2D Porous TiO2 Single‐Crystalline Nanostructure Demonstrating High Photo‐Electrochemical Water Splitting Performance

Porous single crystals are promising candidates for solar fuel production owing to their long range charge diffusion length, structural coherence, and sufficient reactive sites. Here, a simple template‐free method of growing a selectively branched, 2D anatase TiO₂ porous single crystalline nanostructure (PSN) on fluorine‐doped tin oxide substrate is demonstrated. An innovative ion exchange–induced pore‐forming process is designed to successfully create high porosity in the single‐crystalline nanostructure with retention of excellent charge mobility and no detriment to crystal structure. PSN TiO₂ film delivers a photocurrent of 1.02 mA cm^?2 at a very low potential of 0.4 V versus reversible hydrogen electrode (RHE) for photo‐electrochemical water splitting, closing to the theoretical value of TiO₂ (1.12 mA cm^?2). Moreover, the current–potential curve featuring a small potential window from 0.1 to 0.4 V versus RHE under one‐sun illumination has a near‐ideal shape predicted by the Gartner Model, revealing that the charge separation and surface reaction on the PSN TiO₂ photoanode are very efficient. The photo‐electrochemical water splitting performance of the films indicates that the ion exchange–assisted synthesis strategy is effective in creating large surface area and single‐crystalline porous photoelectrodes for efficient solar energy conversion.     

Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

One‐Step Fabrication of Unique Mesoporous NiO Hollow Sphere Film on FTO for High‐Performance P‐Type Dye‐Sensitized Solar Cells

P‐type dye sensitized solar cells (p‐DSCs) deliver much lower overall efficiency than their inverse model, n‐DSCs. However, they have fundamental and practical significance, in particular, their tandem structured solar cells with both p‐ and n‐photoelectrodes could offer great potential to significantly improve the efficiency of existing solar cells. A facile and environmentally friendly method is developed to directly one‐step grow hollow NiO spherical structures on fluorine‐doped tin oxide (FTO) substrate, in which a Ni²⁺ and polymer complex spherical structure is self‐constructed through a controlled solvent evaporation process, followed by calcination‐converting to a unique NiO hollow sphere film. The prepared material is further used as a photocathode in p‐type dye sensitized solar cells, resulting in 41% increase of an open‐circuit voltage and 18% enhancement of power conversion efficiency than NiO nanoparticles photocathode. The improved performance can be ascribed to suppressed charge recombination at the photocathode/electrolyte interface. This template‐free approach could be universally used to fabricate other nanostructured hollow spheres for a wide range of energy conversion applications such as electrochemical capacitors, chemical sensors, and electrochromic devices.     

A Chemical Route to Monolithic Integration of Crystalline Oxides on Semiconductors

This work demonstrates the growth of crystalline SrTiO₃ (STO) directly on germanium via a chemical method. After thermal deoxidation, the Ge substrate is transferred in vacuo to the deposition chamber where a thin film of STO (2 nm) is deposited by atomic layer deposition (ALD) at 225 °C. Following post‐deposition annealing at 650 °C for 5 min, the STO film becomes crystalline with epitaxial registry to the underlying Ge (001) substrate. Thicker STO films (up to 15 nm) are then grown on the crystalline STO seed layer. The crystalline structure and orientation are confirmed via reflection high‐energy electron diffraction, X‐ray diffraction, and transmission electron microscopy. Electrical measurements of a 15‐nm thick epitaxial STO film on Ge show a large dielectric constant (k ≈ 90), but relatively high leakage current of ≈10 A/cm² for an applied field of 0.7 MV/cm. To suppress the leakage current, an aluminum precursor is cycled during ALD growth to grow crystalline Al‐doped STO (SrTi_1‐x­Al_xO_3‐δ) films. With sufficient Al doping (≈13%), the leakage current decreases by two orders of magnitude for an 8‐nm thick film. The current work demonstrates the potential of ALD‐grown crystalline oxides to be explored for advanced electronic applications, including high‐mobility Ge‐based transistors.     

Revealing Nanoscale Chemical Heterogeneities in Polycrystalline Mo‐BiVO4 Thin Films

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi‐modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo‐BiVO₄. By using scanning transmission X‐ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X‐ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V₂O₅ at grain boundaries of Mo‐BiVO₄ thin films, which is further supported by X‐ray photoelectron spectroscopy and many‐body density functional theory calculations. Theoretical calculations also enable to predict the X‐ray absorption spectral fingerprint of polarons in Mo‐BiVO₄. After photo‐electrochemical operation, the degraded Mo‐BiVO₄ films show similar grain center and grain boundary spectra indicating V₂O₅ dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.     

Fabrication of KTa0.65Nb0.35O3 film by pulsed laser deposition on glass substrate with various buffer layers

KTa_0.65Nb_0.35O₃ (KTN) thin films were deposited on amorphous glass substrates using a range of single buffer layers such as indium tin oxide (ITO), zinc oxide (ZnO), 3 at% Al-doped ZnO (AZO), and 3 at% Ga-doped ZnO (GZO), as well as a variety of multi-buffer layers such as SrTiO₃ (STO)/ITO, STO/ZnO, STO/AZO, and STO/GZO using a pulsed laser deposition system. All films showed a polycrystalline perovskite phase with the exception of all single buffer layers and STO/ITO multi-buffer layers. The STO buffer layer is important for crystallizing KTN films due to the similar lattice constant and same crystal structure. The optical transmittance of all films exhibited a transmittance ?90% in the wavelength range.     

Influence of Interfacial LSMO Nanoparticles/Layer on the Vortex Pinning Properties of YBCO Thin Film

YBa₂Cu₃O_7?δ (YBCO) thin films have been deposited on bare and La_0.67Sr_0.33MnO₃ (LSMO) modified single crystal SrTiO₃ (STO) substrates. The effect of randomly distributed ferromagnetic LSMO nanoparticles and a complete LSMO layer, present at STO/YBCO interface, on the superconducting properties of YBCO thin films has been investigated by temperature dependent magnetization studies. The YBCO thin film on LSMO nanoparticles decorated STO substrate shows significant improvement in the critical current density and pinning force density as compared to the YBCO thin film deposited on bare STO substrate and this improvement is more significant at higher applied magnetic field. However, the LSMO/YBCO bilayer showed the improved flux pinning properties only up to a magnetic field of 1.5 T above which it deteriorates. In the case of LSMO/YBCO bilayer, the underlying LSMO layer gives rise to magnetic inhomogeneities due to domain structure, which leads to improved flux pinning properties limited to lower field. However, in the case of LSMO nanoparticles decorated substrate, the presence of LSMO nanoparticles at YBCO/STO interface seems to introduce magnetic inhomogeneities as well as structural defects, which might be acting as correlated pinning sites leading to improved flux pinning properties of the YBCO thin film over a wide range of applied magnetic field.     

Probing the bulk ionic conductivity by thin film hetero-epitaxial engineering

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO₃ and SrTiO₃ grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO₂ and 8 mol% Y₂O₃ stabilized ZrO₂ are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity.     

Epitaxial Bi2FeCrO6 Multiferroic Thin Film as a New Visible Light Absorbing Photocathode Material

Ferroelectric materials have been studied increasingly for solar energy conversion technologies due to the efficient charge separation driven by the polarization induced internal electric field. However, their insufficient conversion efficiency is still a major challenge. Here, a photocathode material of epitaxial double perovskite Bi₂FeCrO₆ multiferroic thin film is reported with a suitable conduction band position and small bandgap (1.9–2.1 eV), for visible‐light‐driven reduction of water to hydrogen. Photoelectrochemical measurements show that the highest photocurrent density up to ?1.02 mA cm^?2 at a potential of ?0.97 V versus reversible hydrogen electrode is obtained in p‐type Bi₂FeCrO₆ thin film photocathode grown on SrTiO₃ substrate under AM 1.5G simulated sunlight. In addition, a twofold enhancement of photocurrent density is obtained after negatively poling the Bi₂FeCrO₆ thin film, as a result of modulation of the band structure by suitable control of the internal electric field gradient originating from the ferroelectric polarization in the Bi₂FeCrO₆ films. The findings validate the use of multiferroic Bi₂FeCrO₆ thin films as photocathode materials, and also prove that the manipulation of internal fields through polarization in ferroelectric materials is a promising strategy for the design of improved photoelectrodes and smart devices for solar energy conversion.     

Reduced graphene oxide/Cu<Subscript>2</Subscript>O nanostructure composite films as an effective and stable hydrogen evolution photocathode for water splitting

An efficient photocathode consisting of reduced graphene oxide/Cu₂O/Cu (rGO/Cu₂O/Cu) has been successfully prepared in this work via a facile two step method, consisting of chemical oxidation of a copper foil in alkaline solution using (NH₄)₂S₂O₈ as the oxidizing agent, dipping the prepared samples in graphene oxide (GO) solution and calcination at vacuum to form a rGO layer onto Cu₂O/Cu photocathode, which acts as a protective layer. The products were composed of a thin Cu₂O layer topped with a thin rGO film as the protective coating. The chemical composition and rGO amount in the composite materials were easily controlled by changing the immersion time to enhance PEC performance. UV–Vis spectroscopy, Raman spectroscopy, XRD, SEM, TEM and FTIR spectroscopy were used in the optical and morphological characterization of the graphene oxide and prepared photocathodes. Distinct patches of GO film are formed on the Cu(OH)₂ nanostructure surface, as shown by SEM results. Linear sweep voltammetry and chronoamperometry analysis have been applied in the photoelectrochemical characterizations in the dark and under illumination conditions. Photocurrent density provided by rGO/Cu₂O/Cu photocathode ??2.54 mA cm^??2 is three times greater than that of bare Cu₂O/Cu photocathode ??0.82 mA cm^??2 at 0 V vs. RHE under illumination. Low photostability of 42% is exhibited by bare Cu₂O/Cu photocathode after 200 s irradiation whereas rGO/Cu₂O/Cu photocathode shows approximately 98% of the initial photocurrent density. Therefore, a strategy has been developed in this work for the synthesis of this new photocathode using Cu₂O/Cu as an effective photocathode for photoelectrochemical (PEC) water splitting.     

Pulsed laser deposition of epitaxial ferroelectric Pb(Zr,Ti)O3 films on silicon substrates

We report on the epitaxial growth and electrical properties of Pb_0.52Zr_0.48TiO₃ (PZT) thin films deposited by Pulsed Laser Deposition (PLD) on SrTiO₃ (STO)-buffered Si(001). Previously to PZT growth, 40 nm-thick (La,Sr)MnO₃ (LSMO) layer was deposited to serve as electrical bottom electrode. The 200 nm-thick PZT film epitaxy was optimized by PLD on STO-buffered Si(001).The high contrast of stable artificially poled ferroelectric surfaces evidences the good ferroelectric properties of the PZT thin film. The structural as well as the physical properties of the PZT/LSMO/STO/Si(001) structure prove that very good quality layers have been obtained for films grown on silicon substrate.     

A Low‐Cost NiO Hole Transfer Layer for Ohmic Back Contact to Cu2O for Photoelectrochemical Water Splitting

Cuprous oxide (Cu₂O) photocathode is reported as a promising candidate for photoelectrochemical water splitting. The p‐type Cu₂O usually forms a Schottky junction with the conductive substrate due to its large work function, which blocks the collection of photogenerated holes. NiO is considered as one of the most promising hole transfer layers (HTL) for its high hole mobility, good stability, and easy processability to form a film by spin coating. The utilization of NiO HTL to form an Ohmic back contact to Cu₂O is described, thus achieving a positive onset potential of 0.61 V versus reversible hydrogen electrode and a twofold increase of solar conversion efficiency.     

Strain-Induced First-Order Magnetic Phase Transition in Epitaxial Sm<Subscript>0.35</Subscript>Pr<Subscript>0.15</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Thin Film

Epitaxial Sm_0.35Pr_0.15Sr_0.5MnO₃ thin films were deposited on LaAlO₃ (LAO, (001)), SrTiO₃ (STO, (001)), and (La_0.18Sr_0.82)(Al_0.59Ta_0.41)O₃ (LSAT, (001)) single-crystalline substrates by using pulsed laser deposition technique. In order to examine the strain effect on electronic and magnetic properties, films were studied by X-ray diffraction, electrical resistivity, and dc magnetization measurements. The film grown on LAO substrate is under compressive strain, and it undergoes ferromagnetic → paramagnetic transition at Curie temperature (T _C) of ～ 165 K and metal → insulator transition at ～ 107 K. The films grown on STO and LSAT substrates are under tensile strain and have T _C of ～ 120 and 130 K, respectively, and show metal → insulator transition at ～ 145 and 137 K, respectively. At T < T _C, the zerofield and fieldcooled magnetization curves of all the films show a huge bifurcation. In the case of films on STO and LSAT substrates, hysteresis is also observed in fieldcooled cooling and warming magnetization vs. temperature measurement protocols at low magnetic field. All the signatures of the firstorder magnetic phase transition are absent in the case of film on LAO substrate. The occurrence and absence of firstorder magnetic phase transition in films on LAO, STO, and LSAT substrates, respectively, have been well explained through the substrateinduced film lattice strain.     

Surface,Bulk, and Interface: Rational Design of Hematite Architecture toward Efficient Photo‐Electrochemical Water Splitting

Collecting and storing solar energy to hydrogen fuel through a photo‐electrochemical (PEC) cell provides a clean and renewable pathway for future energy demands. Having earth‐abundance, low biotoxicity, robustness, and an ideal n‐type band position, hematite (α‐Fe₂O₃), the most common natural form of iron oxide, has occupied the research hotspot for decades. Here, a close look into recent progress of hematite photoanodes for PEC water splitting is provided. Effective approaches are introduced, such as cocatalysts loading and surface passivation layer deposition, to improve the hematite surface reaction in thermodynamics and kinetics. Second, typical methods for enhancing light absorption and accelerating charge transport in hematite bulk are reviewed, concentrating upon doping and nanostructuring. Third, the back contact between hematite and substrate, which affects interface states and electron transfer, is deliberated. In addition, perspectives on the key challenges and future prospects for the development of hematite photoelectrodes for PEC water splitting are given.     

High Quality YBCO Film Growth on SrTiO_3-Buffered LaAlO_3 Substrate by Full Solution Method

A full solution method has been developed as a low cost process of YBa2Cu3OT-x （YBCO） coated conductor fabrication. In this study, highly biaxially textured SrTiO3 （STO） buffer layers were fabricated on LaAlO3 （LAO） single crystal substrates by sol-gel method using metal alkoxides as the staring precursor materials. High quality YBCO superconducting film was then fabricated on STO-buffered LAO substrate by trifluoroacetic metalorganic deposition （TFA-MOD） method. For the YBCO superconducting film, only （001） diffraction peaks can be detected by XRD （X-ray diffraction） analysis with no other phases detectable. Especially, Inplane texture of YBCO film is improved compared to that of STO buffer layer from phi scans analysis, which indicates the self-epitaxy phenomenon explained by considering interracial energy. STO and YBCO films both show c-axis oriented grains growth and have uniform surface microstructure. A critical transition temperature, TC （R=0） of 89.5 K and a critical current density of 2 mA/cm2 （77 K, self-field） were obtained for a 0.2μm thick YBCO film on STO-buffered LAO substrate. No reaction between YBCO and STO was detected by XRD analysis. This full solution process may provide a promising low cost fabrication route for YBCO coated conductors on metal tape.     

Thickness dependence of (001) texture evolution in FePt thin films on an amorphous substrate

Thickness dependency of (001) texture evolution in Fe₅₄Pt₄₆ thin films on an amorphous substrate was investigated using in-house X-ray diffraction or a synchrotron source. The (001) texture was well developed in Fe₅₄Pt₄₆ thin films, especially when its thickness was equivalent to the grain height. The findings show that strain relaxation anisotropy along the film axis, which leads to a (001) crystal (a crystal with a (001) plane parallel to the film plane) that is more stable than others, was large for a low thickness film. In addition, abnormal grain growth was used to explain the abrupt development of a (001) texture. The advantage of multilayered as-deposited structure is also discussed.     

Epitaxial La0.7Sr0.3MnO3 thin films on silicon with excellent magnetic and electric properties by combining physical and chemical methods

Half-metallic ferromagnetic La_0.7Sr_0.3MnO₃ (LSMO) represents an appealing candidate to be integrated on silicon substrates for technological devices such as sensors, data storage media, IR detectors, and so on. Here, we report high-quality epitaxial LSMO thin films obtained by an original combination of chemical solution deposition (CSD) and molecular beam epitaxy (MBE). A detailed study of the thermal, chemical, and physical compatibility between SrTiO₃ (STO)/Si buffer layers and LSMO films, grown by MBE and CSD, respectively, enables a perfect integration of both materials. Importantly, we show a precise control of the coercive field of LSMO films by tuning the mosaicity of the STO/Si buffer layer. These results demonstrate the enormous potential of combining physical and chemical processes for the development of low-cost functional oxide-based devices compatible with the complementary metal oxide semiconductor technology.     

Crystallographic properties of four-fold grain K3Li2Nb5O15 thin films

The structural properties of a potassium lithium niobate (KLN; K₃Li₂Nb₅O₁₅) thin film deposited by rf-magnetron sputtering on a Pt/Ti/SiO₂/Si(100) substrate were investigated. The crystalline structures of the Pt under layer and KLN thin films were examined using θ-2θ, θ-rocking, and mesh scan X-ray diffraction (XRD). The XRD results revealed that the Pt under layer was a strong (111) direction orientated poly crystal. Unlike the Pt under layer film, the KLN(001) peak was found to consist of two separate peaks, one with a broad full width half maximum (FWHM) and the other with a narrow FWHM, indicating that the KLN film had a single crystalline structure. The surface and cross-section morphology were investigated using a scanning electron microscope (SEM). Accordingly, from the results of the SEM and XRD experiments, it was concluded that the KLN film was composed of small single crystals, which had a four-fold symmetry morphology with a c-axis normal to the substrate.     

Onset of hard magnetic L10 FePt phase with (001) texture

The perpendicular anisotropic magnetic properties of in-situ deposited FePt/Pt/Cr trilayer films were elucidated as functions of the deposition temperature and the sputtering rate of the FePt magnetic layer. Ordered L1₀ FePt thin films with perpendicular anisotropy and a (001) texture can be developed at a temperature as low as 300 °C with the sputtering of a FePt layer at a low rate. The larger Pt(001)[100] lattice induced an expansion of the FePt a- and b-axis, leading to the contraction of the FePt c-axis, enabling the epitaxial growth of the L1₀ FePt(001) texture to occur. A low rate of sputtering of the FePt thin film promotes the formation of the magnetically hard FePt(001) texture on the surface of the Pt(001) buffer layer at low temperature, while the high sputtering rate of FePt layer suppresses the phase transformation.     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.