Single-crystalline Nanostructures Research Articles

Single-crystalline HfO2 nanostructures with novel ferromagnetic properties

Hafnium oxide (HfO2) has special technological significance due to its superior properties such as high dielectric constant (κ∼25), wide bandgap (∼5.7 eV), and superb thermal and chemical stabilities. Its room-temperature ferromagnetism and excellent CMOS technology compatibility make it a promising candidate for seamless CMOS-spintronics integration. Low-dimensional single-crystalline HfO2 nanostructures, particularly one dimensional (1D) nanostructures, are expected to exhibit enhanced ferromagnetic properties due to large specific surface areas and potentially more surface defects. To date, the synthesis of single-crystalline HfO2 1D nanostructures has, however, remained elusive. Here, single-crystalline dopant-free HfO2 nanostructures with notable morphologies, including HfO2 1D nanostructures, are grown using catalyst-assisted pulsed laser deposition. It is shown that Sn plays a crucial role in producing these 1D nanostructures by increasing both the VLS nucleation and growth rates. Magnetization measurements reveal room-temperature ferromagnetism in HfO2 nanowires, contrasting with weak paramagnetic responses in HfO2 nanostructured films. We also provide the first direct evidence of oxygen vacancies as the source of room-temperature ferromagnetism in HfO2. To account for the observed magnetic property, we employ a modified bound magnetic polaron-band ferromagnetism hybrid model, which is also generally applicable to dopant-free nanostructures of other metal oxides. This work provides new insights into the growth of novel metal oxide 1D nanostructures and the design of new dilute magnetic semiconducting oxides for potential integrated CMOS-spintronics applications.

Shaping single crystalline BaTiO3 nanostructures by focused neon or helium ion milling

The realization of perovskite oxide nanostructures with controlled shape and dimensions remains a challenge. Here, we investigate the use of helium and neon focused ion beam (FIB) milling in an ion microscope to fabricate BaTiO3 nanopillars of sub-500 nm in diameter starting from BaTiO3 (001) single crystals. Irradiation of BaTiO3 with He ions induces the formation of nanobubbles inside the material, eventually leading to surface swelling and blistering. Ne-FIB is shown to be suitable for milling without inducing surface swelling. The resulting structures are defect-free single crystal nanopillars, which are enveloped, on the top and lateral sidewalls, by a point defect-rich crystalline region and an outer Ne-rich amorphous layer. The amorphous layer can be selectively etched by dipping in diluted HF. The geometry and beam-induced damage of the milled nanopillars depend strongly on the patterning parameters and can be well controlled. Ne ion milling is shown to be an effective method to rapidly prototype BaTiO3 crystalline nanostructures.

Single crystalline molybdenum nanostructure for generating reflective micro-focal spot X-rays: Structure-controllable preparation and characteristic-selectable radiation

The use of properly designed nanostructured anode targets enables direct generation of high performance X-rays. In particular, this scheme has attracted widespread research interest for obtaining micro-focal spot X-ray radiation. In this study, we developed a thermal evaporating deposition technique and achieved controllable preparation of different single crystalline molybdenum (Mo) nanostructures by exploiting the lattice matching relationship between the substrate and the product crystal orientation. When used as an anode target for a reflective X-ray radiation device, these nanostructured Mo single crystals exhibit advantages over traditional targets at larger radiation angles. Further experimental and simulation results demonstrate the geometric characteristics of these Mo nanostructures and their correlation with the radiation intensity, focal spot size, and brightness of the generated X-rays. Among them, a unique frustum of square pyramid single crystalline Mo nanostructure stands out, due to its combination of three-dimensional body feature of nanostructures and radiation plane feature of planar targets. The research results not only provide a class of nanostructured anode target materials for reflective X-ray sources with different radiation angle requirements, but also make it possible to design and develop miniaturized devices for X-ray sources with selectable radiation performance and micro-focal spot.

Selective Flocculation and H2O2-Free Oxidative Etching-Based Synthesis of Highly Monodisperse Ag Nanospheres for Uniform Quantum Dot Photoluminescence-Enhancing Plasmonic Cavity Applications.

Ag nanoparticles have garnered significant attention for their excellent plasmonic properties and potential use as plasmonic cavities, primarily because of their intrinsically low ohmic losses and optical properties in the visible range. These are particularly crucial in systems involving quantum dots that absorb light at low wavelengths, where the need for a high threshold energy of interband transitions necessitates the incorporation of Ag nanostructures. However, the synthesis of Ag nanoparticles still encounters challenges in achieving structural uniformity and monodispersity, along with chemical stability, consequentially inducing inconsistent and poorly reliable optical responses. Here, we present a two-step approach for synthesizing highly uniform spherical Ag nanoparticles involving depletion-induced flocculation and Cu(II)-mediated oxidative etching. We found that the selective flocculation of multitwinned Ag nanocrystals significantly enhances the uniformity of the resulting Ag nanostructures, leaving behind only single-crystalline and single-twinned nanostructures. Subsequent oxidative etching, in which cupric ions are directly involved in the reaction, was designed based on Pourbaix diagrams to proceed following thermodynamically favorable states and circumvent the generation of reactive chemical species such as H2O2. This leads to perfectly spherical shapes of final Ag nanoparticles with a synthetic yield of 99.5% and additionally reduces the overall reaction time. Furthermore, we explore the potential applications of these monodisperse Ag nanospheres as uniform plasmonic cavities. The fabricated Ag nanosphere films uniformly enhanced the photoluminescence of InP/ZnSe/ZnS quantum dots, showcasing their capabilities in exhibiting consistent plasmonic responses across a large area.

Concentrated Solar Light Photoelectrochemical Water Splitting for Stable and High-Yield Hydrogen Production.

Photoelectrochemical water splitting is a promising technique for converting solar energy into low-cost and eco-friendly H2 fuel. However, the production rate of H2 is limited by the insufficient number of photogenerated charge carriers in the conventional photoelectrodes under 1 sun (100mWcm-2) light. Concentrated solar light irradiation can overcome the issue of low yield, but it leads to a new challenge of stability because the accelerated reaction alters the surface chemical composition of photoelectrodes. Here, it is demonstrated that loading Pt nanoparticles (NPs) on single crystalline GaN nanowires (NWs) grown on n+-p Si photoelectrode operates efficiently and stably under concentrated solar light. Although a large number of Pt NPs detach during the initial reaction due to H2 gas bubbling, some Pt NPs which have an epitaxial relation with GaN NWs remain stably anchored. In addition, the stability of the photoelectrode further improves by redepositing Pt NPs on the reacted Pt/GaN surface, which results in maintaining onset potential >0.5V versus reversible hydrogen electrode and photocurrent density >60mAcm-2 for over 1500 h. The heterointerface between Pt cocatalysts and single crystalline GaN nanostructures shows great potential in designing an efficient and stable photoelectrode for high-yield solar to H2 conversion.

Modeling the Conduction Mechanism in Chemoresistive Gas Sensor Based on Single-Crystalline Sn3O4 Nanobelts: A Phenomenological In Operando Investigation.

Investigating the sensing mechanisms in semiconducting metal oxide (SMOx) gas sensors is essential for optimizing their performance across a wide range of potential applications. Despite significant progress in the field, there are still many gaps in comprehending the phenomenological processes occurring in one-dimensional (1D) nanostructures. This article presents the first insights into the conduction mechanism of chemoresistive gas sensors based on single-crystalline Sn3O4 nanobelts using the operando Kelvin Probe technique. From this approach, direct current (DC) electrical resistance and work function changes were simultaneously measured in different working conditions, and a correlation between the conductance and the surface band bending was established. Appropriate modeling was proposed, and the results revealed that the conduction mechanism in the single-crystalline one-dimensional nanostructures closely aligns with the behavior observed in single-crystalline epitaxial layers rather than in polycrystalline grains. Based on this assumption, relevant parameters were further estimated, including Debye length, concentration of free charge carriers, effective density of states in the conduction band, and position of the Fermi level. Overall, this study provides an effective contribution to understanding the role of surface chemistry in the transduction of the electrical signal generated from gas adsorption in single-crystalline one-dimensional nanostructures.

Progressively Oriented Attachment-Enabled Ultralong Single-Crystalline Upconversion Nanowires for Multidirectional Strain Sensing.

Fabricating one-dimensional (1D) single-crystalline nanostructures with the necessary characteristics for interconnects and functional units in nanodevices poses a major challenge. Traditional solution-based synthesis methods, driven by oriented attachment mechanisms, have limited the growth of either ultrathin crystalline nanowires or short rod-like nanocrystals due to stringent orientation requirements. The construction of single-crystalline ultralong nanowires with both an elongated length and moderate thickness has remained elusive. Here we introduce a growth mechanism based on progressively oriented attachment that enables the attachment of larger crystals while preserving the alignment of the crystal lattice. Using this mechanism, we achieve 1D single-crystalline lanthanide-doped nanowires (K2YF5:Yb/Er) with lengths up to 9 μm and a moderate thickness of approximately 20 nm. These nanowires can be integrated into a flexible film that exhibits stretching-dependent upconverted luminescence behavior. The mechanical toughness and elongated morphology of the nanowires facilitate the development of a wearable device dedicated to multidirectional strain sensing with high responsivity and excellent stability, withstanding repeated stretching and releasing for up to 1000 cycles.

Multiterminal epitaxial tungsten nanostructures on MgO/GaAs(001) substrates: Temperature effects in ballistic electron transport

High-quality single-crystalline multiterminal tungsten nanostructures were fabricated on MgO/GaAs (001) substrates using subtractive lithography. Single-crystalline tungsten films with a thickness of d = 80 nm and low roughness were grown using sequential epitaxy of MgO (001) and W (001) layers on GaAs (001) via pulsed laser deposition. The temperature dependence of bridge-type nanostructure electron conductivity indicates that they are high-quality metal conductors. The electron mean free path reached 760 nm at low temperatures and was approximately an order of magnitude greater than the tungsten film thickness. Strong non-local effects resulting from ballistic electron transport were observed in the multiterminal cross-type W (001) nanostructures with an arm width Wc = 400 nm below T = 80 K. Such effects can be explained by the exponential damping of ballistic properties of nanostructures as a function of the electron mean free path in the wide temperature range 4.2–100 K. Simulations predict that the ballistic effects in such nanostructures can be significant even at room temperature with an arm width approaching 10 nm and a size ratio of Wc/d ∼ 1.

Complementary switching in single Nb3O7(OH) nanowires

Single nanowires and networks are considered as promising candidates for miniaturized memristive devices for brain-inspired systems. Moreover, single crystalline nanostructures are useful model systems to gain a deeper understanding in the involved switching mechanism of the investigated material. Here, we report on hydrothermally grown single crystalline Nb3O7(OH) nanowires showing a complementary resistive switching (CRS) behavior. The CRS characteristics can be related to an oxygen vacancy migration at the electrode/metal hydroxide interface. Therefore, an oxygen plasma treatment is used to reduce the oxygen vacancy content, resulting in a total reduction of the device conductivity. Furthermore, temporal resolved current–voltage measurements demonstrate the dependence of the destructive readout process of the resistance states on the voltage amplitude and polarity.

Single-Crystalline Mesoporous Palladium and Palladium-Copper Nanocubes for Highly Efficient Electrochemical CO 2 Reduction

Single-Crystalline Mesoporous Palladium and Palladium-Copper Nanocubes for Highly Efficient Electrochemical CO ₂ Reduction

Effect of minute compositional variations on the photoelectrochemical properties of InGaN/TiO2 heterostructure electrodes

We report on the growth of single crystalline InGaN nanostructures with minute compositional variation on sapphire at a low substrate temperature of 350 °C that shows good optical and electrical properties. We investigate the photoelectrochemical performance of InGaN with two different average In compositions (13 and 16%) and compare the properties by forming their heterostructures with TiO2 (InGaN/TiO2). A significant enhancement in photocurrent density has been observed by using the heterostructures with more In content, in comparison to the InGaN having the same In content and also with the heterostructure having lesser In content. Though the average In compositional difference is only 3%, the de-convoluted XRD (0002) curve shows significant change in one of the phases (In0.29Ga0.71N) with an increment in both indium composition (6%) and in the phase area, which results in the significant difference in photoelectrochemical properties. The transient photo response analysis shows that both samples are fast responsive, while the photocurrent density is significantly different with the fabrication of heterostructures. A suitable change in band diagram of the system is sketched, which shows the band bending enhances the separation and migration of the photogenerated carriers to the semiconductor/electrolyte interface, thereby the photocurrent density.

Pyramid-Shaped Single-Crystalline Nanostructure of Molybdenum with Excellent Mechanical, Electrical, and Optical Properties.

Specific geometric morphology and improved crystalline properties are of great significance for the development of materials in micro-nano scale. However, for high-melting molybdenum (Mo), it is difficult to get high-quality structures exhibiting a single-crystalline nature and preconceived morphology simultaneously. In this paper, a pyramid-shaped single-crystalline Mo nanostructure was prepared through a thermal evaporation technique, as well as a series of experimental controls. Based on detailed characterizations, the growth mechanism was demonstrated to follow a sequential process that includes MoO2 decomposition and Mo deposition, single-crystalline islands formation, layered nucleation, and competitive growth. Furthermore, the product was measured to show excellent physical properties. The prepared nanostructures exhibited strong nano-indentation hardness, elastic modulus, and tensile strength in mechanical measurements, which are much higher than those of the Mo bulks. In the measurement of electronic characteristics, the individual structures indicated very good electrical transport properties, with a conductance of ∼0.16 S. The prepared film with an area of 0.02 cm2 showed large-current electron emission properties with a maximum current of 33.6 mA and a current density of 1.68 A cm-2. Optical properties of the structures were measured to show obvious electromagnetic field localization and enhancement, which enabled it to have good surface enhanced Raman scattering (SERS) activity as a substrate material. The corresponding structure-response relationships were further discussed. The reported physical properties profit from the basic features of the Mo nanostructures, including the micro-nano scale, the single-crystalline nature in each grain, as well as the pyramid-shaped top morphology. The findings may provide a potential material for the research and application of micro-nano electrons and photons.

Layered-Perovskite Nanowires with Long-Range Orientational Order for Ultrasensitive Photodetectors.

2D layered metal-halide perovskites combine efficient exciton radiative recombination in crystal interior with long-distance free-carrier conduction at layer edges, which are promising candidates for realizing high-performance photovoltaic, light-emission and photodetection devices. The anisotropic electrical conductivity in layered perovskites imposes an additional requirement of orientational control for enabling favorable charge transport. However, rational fabrication of single-crystalline nanostructures with pure crystallographic orientation is still elusive. Herein, large-scale pure (101)-orientated 2D-perovskite single-crystalline nanowire arrays are realized by combining solvent engineering with the capillary-bridge lithography technique. Ordered nucleation at liquid-air interface and unidirectional growth along the dewetting direction are demonstrated by fluorescence microscopy and grazing-incidence X-ray scattering in discrete capillary bridges. In consideration of crystal interior exhibiting high resistance arising from the serial insulating organic barriers and ultrafast dissociation of excitons to generate long-lived free carriers at layer edges, ultrasensitive photodetectors are demonstrated with average responsivity exceeding 1.1 × 104 A W-1 and detectivity exceeding 9.1 × 1015 Jones.

Single-Crystalline γ-Ga2S3 Nanotubes via Epitaxial Conversion of GaAs Nanowires.

The chemical transformation of nanowire templates into nanotubes is a promising avenue toward hollow one-dimensional (1D) nanostructures. To date, high-quality single crystalline tubes of nonlayered inorganic crystals have been obtained by solid-state reactions in diffusion couples of nanowires with deposited thin film shells, but this approach presents issues in achieving single-phase tubes with a desired stoichiometry. Chemical transformations with reactants supplied from the gas- or vapor-phase can avoid these complications, allowing single-phase nanotubes to be obtained through self-termination of the reaction once the sacrificial template has been consumed. Here, we demonstrate the realization of this scenario with the transformation of zincblende GaAs nanowires into single-crystalline cubic γ-Ga2S3 nanotubes by reaction with sulfur vapor. The conversion proceeds via the formation of epitaxial GaAs-Ga2S3 core-shell structures, vacancy injection and aggregation into Kirkendall voids, elastic relaxation of the detached Ga2S3 shell, and finally complete incorporation of Ga in a crystalline chalcogenide tube. Absorption and luminescence spectroscopy on individual nanotubes show optoelectronic properties, notably a ∼3.1 eV bandgap and intense band-edge and near band-edge emission consistent with high-quality single crystals, along with transitions between gap-states due to the inherent cation-vacancy defect structure of Ga2S3. Our work establishes the transformation of nanowires via vapor-phase reactions as a viable approach for forming single-crystalline hollow 1D nanostructures with promising properties.

Manipulation of a Single Crystal Nanowire on an Atomic Level

In recent years, metal oxide nanostructures (MO) have been intensively studied due to a wide variety of applications on multiple fields, for example in optoelectronics, gas sensing, photovoltaics, field-effect transistors, UV lasers, field emission sources etc. [1]. However, for applications, other types of structures are also interesting such as sulfides and nitrides. Here the question that raises is can we manipulate nanomaterials like nanowires on an atomic level. Knowing the exact mechanism of sulfur-oxygen exchange in the metal oxide crystal lattice can be utilized for the synthesis of metal sulfides with specific morphologies. When compared to metal oxides, single-crystalline metal sulfide nanostructures of specific morphologies are usually harder to produce than MOs. Generally, metal sulfide nanostructures represent unconventional materials in areas such as batteries or photovoltaics with yet unexploited potential, where their efficiency is mainly limited by the purity of crystalline phases and structural defects [2]. A promising path for novel synthesis route is incorporation of the sulfur in the crystal structure of a metal oxide nanoparticle, while during this transition the morphology of the nanostructure does not change. In this way, it is possible to obtain single crystal metal sulfide nanostructures from metal oxide nanostructures in the single crystal to single crystal (SCSC) transformation. A promising method to achieve such transformation in a short period of time is a treatment of metal oxide nanostructures with the plasma of sulfur-containing gas. In this research, we studied the mechanism of sulfur incorporation in the metal oxide crystal structure. The procedure was carried out by synthesis of ultra-thin metal oxide nanowires, which were then treated with sulfur-containing gases under increased temperature (in thermodynamic equilibrium conditions) and in the plasma of the same gases (under thermodynamically non-equilibrium conditions). Experiments were conducted at different temperatures and pressures to evaluate the influence of plasma on transformation process. Mechanisms involved in the interaction of sulfur-containing species with metal oxides were studied on isolated single ultra-thin metal oxide nanowire. Furthermore, changes in crystal structures and their effect on the material properties before and after sulfurization were studied. [1] Umar A. & Hahn Y. B. (Eds.). (2010), Metal Oxide Nanostructures and their Applications. American Scientific Publishers, CA, USA [2] Zavašnik, J., & Rečnik, A. (2013). Electron microscopy study of CVT grown Fe-sulphides. Journal of Crystal Growth, 367, 18-23.

Synthesis and characterization of zinc oxide incorporated iron borate glass-ceramic

Here, zinc oxide (ZnO) incorporated iron borate (Fe3BO6) glass-ceramics have been synthesized using the traditional melt-quenching technique, and the role of ZnO has been investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveals that the prepared samples have a single crystalline phase and crystalline nanostructures, respectively. The orthorhombic crystal structure has been retained without the formation of a new crystalline phase. The addition of ZnO is found to distort the Fe3BO6 lattice by substituting Zn2+ in the Fe3+ sites, with the formation of ZnO6 structural units as revealed by Fourier transform infrared spectroscopy (FTIR). FTIR and Raman spectroscopy conducted to study the structure of glass-ceramic, have also revealed the formation of other structural units like ZnO4, BO3, BO4, and FeO6 in the system. Surface analysis conducted by X-ray photoelectron spectroscopy (XPS) reveals that the addition of ZnO diminishes the formation of surface B2O3 layer which forms over the Fe3BO6 phase in the Fe3BO6 iron borate glass-ceramic system. ZnO addition has also shown a remarkable difference in the volume of the crystallization in the system, thereby paving the way for controlled crystallization in the iron borate glass-ceramic system. The controlled crystallization was achieved through additive content, retaining the iron borate (Fe3BO6) glass-ceramic system without the evolution of any secondary phases even with large additive concentrations up to 10 mol%.

Inorganic and Layered Perovskites for Optoelectronic Devices.

Organic-inorganic halide perovskites are making breakthroughs in a range of optoelectronic devices. Reports of >23% certified power conversion efficiency in photovoltaic devices, external quantum efficiency >21% in light-emitting diodes (LEDs), continuous-wave lasing and ultralow lasing thresholds in optically pumped lasers, and detectivity in photodetectors on a par with commercial GaAs rivals are being witnessed, making them the fastest ever emerging material technology. Still, questions on their toxicity and long-term stability raise concerns toward their market entry. The intrinsic instability in these materials arises due to the organic cation, typically the volatile methylamine (MA), which contributes to hysteresis in the current-voltage characteristics and ion migration. Alternative inorganic substitutes to MA, such as cesium, and large organic cations that lead to a layered structure, enhance structural as well as device operational stability. These perovskites also provide a high exciton binding energy that is a prerequisite to enhance radiative emission yield in LEDs. The incorporation of inorganic and layered perovskites, in the form of polycrystalline films or as single-crystalline nanostructure morphologies, is now leading to the demonstration of stable devices with excellent performance parameters. Herein, key developments made in various optoelectronic devices using these perovskites are summarized and an outlook toward stable yet efficient devices is presented.

Investigation of electrochemical performances of ceramic oxide CaCu3Ti4O12 nanostructures

Herein, we report an electrochemical property of giant dielectric quaternary oxide CaCu3Ti4O12 (CCTO) nanocubes. Single crystalline nanostructures of CCTO are synthesized by simple molten salt method. X-ray diffraction (XRD), Field-emission scanning electron microscopy (FESEM), High resolution transmission electron microscopic (HRTEM) techniques are used to study the structural and morphological properties. XRD and HRTEM analysis confirm the formation of phase pure and single crystalline CCTO nanocubes. Detailed electrochemical performance of as synthesized samples has been carried out by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS) techniques. Electrochemical properties of three different CCTO nanstructure synthesized at 800 °C for three different holding time (30 min, 1 h and 5 h) has been compared. CCTO nanocube electrodes provide maximum areal capacitance of 1185 mF cm−2 at a scan rate of 10 mV s−1 in aqueous KOH solution. An all-solid-state symmetric device has been fabricated by using CCTO nanocubes. The device delivers maximum areal capacitance 76 mF cm−2 at a scan rate of 10 mV s−1. Furthermore, the electrodes exhibit an excellent cycling stability with 94.8% capacitance retention even after 3000 cycles of charging discharging at a current density 10 mA cm−2. The present investigation explores possible use of single crystalline CCTO nanocubes as next generation supercapacitor material having a double perovskite structure.

Porous Single-Crystalline CdSe Nanobelts: Cation-Exchange Synthesis and Highly Selective Photoelectric Sensing toward Cu2.

Porous single-crystalline nanostructures are of tremendous interest for their application in the catalytic, electronic and sensing fields due to their large active surfaces, favorable diffusion, and good electronic transport. Despite the recent advances of various other components, photoelectric chalcogenides remain almost undeveloped. The present study contributes a facile strategy to prepare porous single-crystalline CdSe nanobelts through a cation-exchange reaction, in which ZnSe⋅0.5 N2 H4 hybrid nanobelts are employed as precursors. The detailed characterizations indicate the preservation of the belt-like morphology of the precursors due to the spatial confinement effect, which arises from the coated surfactant layer during the cation-exchange process. Simultaneously, CdSe nanobelts with porous and single-crystalline structures are formed following a complete exchange between Zn2+ and Cd2+ , the release of N2 H4 , and the atomic arrangement. The native photoelectric properties of the as-prepared porous single-crystalline CdSe nanobelts are systematically addressed based on the nanodevices fabricated with a single nanobelt and assembled nanobelt array. The results indicate that they present a rapid, stable, and repeatable photoelectric response. Moreover, as-prepared nanobelts exhibit highly selective photoelectric sensing toward Cu2+ with a low detection limit down to 0.1 ppm. To illuminate this phenomenon, a possible sensing mechanism is also discussed.

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.