting high performance, good packing density and low surface/interface roughness are deposited on silica glass substrates by the sol–gel method. The crystal and microstructural properties of the TCO thin films are evaluated as an alternate to films prepared by ultra‐high vacuum deposition. Tin‐doped indium oxide (ITO) thin films produced using a two‐step drying process showed low surface roughness because of dense packing structure not only horizontal but also vertical directions. As a result, electrical conductivity, carrier concentration, carrier mobility, and optical transmittance of 2.3 × 10³ S/cm, 8 × 10²⁰ cm^?3, 18 cm²/Vs, and over 98% at 500 nm, respectively, were achieved. A multilayer ZnO/ITO stacked structure was also fabricated using the sol–gel process. Our findings suggest that solution‐based methods show promise as an alternative to existing ultra‐high vacuum methods to fabricate TCO thin films.     

Thickness dependent growth and ferroelectric/dielectric properties of phase-pure 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 thin film derived from a modified sol-gel process

Annealing parameter and thickness are two significant factors affecting microstructure and electrical performance of sol-gel derived 0.65Pb(Mg_1/3Nb_2/3)O₃?0.35PbTiO₃ (0.65PMN-0.35PT) thin film. In this paper, various durations are firstly selected for the investigations on annealing parameter of 0.65PMN-0.35PT thin film. Enhanced insulating and ferroelectric properties can be obtained for the film annealed for 1 min due to its phase-pure and homogeneous perovskite structure. Based on this, a series of 0.65PMN-0.35PT thin films with various thicknesses by modifying deposition layer are synthesized annealed for 1 min and the effects of thickness on crystalline, insulating, ferroelectric and dielectric properties are characterized. It reveals that thickness-dependent behavior can be noticed for 0.65PMN-0.35PT thin film with the results that the 8-layered film possesses a relative large remanent polarization (P_r) of 23.34 μC/cm², and reduced leakage current density of 10^?9 A/cm² with low dissipation factor (tanδ) of 0.03 can be achieved for the 14-layered film.     

Dual active layer a-IGZO TFT via homogeneous conductive layer formation by photochemical H-doping

In this study, InGaZnO (IGZO) thin film transistors (TFTs) with a dual active layer (DAL) structure are fabricated by inserting a homogeneous embedded conductive layer (HECL) in an amorphous IGZO (a-IGZO) channel with the aim of enhancing the electrical characteristics of conventional bottom-gate-structure TFTs. A highly conductive HECL (carrier concentration at 1.6 × 10¹³ cm^-2, resistivity at 4.6 × 10^-3 Ω∙cm, and Hall mobility at 14.6 cm²/Vs at room temperature) is fabricated using photochemical H-doping by irradiating UV light on an a-IGZO film. The electrical properties of the fabricated DAL TFTs are evaluated by varying the HECL length. The results reveal that carrier mobility increased proportionally with the HECL length. Further, a DAL TFT with a 60-μm-long HECL embedded in an 80-μm-long channel exhibits comprehensive and outstanding improvements in its electrical properties: a saturation mobility of 60.2 cm²/Vs, threshold voltage of 2.7 V, and subthreshold slope of 0.25 V/decade against the initial values of 19.9 cm²/Vs, 4.7 V, and 0.45 V/decade, respectively, for a TFT without HECL. This result confirms that the photochemically H-doped HECL significantly improves the electrical properties of DAL IGZO TFTs.     

Preparation and properties of AZO/PS/AZO tri-layer transparent conductive film with a light-trapping structure

The light-trapping structure is an effective method to increase solar light capture efficiency in the solar cells. In this study, Al-doped ZnO (AZO)/polystyrene (PS)/AZO tri-layer transparent conductive film with light-trapping structure was fabricated by magnetron sputtering and liquid phase methods. The structural, optical and electrical properties of the AZO films could be controlled by different growth conditions. When the sputtering pressure of the under-layer AZO film was 0.2 Pa, the discharge voltage was around 80 V, which was within the optimal process window for obtaining AZO film with high crystallinity. The optimal under-layer AZO film had a large surface roughness and a very low static water contact angle of 75.71°, promoting the relatively uniform distribution of PS spheres. Under this sputtering condition, the prepared AZO/PS/AZO tri-layer film had the highest crystallinity and least point defects. The highest carrier concentration and Hall mobility are 3.0 × 10²¹ cm^-3and 5.39 cm² V^-1 s^-1, respectively. Additionally, a transparent conductive film with the lowest resistivity value (3.88 × 10^-4 Ω cm) and the highest average haze value (26.5%) was obtained by optimizing the process parameters. These properties were comparable to or exceed the reported values of surface-textured SnO₂-based as well as ZnO-based TCOs films, making our films suitable for transparent electrode applications, especially in thin-film solar cells.     

Influence of nucleation density on film quality,growth rate and morphology of thick CVD diamond films

The optimum growth parameters of our 5 kW microwave plasma CVD reactor were obtained using CH₄/H₂/O₂ plasma and high quality transparent films can be produced reproducibly. Among the films prepared in this system, the film of best quality has very smooth crystalline facets free of second nucleation and the full width at half maximum (FWHM) of the diamond Raman peak is 2.2 cm⁻¹, as narrow as that of IIa natural diamond. For this study, diamond films were grown on silicon substrates with low (10⁴–10⁵ cm⁻²) and high nucleation densities (>10¹⁰ cm⁻²), respectively. From the same growth run, a highly 〈110〉 textured 300 μm thick white diamond film with a growth rate of 2.4 μm/h was obtained from high nucleation densities (>10¹⁰ cm⁻²), and a white diamond film of 370 μm in thickness with a higher growth rate of 3 μm/h was obtained from low nucleation densities (5×10⁴–10⁵ cm⁻²) too. The effect of nucleation density on film quality, growth rate, texture and morphology was studied and the mechanism was discussed. Our results suggest that under suitable growth conditions, nucleation density has little effect on film quality and low nucleation density results in higher growth rate than high nucleation density due to less intense grain growth competition.     

Structural,electrical and optical properties of molybdenum-doped TiO2 thin films

Molybdenum doped TiO₂ (MTO) thin films were prepared by radio frequency (RF) magnetron sputtering at room temperature and followed by a heat treatment in a reductive atmosphere containing 90% N₂ and 10% H₂. XRD and FESEM were employed to evaluate the microstructure of the MTO films, revealing that the addition of molybdenum enhances the crystallization and increases the grain size of TiO₂ films. The optimal electrical properties of the MTO films were obtained with 3 wt% Mo doping, producing a resistivity of 1.1×10^?3 Ω cm, a carrier density of 9.7×10²⁰ cm^?3 and a mobility of 5.9 cm²/Vs. The refractive index and extinction coefficient of MTO films were also measured as a function of film porosity. The optical band gap of the MTO films ranged from 3.28 to 3.36 eV, which is greater than that of the un-doped TiO₂ film. This blue shift of approximately 0.14 eV was attributed to the Burstein–Moss effect.     

Evolution and properties of adherent diamond films with ultra high nucleation density deposited onto alumina

In this work, we report on adherent diamond films with thickness of up to 4.5 μm grown on polycrystalline alumina substrates. Prior to deposition, alumina substrates were ultrasonically abraded with mixed poly-disperse slurry that allows high nucleation density of values up to ∼5×10¹⁰ particles/cm². It was estimated that the minimal film thickness achieved for continuous films was ∼320 nm, obtained after a deposition time of 15 min with diamond particles density (DPD) of ∼4×10⁹ particles/cm². Continuous adherent diamond films with high DPD (∼10⁹ particles/cm²) were obtained also on sapphire surface after abrasion with mixed slurry and 15 min of deposition. However, after longer deposition time, diamond films peeled off from the substrates during cooling.The poor adhesion between the diamond and sapphire is attributed to the weak interface interaction between the film and the substrate and to difference in coefficient of thermal expansion. On the other hand, it is suggested that the reason for good adhesion between diamond film and alumina substrate is that high carbon diffusivity onto alumina grain boundaries allows strong touch-points at the grooves of alumina grains, and this prevents the delamination of diamond film. This adhesion mechanism, promoted by sub-micron diamond grain-size, is allowed by initial high nucleation density.The surface properties, phase composition and microstructure of the diamond films deposited onto alumina were examined by electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and high-resolution scanning electron microscopy (HR-SEM). The residual stress in the diamond films was evaluated by diamond Raman peak position and compared to a theoretical model with good agreement. Due to the sub-micron grain-size, the intrinsic tensile stress is high enough to partially compensate the thermal compressive stress, especially in diamond films with thickness lower than 1 μm.     

Photocarrier mobility in poly(2‐methoxyaniline)

In the current study the mobility of photogenerated charge carriers in PMA [poly(2‐methoxyaniline)] and their transport were investigated using time‐of‐flight (TOF) techniques. Also studied was the effect on hole mobility of film thickness and of the method of polymer processing during device fabrication. The highest value of hole mobility found was 4.5 × 10⁻⁴ cm² V⁻¹ s⁻¹ at an applied field of 1.3 × 10⁶ V/cm and 293 K in solution‐cast film of PMA. The hole mobility of solution‐cast films was about 2 orders of magnitude higher compared to spin‐coated films, for which the ordering of the polymer chains may be the reason. To our knowledge, this is the first time the TOF mobility of this material has been presented. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1506–1512, 2001     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Free-standing diamond films grown on cobalt substrates

Diamond films were grown directly on cobalt substrates, using microwave plasma-assisted chemical vapour deposition. Although cobalt is known to inhibit the nucleation of diamond and enhancing the formation of graphite, we were able to grow relatively thick films (∼190 μm). The films were easily detached from the substrates. The poor adhesion allows the possibility of obtaining free-standing diamond films without chemical etching. Micro-Raman spectroscopy showed the 1332 cm⁻¹ characteristic Raman peak of diamond and the 1580 cm⁻¹, 1360 cm⁻¹ bands of graphite, on the growth surface and backside of the films, respectively. Through scanning electron microscopy and X-ray diffraction we were able to monitor film thickness and morphology with growth evolution. The results showed the (111) preferential growth morphology for the film with higher growth rate. By energy dispersive X-ray spectroscopy it was only possible to detect cobalt in the back of the films, but not in the surface. The role of cobalt in the film growth is discussed.     

High thermoelectric performance of high-mobility Ga-doped ZnO films via homogenous interface design

Ga-doped ZnO (GZO) thin films grown on sapphire substrates have been widely investigated as a promising transparent thermoelectric (TE) material. However, due to the large lattice mismatch and thermal expansion between the sapphire substrate and GZO film, strain-induced lattice distortion impedes the transport of electrons, leading to low carrier mobility. In this study, ZnO homo-buffer layers with different thicknesses were inserted between sapphire substrates and GZO films, and their effect on the TE properties was investigated. A thin ZnO interlayer (10 nm) effectively reduced the lattice mismatch of the GZO film and improved the carrier mobility, which contributed to the large enhancement in the electrical conductivity. Simultaneously, energy filtering occurred at the interface between GZO and ZnO, resulting in a relatively high density of states (DOS) effective mass and maintaining a high Seebeck coefficient compared to that of the unbuffered GZO films. Consequently, the GZO film with a 10 nm thick ZnO buffer layer possessed a high power factor value of 449 μW m⁻¹ K⁻² at 623 K. This study provides a facile and effective method for optimizing the TE performance of oxide thin films by synergistically improving their carrier mobility and enhancing their effective mass.     

CIGS absorbing layers prepared by RF magnetron sputtering from a single quaternary target

Cu(In_1−xGa_x)Se₂ (CIGS) thin films were prepared by RF magnetron sputtering from a single quaternary target at multiple processing parameters. The structural, compositional, and electrical properties of the as-deposited films were systematically investigated by XRD, Raman, SEM, and Hall effects analysis. The results demonstrate that by adjusting the processing parameters, the CIGS thin films with a preferential orientation along the (112) direction which exhibited single chalcopyrite phase were obtained. The films deposited at relatively higher substrate temperature, sputtering power, and Ar pressure exhibited favorable stoichiometric ratio (Cu/(In+Ga):0.8–0.9 and Ga/(In+Ga):0.25–0.36) with grain size of about 1–1.5 µm, and desirable electrical properties with p-type carrier concentration of 10¹⁶−10¹⁷ cm⁻³ and carrier mobility of 10–60 cm²/Vs. The CIGS layers are expected to fabricate high efficiency thin film solar cells.     

Strain effects in epitaxial La-doped SrSnO3 films on lattice-matched PMN-PT substrates

Here we report the effect of the strain states on the structure, optical and electrical transport properties of the La_0.05Sr_0.95SnO₃ (LSSO) thin films grown epitaxially on (001)-oriented 0.70 Pb(Mg_1/3Nb_2/3)O₃-0.30PbTiO₃ (PMN-PT) substrates by pulsed laser deposition. X-ray diffraction results indicate that the films are fully strained up to at least 100 nm thickness, and the in-plane compressive strain gradually releases in thicker films. High-resolution transmission electron microscopy characterizations demonstrate that the LSSO films were grown coherently on PMN-PT(001) substrates. With varying the thicknesses of the fully strained films from 20 to 100 nm, the electrical transport properties are improved significantly. A lowest room-temperature resistivity of 1.88 mΩcm and the highest mobility of 28.1 cm²/Vs are obtained in the 100 nm film. The optical band gap determined from spectroscopic ellipsometry is found to increase from 4.58 to 4.88 eV with the film thicknesses varying from 20 to 500 nm. The results imply that the LSSO epitaxial films exhibit tunable electrical performances and optical band gaps through strain, which may have potential applications in optoelectrical devices.     

Defect chemistry and electrical characteristics of undoped and Mn-doped ZnO

Undoped and Mn-doped ZnO samples were sintered at 1373, 1473, and 1573 K, for 2 h, in air, and then quenched to room temperature. Defect concentrations in these samples at the sintering temperatures and at room temperature and below were calculated using a refined defect model. Using the calculated electron concentrations and assuming a constant electron mobility of 100 cm²/Vs, conductivities at room temperature were calculated and compared with experimental ones. The agreement between the experimental and calculated conductivities is very good for all the samples of undoped and Mn-doped ZnO. In the Mn-doped ZnO case, the ionisation energy of the Mn defect in ZnO was estimated to be ∼2.0 eV. Using the experimental conductivities and the calculated electron concentrations, the electron mobilities were calculated between 70 and 300 K. The results show that the temperature dependence of the mobility in undoped ZnO is similar to that in ZnO single crystals observed in other works, and heavy Mn doping significantly reduces the electron mobility below room temperature probably due to impurity scattering. The role of Mn on the electrical conductivity of ZnO could be understood.