X‐Ray Writing of Metallic Conductivity and Oxygen Vacancies at Silicon/SrTiO3 Interfaces

Tunable electronic properties of transition metal oxides and their interfaces offer remarkable functionalities for future devices. The interest in these materials has been boosted with the discovery of a 2D electron gas (2DEG) at SrTiO₃ (STO)‐based interfaces. For the majority of these systems, oxygen vacancies play a crucial role in the emergence of interface conductivity, ferromagnetism, and high electron mobility. Despite its great importance, controlling the density and spatial distribution of oxygen vacancies in a dynamic way remains extremely challenging. Here, lithography‐like writing of a metallic state at the interface between SrTiO₃ and amorphous Si using X‐ray irradiation is reported. Using a combination of transport techniques and in operando photoemission spectroscopy, it is revealed in real time that the X‐ray radiation induces transfer of oxygen across the interface leading to the on‐demand formation of oxygen vacancies and a 2DEG in STO. The formed 2DEG stays stable in ambient conditions as the interface oxygen vacancies are stabilized by the capping of Si. The study provides a fundamental understanding of X‐ray‐induced redox reactions at the SrTiO₃‐based interfaces and in addition shows the potential of X‐ray radiation for patterning stabile conductive pathways for future oxide‐based electronic devices.     

Amplifying Charge‐Transfer Characteristics of Graphene for Triiodide Reduction in Dye‐Sensitized Solar Cells

The fabrication and functionalization of large‐area graphene and its electrocatalytic properties for iodine reduction in a dye‐sensitized solar cell are reported. The graphene film, grown by thermal chemical vapor deposition, contains three to five layers of monolayer graphene, as confirmed by Raman spectroscopy and high‐resolution transmission electron microscopy. Further, the graphene film is treated with CF₄ reactive‐ion plasma and fluorine ions are successfully doped into graphene as confirmed by X‐ray photoelectron spectroscopy and UV‐photoemission spectroscopy. The fluorinated graphene shows no structural deformations compared to the pristine graphene except an increase in surface roughness. Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction increases with increasing plasma treatment time, which is attributed to an increase in catalytic sites. Further, the fluorinated graphene is characterized in use as a counter‐electrode in a full dye‐sensitized solar cell and shows ca. 2.56% photon to electron conversion efficiency with ca. 11 mA cm^?2 current density. The shift in work function in F^? doped graphene is attributed to the shift in graphene redox potential which results in graphene's electrocatalytic‐activity enhancement.     

Enhanced Performance of I2‐Free Solid‐State Dye‐Sensitized Solar Cells with Conductive Polymer up to 6.8%

An iodine‐free solid‐state dye‐sensitized solar cell (ssDSSC) is reported here, with 6.8% energy conversion efficiency—one of the highest yet reported for N719 dye—as a result of enhanced light harvesting from the increased transmittance of an organized mesoporous TiO₂ interfacial layer and the good hole conductivity of the solid‐state‐polymerized material. The organized mesoporous TiO₂ (OM‐TiO₂) interfacial layer is prepared on large‐area substrates by a sol‐gel process, and is confirmed by scanning electron microscopy (SEM) and grazing incidence small‐angle X‐ray scattering (GISAXS). A 550‐nm‐thick OM‐TiO₂ film coated on fluorine‐doped tin oxide (FTO) glass is highly transparent, resulting in transmittance increases of 8 and 4% compared to those of the bare FTO and conventional compact TiO₂ film on FTO, respectively. The high cell performance is achieved through careful control of the electrode/hole transport material (HTM) and nanocrystalline TiO₂/conductive glass interfaces, which affect the interfacial resistance of the cell. Furthermore, the transparent OM‐TiO₂ film, with its high porosity and good connectivity, exhibits improved cell performance due to increased transmittance in the visible light region, decreased interfacial resistance ( Ω ), and enhanced electron lifetime ( τ ). The cell performance also depends on the conductivity of HTMs, which indicates that both highly conductive HTM and the transparent OM‐TiO₂ film interface are crucial for obtaining high‐energy conversion efficiencies in I₂‐free ssDSSCs.     

X‐Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects

Chemical doping of graphene represents a powerful means of tailoring its electronic properties. Synchrotron‐based X‐ray spectroscopy offers an effective route to investigate the surface electronic and chemical states of functionalizing dopants. In this work, a suite of X‐ray techniques is used, including near edge X‐ray absorption fine structure spectroscopy, X‐ray photoemission spectroscopy, and photoemission threshold measurements, to systematically study plasma‐based chlorinated graphene on different substrates, with special focus on its dopant concentration, surface binding energy, bonding configuration, and work function shift. Detailed spectroscopic evidence of C–Cl bond formation at the surface of single layer graphene and correlation of the magnitude of p‐type doping with the surface coverage of adsorbed chlorine is demonstrated for the first time. It is shown that the chlorination process is a highly nonintrusive doping technology, which can effectively produce strongly p‐doped graphene with the 2D nature and long‐range periodicity of the electronic structure of graphene intact. The measurements also reveal that the interaction between graphene and chlorine atoms shows strong substrate effects in terms of both surface coverage and work function shift.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Enhancement in Organic Photovoltaic Efficiency through the Synergistic Interplay of Molecular Donor Hydrogen Bonding and π‐Stacking

For organic photovoltaic (OPV) cells based on the bulk heterojunction (BHJ) structure, it remains challenging to rationally control the degree of phase separation and percolation within blends of donors and acceptors to secure optimal charge separation and transport. Reported is a bottom‐up, supramolecular approach to BHJ OPVs wherein tailored hydrogen bonding (H‐bonding) interactions between π‐conjugated electron donor molecules encourage formation of vertically aligned donor π‐stacks while simultaneously suppressing lateral aggregation; the programmed arrangement facilitates fine mixing with fullerene acceptors and efficient charge transport. The approach is illustrated using conventional linear or branched quaterthiophene donor chromophores outfitted with terminal functional groups that are either capable or incapable of self‐complementary H‐bonding. When applied to OPVs, the H‐bond capable donors yield a twofold enhancement in power conversion efficiency relative to the comparator systems, with a maximum external quantum efficiency of 64%. H‐bond promoted assembly results in redshifted absorption (in neat films and donor:C₆₀ blends) and enhanced charge collection efficiency despite disparate donor chromophore structure. Both features positively impact photocurrent and fill factor in OPV devices. Film structural characterization by atomic force microscopy, transmission electron microscopy, and grazing incidence wide angle X‐ray scattering reveals a synergistic interplay of lateral H‐bonding interactions and vertical π‐stacking for directing the favorable morphology of the BHJ.     

Large area dye‐sensitized solar cells: material aspects of fabrication

Dye‐sensitized photoelectrochemical solar cells of large area are fabricated using highly conducting and optically transparent glass consisting of an inner layer of indium‐tin oxide and an outer layer of fluorine doped tin oxide. A method is described for the deposition of nanocrystalline films of TiO₂ consisting of large and small median size particles (30 and 5 nm, respectively) which promote porosity and light scattering. Incorporation of trace quantities of magnesium oxide into TiO₂ increased the efficiency of the cells. The energy conversion efficiency of a cell (AM 1·5, 1000 W m⁻² simulated sunlight) of area 21 cm² was found to be 7·2% compared to 5·6% in the absence of magnesium oxide. The mechanisms by which the magnesium oxide improves the cell performance are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

Tuning Conversion Efficiency in Metallo Endohedral Fullerene‐Based Organic Photovoltaic Devices

Here the influence that 1‐(3‐hexoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐Lu₃N@C₈₁, Lu₃N@C₈₀–PCBH, a novel acceptor material, has on active layer morphology and the performance of organic photovoltaic (OPV) devices using this material is reported. Polymer/fullerene blend films with poly(3‐hexylthiophene), P3HT, donor material and Lu₃N@C₈₀–PCBH acceptor material are studied using absorption spectroscopy, grazing incident X‐ray diffraction and photocurrent spectra of photovoltaic devices. Due to a smaller molecular orbital offset the OPV devices built with Lu₃N@C₈₀–PCBH display increased open circuit voltage over empty cage fullerene acceptors. The photovoltaic performance of these metallo endohedral fullerene blend films is found to be highly impacted by the fullerene loading. The results indicate that the optimized blend ratio in a P3HT matrix differs from a molecular equivalent of an optimized P3HT/[6,6]‐phenyl‐C₆₁‐butyric methyl ester, C₆₀–PCBM, active layer, and this is related to the physical differences of the C₈₀ fullerene. The influence that active layer annealing has on the OPV performance is further evaluated. Through properly matching the film processing and the donor/acceptor ratio, devices with power conversion efficiency greater than 4% are demonstrated.     

Edge‐Fluorinated Graphene Nanoplatelets as High Performance Electrodes for Dye‐Sensitized Solar Cells and Lithium Ion Batteries

Edge‐selectively fluorinated graphene nanoplatelets (FGnPs) are prepared by mechanochemically driven reaction between fluorine gas (20 vol% in argon) and activated carbon species from graphitic C–C bonds unzipped by high‐speed stainless steel balls with a high kinetic energy. The fluorination at edges of the unzipped graphene nanoplatelets (GnPs) is confirmed by various analytical techniques while the content of fluorine in FGnPs is determined to be 3.0 and 3.4 at% by X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectroscopy, respectively. Because of the large difference in electronegativity between carbon (χ = 2.55) and fluorine (χ = 3.98) and the strong C–F bond, the edge‐fluorination of GnPs can provide the maximized charge polarization with an enhanced chemical stability. Thus, electrodes based on the resultant FGnPs demonstrate superb electrochemical performance with excellent stability/cycle life in dye‐sensitized solar cells (FF: 71.5%; J_sc: 14.44 mA cm^?2; V_oc: 970 mV; PCE: 10.01%) and lithium ion batteries (650.3 mA h g^?1 at 0.5 C, charge retention of 76.6% after 500 cycles).     

Tuning the Molecular Weight of the Electron Accepting Polymer in All‐Polymer Solar Cells: Impact on Morphology and Charge Generation

Molecular weight is an important factor determining the morphology and performance of all‐polymer solar cells. Through the application of direct arylation polycondention, a series of batches of a fluorinated naphthalene diimide‐based acceptor polymer are prepared with molecular weight varying from M_n = 20 to 167 kDa. Used in conjunction with a common low bandgap donor polymer, the effect of acceptor molecular weight on solar cell performance, morphology, charge generation, and transport is explored. Increasing the molecular weight of the acceptor from M_n = 20 to 87 kDa is found to increase cell efficiency from 2.3% to 5.4% due to improved charge separation and transport. Further increasing the molecular weight to M_n = 167 kDa however is found to produce a drop in performance to 3% due to liquid–liquid phase separation which produces coarse domains, poor charge generation, and collection. In addition to device studies, a systematic investigation of the microstructure and photophysics of this system is presented using a combination of transmission electron microscopy, grazing‐incidence wide‐angle X‐ray scattering, near‐edge X‐ray absorption fine‐structure spectroscopy, photoluminescence quenching, and transient absorption spectroscopy to provide a comprehensive understanding of the interplay between morphology, photophysics, and photovoltaic performance.     

Direct Threat of a UV‐Ozone Treated Indium‐Tin‐Oxide Substrate to the Stabilities of Common Organic Semiconductors

Ultraviolet‐ozone treated indium‐tin‐oxide (UV‐ITO) glass substrates have been widely and unquestioningly used in the field of organic electronics to improve both device performance and stability. Evidence is presented here for rapid decay of common organic films such as N,N′‐bis(naphthalen‐1‐ yl)‐N,N′‐bis(phenyl)‐benzidine (NPB), tris(8‐hydroxy‐quinolinato)aluminum (Alq₃), and rubrene when they are in contact with an UV‐ITO substrate. While the photoluminescence (PL) of these organic films deposited on an UV‐ITO substrate decay rapidly under illumination; those on quartz substrates are comparatively much more stable. Results from X‐ray and UV photoemission spectroscopies (XPS and UPS) further suggest that degradations of the rubrene films on UV‐ITO substrate are mainly attributed to active oxygen species generated upon UV‐ozone treatment. These reactive oxygen species on the UV‐ITO surface behave as a reservoir of oxygen that interacts with rubrene and shifts its highest occupied molecular orbital (HOMO) level away from the Fermi level. This interaction induces a gap‐state in the energy gap of rubrene, which acts as a charge recombination center. More importantly, enhanced stabilities of rubrene‐based organic photovoltaic (OPV) devices are demonstrated when they are fabricated on gold‐coated or trifluoromethane (CHF₃) plasma‐treated ITO. The presented works shows that the commonly used UV‐ITO substrate is a threat to the stability of addlayer organic semiconducting films.     

Self‐Compensated Insulating ZnO‐Based Piezoelectric Nanogenerators

Remarkable enhancement of piezoelectric power output from a nanogenerator (NG) based on a zinc oxide (ZnO) thin film is achieved via native defect control. A large number of unintentionally induced point defects that act as n‐type carriers in ZnO have a strong influence on screening the piezoelectric potential into a piezoelectric NG. Here, additional oxygen molecules bombarded into ZnO lead to oxygen‐rich conditions, and the n‐type conductivity of ZnO is decreased dramatically. The acceptor‐type point defects such as zinc vacancies created during the deposition process trap n‐type carriers occurring from donor‐type point defects through a self‐compensation mechanism. This unique insulating‐type ZnO thin film‐based NGs (IZ‐NGs) generates output voltage around 1.5 V that is over ten times higher than that of an n‐type ZnO thin film‐based NG (around 0.1 V). In addition, it is found that the power output performance of the IZ‐NG can be further increased by hybridizing with a p‐type polymer (poly(3‐hexylthiophene‐2,5‐diyl):phenyl‐C₆₁‐butyric acid methyl ester) via surface free carrier neutralization.     

Assessing Antisite Defect and Impurity Concentrations in Bi2Te3 Based Thin Films by High‐Accuracy Chemical Analysis

In Bi₂Te₃‐based materials charge‐carrier densities are determined by antisite defects and controlling these defects is a key issue for thermoelectric and topological insulator materials. Bi‐Te thin films with high‐quality thermoelectric properties are deposited using a nano‐alloying approach by molecular beam epitaxy (MBE) and sputtering. The in‐plane transport properties are measured at room temperature as a function of charge‐carrier density. High‐accuracy chemical analysis by wavelength‐dispersive X‐ray spectrometry (WDX) is applied for the first time to these Bi₂Te₃‐based thin films. The acquisition conditions for WDX spectrometry are established using Monte Carlo simulations for the electron trajectories, which guarantees a high lateral resolution and rules out stray radiation generated in the substrate of the films. In contrast to energy‐dispersive X‐ray spectrometry (EDX), which is usually applied, WDX offers unprecedented accuracy for measuring antisite defect concentrations and thus has a high impact on improving the quality of thin films. The charge‐carrier densities are calculated from the WDX results according to the point‐defect model of Miller and Li and the thermopower and electrical conductivity are calculated for different charge‐carrier densities by solving the linearized Boltzmann transport equation. A good quantitative agreement is found for the dependence of the thermopower on stoichiometry, whereas the electrical conductivity is sensitively affected by contaminants.     

Insights into Fullerene Passivation of SnO2 Electron Transport Layers in Perovskite Solar Cells

Interfaces between the photoactive and charge transport layers are crucial for the performance of perovskite solar cells. Surface passivation of SnO₂ as electron transport layer (ETL) by fullerene derivatives is known to improve the performance of n–i–p devices, yet organic passivation layers are susceptible to removal during perovskite deposition. Understanding the nature of the passivation is important for further optimization of SnO₂ ETLs. X‐ray photoelectron spectroscopy depth profiling is a convenient tool to monitor the fullerene concentration in passivation layers at a SnO₂ interface. Through a comparative study using [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) and [6,6]‐phenyl‐C₆₁‐butyric acid (PCBA) passivation layers, a direct correlation is established between the formation of interfacial chemical bonds and the retention of passivating fullerene molecules at the SnO₂ interface that effectively reduces the number of defects and enhances electron mobility. Devices with only a PCBA‐monolayer‐passivated SnO₂ ETL exhibit significantly improved performance and reproducibility, achieving an efficiency of 18.8%. Investigating thick and solvent‐resistant C₆₀ and PCBM‐dimer layers demonstrates that the charge transport in the ETL is only improved by chemisorption of the fullerene at the SnO₂ surface.     

Controlled Growth of MoS2 Nanosheets on 2D N‐Doped Graphdiyne Nanolayers for Highly Associated Effects on Water Reduction

The first utilization of nitrogen‐doped graphdiyne (NGDY) as an efficient catalytic promoter for hydrogen evolution reaction (HER) is reported. X‐ray powder diffraction and X‐ray photoelectron spectroscopy studies indicate the presence of strong interactions between NGDY and MoS₂, which should effectively facilitate the charge transport behavior and improvement of the HER kinetics. The creative hybridization of MoS₂ and NGDY endows such heterostructure with structural and compositional advantages for boosting the catalytic activity (low overpotential of 186 mV at 10 mA cm^?2 and Tafel slope of 63 mV dec^?1) and extraordinary stability (higher than all reported MoS₂‐based materials and even better than that of commercial Pt and almost all benchmarked electrocatalysts). All of the results not only demonstrate that NGDY can be used as an effective catalytic promoter for hydrogen production, but also provide new strategy for fabricating efficient water‐splitting electrodes.     

Multistep hydrothermal route for nanocoral architecture of anatase TiO2: synthesis and characterization of dye‐sensitized solar cell performance

Multistep hydrothermal (MSH) process is employed for growth of TiO₂ nanocorals onto the conducting fluorine‐doped tin oxide‐coated glass substrates. The surface morphological features and physical properties of TiO₂ films were investigated by field emission scanning electron microscopy, high resolution transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, room temperature photoluminescence spectroscopy and X‐ray photoelectron spectroscopy. The surface morphology revealed the formation of TiO₂ corals having nanosized (30–40 nm) polyps. The photoelectrochemical properties of the TiO₂ nanocoral electrodes were investigated in 0.1 M NaOH electrolyte under ultraviolet illumination. The results presented in this study highlight two major findings: (i) tuning the photoelectrochemical response and photoconversion efficiency via controlled thickness of TiO₂ nanocorals by MSH route and (ii) the substantial increase in short‐circuit photocurrent (J_sc) because of the improved charge transport through TiO₂ nanocorals prepared via MSH process. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and Lithium Storage Properties of Co3O4 Nanosheet‐Assembled Multishelled Hollow Spheres

Single‐, double‐, and triple‐shelled hollow spheres assembled by Co₃O₄ nanosheets are successfully synthesized through a novel method. The possible formation mechanism of these novel structures was investigated using powder X‐ray diffraction, scanning and transmission electron microscopies, Fourier transform IR, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. Both poly(vinylpyrrolidone) (PVP) soft templates and the formation of cobalt glycolate play key roles in the formation of these novel multishelled hollow structures. When tested as the anode material in lithium‐ion batteries (LIBs), these multishelled microspheres exhibit excellent cycling performance, good rate capacity, and enhanced lithium storage capacity. This superior cyclic stability and capacity result from the synergetic effect of small diffusion lengths in the nanosheet building blocks and sufficient void space to buffer the volume expansion. This facile strategy may be extended to synthesize other transition metal oxide materials with hollow multishelled micro‐/nanostrucutures, which may find application in sensors and catalysts due to their unique structural features.     

Cu2O Nanocrystal‐Templated Growth of Cu2S Nanocages with Encapsulated Au Nanoparticles and In‐Situ Transmission X‐ray Microscopy Study

Cubic and octahedral Cu₂O nanocrystals and Au–Cu₂O core–shell heterostructures are used as sacrificial templates for the growth of Cu₂S nanocages and Au–Cu₂S core–cage structures. A rapid sulfidation process involving a surface reaction of Cu₂O nanocrystals with Na₂S, followed by etching of the Cu₂O cores with HCl solution for ≈5 sec, results in the fabrication of Cu₂S cages with a wall thickness of 10–20 nm. Transmission electron microscopy characterization reveals the formation of crystalline walls and the presence of ultrasmall pores with sizes of 1 nm or less. Formation of Cu₂O–Cu₂S core–shell structures and their conversion into Cu₂S cages is verified by UV–vis absorption spectroscopy. X‐ray photoelectron spectra further confirm the composition of the cages as Cu₂S. The entire hollowing process via the Kirkendall effect is recorded using in‐situ transmission X‐ray microscopy. After shell formation, continuous ionic diffusion removes the interior Cu₂O. Intermediate structures with remaining central Cu₂O portions and bridging arms to the surrounding cages are observed. The nanocages are also shown to allow molecular transport: anthracene and pyrene penetration into the cages leads to enhanced fluorescence quenching immediately upon adsorption onto the surfaces of the encapsulated gold nanocrystals.     

Charge‐Transport Properties of F6TNAP‐Based Charge‐Transfer Cocrystals

The crystal structures of the charge‐transfer (CT) cocrystals formed by the π‐electron acceptor 1,3,4,5,7,8‐hexafluoro‐11,11,12,12‐tetracyanonaphtho‐2,6‐quinodimethane (F₆TNAP) with the planar π‐electron‐donor molecules triphenylene (TP), benzo[b]benzo[4,5]thieno[2,3‐d]thiophene (BTBT), benzo[1,2‐b:4,5‐b′]dithiophene (BDT), pyrene (PY), anthracene (ANT), and carbazole (CBZ) have been determined using single‐crystal X‐ray diffraction (SCXRD), along with those of two polymorphs of F₆TNAP. All six cocrystals exhibit 1:1 donor/acceptor stoichiometry and adopt mixed‐stacking motifs. Cocrystals based on BTBT and CBZ π‐electron donor molecules exhibit brickwork packing, while the other four CT cocrystals show herringbone‐type crystal packing. Infrared spectroscopy, molecular geometries determined by SCXRD, and electronic structure calculations indicate that the extent of ground‐state CT in each cocrystal is small. Density functional theory calculations predict large conduction bandwidths and, consequently, low effective masses for electrons for all six CT cocrystals, while the TP‐, BDT‐, and PY‐based cocrystals are also predicted to have large valence bandwidths and low effective masses for holes. Charge‐carrier mobility values are obtained from space‐charge limited current (SCLC) measurements and field‐effect transistor measurements, with values exceeding 1 cm² V^?1 s¹ being estimated from SCLC measurements for BTBT:F₆TNAP and CBZ:F₆TNAP cocrystals.     

Growth of Heteroepitaxial ZnO Thin Films on GaN‐Buffered Al2O3 (0001) Substrates by Low‐Temperature Hydrothermal Synthesis at 90 °C

Heteroepitaxial ZnO films are successfully grown on nondoped GaN‐buffered Al₂O₃ (0001) substrates in water at 90 °C using a two‐step process. In the first step, a discontinuous ZnO thin film (ca. 200 nm in thickness) consisting of hexagonal ZnO crystallites is grown in a solution containing Zn(NO₃)·6 H₂O and NH₄NO₃ at ca. pH 7.5 for 24 h. In the second step, a dense and continuous ZnO film (ca. 2.5 μm) is grown on the first ZnO thin film in a solution containing Zn(NO₃)·6 H₂O and sodium citrate at ca. pH 10.9 for 8 h. Scanning electron microscopy, X‐ray diffraction, UV‐vis absorption spectroscopy, photoluminescence spectroscopy, and Hall‐effect measurement are used to investigate the structural, optical, and electrical properties of the ZnO films. X‐ray diffraction analysis shows that ZnO is a monocrystalline wurtzite structure with an epitaxial orientation relationship of (0001)[11 0]_ZnO∥(0001)[11 0]_GaN. Optical transmission spectroscopy of the two‐step grown ZnO film shows a bandgap energy of 3.26 eV at room temperature. A room‐temperature photoluminescence spectrum of the ZnO film reveals only a main peak at ca. 380 nm without any significant defect‐related deep‐level emissions. The electrical property of ZnO film showed n‐type behavior with a carrier concentration of 3.5 × 10¹⁸ cm^–3 and a mobility of 10.3 cm² V^–1 s^–1.