TiO2 Coating for SnO2:F Films Produced by Filtered Cathodic Arc Evaporation for Improved Resistance to H+ Radical Exposure

Titanium dioxide thin films were deposited by filtered cathodic arc evaporation (FCAE) from a Ti target in an oxygen atmosphere onto (a) fluorine-doped tin oxide substrates SnO₂:F (FTO) and (b) glass microscope slides. The growth rate calculated from film thickness profilometry measurements was found to be approximately 0.8?nm/s. The films were highly transparent to visible light. x-Ray photoemission spectroscopy analysis of the Ti 2p electron binding- energy shift confirmed the presence of a TiO₂ stoichiometric compound. The results for the root-mean-square (RMS) surface roughness of the films deposited onto FTO substrates evaluated by atomic force microscopy suggested nanostructured film surfaces. When exposed to hydrogen plasma, TiO₂ films revealed insignificant changes in the optical spectra. The initial sheet resistance of the SnO₂:F layer was 14?Ω/sq. The deposition of the top TiO₂ layer (45?nm thick) over the FTO electrode resulted in an increase of the sheet resistance of 2?Ω/sq. In addition, the sheet resistance of the double-layer FTO/TiO₂ transparent conductive oxide (TCO) electrode increased by 1?Ω/sq as a result of H⁺ plasma exposure. Regardless of the TiO₂ film’s low conductivity, a thin protective layer could be coated onto FTO films (presumably 15?nm thick) due to their high transparency, offering high resistance to aggressive H⁺ plasma conditions. In this paper we show that ～50-nm-thick TiO₂ coating on FTO films provides sufficient protection against deterioration of transparency and conductivity due to hydrogen radical exposure.     

Combinatorial Atmospheric Pressure Chemical Vapor Deposition of F:TiO2; the Relationship between Photocatalysis and Transparent Conducting Oxide Properties

Combinatorial atmospheric pressure chemical vapor deposition (APCVD) is used to deposit anatase TiO₂ with a graded level of F‐doping between 1.10 ≤ F:Ti (at%) ≤ 2.57 from the reaction of titanium tetrachloride, ethyl acetate and trifluoroacetic acid at 500 °C on glass. The photocatalytic activity and electrical resistivity of 200 allotted positions across a grid are screened using high‐throughput techniques. A blue region of film is singled out for containing the lowest electrical resistivities of any previously reported doped or undoped TiO₂‐based system formed by APCVD (ρ ≈ 0.22–0.45 Ω cm, n = 0.8–1.2 × 10¹⁸ cm^?3, μ = 18–33 cm² V^?1 s^?1). The blue region contains a lower fluorine doping level (F:Ti ≈ 1.1–1.6%, E_bg ≈ 3.06 eV) than its neighboring colorless region (F:Ti ≈ 2.3–2.6%, E_bg ≈ 3.15–3.21 eV, ρ ≈ 0.61–1.3 Ω cm). State‐of‐the‐art hybrid density functional theory calculations were employed to elucidate the nature of the different doping behaviors. Two distinct fluorine doping environments were present. At low concentrations, F substituting for O (F_O) dominates, forming blue F:TiO₂. At high concentrations, negatively charged fluorine interstitials (F_i^?1) begin to dominate, forming transparent F:TiO₂.     

Thermoelectric Properties of Nb-Doped Ordered Mesoporous TiO<Subscript>2</Subscript>

Mesoporous materials have pores with diameters between 2 nm and 50 nm, the presence of which generally decreases the thermal conductivity of the material. By incorporating mesoporous structures into thermoelectric materials, the thermoelectric properties of these materials can be improved. Although TiO₂ is an ordinary insulator, reduced TiO₂ shows better electrical conductivity and is therefore a potential thermoelectric material. Furthermore, the addition of a dopant to TiO₂ can improve its electrical conductivity. We hypothesized that, by doping ordered mesoporous TiO₂ films with niobium, we would be able to minimize the thermal conductivity and maximize the electrical conductivity. To investigate the effects of Nb doping and a mesoporous structure on the thermoelectric characteristics of TiO₂ films, Nb-doped mesoporous films were investigated using x-ray diffraction, ellipsometry, four-point probe measurements, and thermal conductivity analysis. We found that Nb doping of ordered mesoporous TiO₂ films improved their thermoelectric properties.     

Improved‐Performance Dye‐Sensitized Solar Cells Using Nb‐Doped TiO2 Electrodes: Efficient Electron Injection and Transfer

Well‐crystallized Nb‐doped anatase TiO₂ nanoparticles are prepared by a novel synthetic route and successfully used as the photoanode of dye‐sensitized solar cells (DSSCs). The homogenous distribution of Nb in the TiO₂ lattice is confirmed by scanning transmission electron microscopy (STEM) elemental mapping and line‐scanning analyses. After Nb doping, the conductivity of the TiO₂ powder increases, and its flat‐band potential (V_fb) has a positive shift. The energy‐conversion efficiency of a cell based on 5.0 mol% Nb‐doped TiO₂ is significantly better, by about 18.2%, compared to that of a cell based on undoped TiO₂. The as‐prepared Nb‐doped TiO₂ material is proven in detail to be a better photoanode material than pure TiO₂, and this new synthetic approach using a water‐soluble precursor provides a simple and versatile way to prepare excellent photoanode materials.     

Ti3+ Self‐Doped Dark Rutile TiO2 Ultrafine Nanorods with Durable High‐Rate Capability for Lithium‐Ion Batteries

Dark‐colored rutile TiO₂ nanorods doped by electroconducting Ti³⁺ have been obtained uniformly with an average diameter of ≈7 nm, and have been first utilized as anodes in lithium‐ion batteries. They deliver a high reversible specific capacity of 185.7 mAh g^?1 at 0.2 C (33.6 mA g^?1) and maintain 92.1 mAh g^?1 after 1000 cycles at an extremely high rate 50 C with an outstanding retention of 98.4%. Notably, the coulombic efficiency of Ti³⁺–TiO₂ has been improved by approximately 10% compared with that of pristine rutile TiO₂, which can be mainly attributed to its prompt electron transfer because of the introduction of Ti³⁺. Again the synergetic merits are noticed when the promoted electronic conductivity is combined with a shortened Li⁺ diffusion length resulting from the ultrafine nanorod structure, giving rise to the remarkable rate capabilities and extraordinary cycling stabilities for applications in fast and durable charge/discharge batteries. It is of great significance to incorporate Ti³⁺ into rutile TiO₂ to exhibit particular electrochemical characteristics triggering an effective way to improve the energy storage properties.     

Structural phase-dependent resistivity of intrinsic-extrinsic co-doped transparent titanium dioxide films

The authors report a method of enhancing the conductivity of TiO₂ films by controlling their structural phases. Thin films of Nb:TiO₂ (TNO) were prepared on glass and silicon substrates by RF sputtering with varying Nb content at 200 °C. It is shown that fine control over the structural phases of TiO₂ is critical for achieving low resistivity. The resistivity values of the films doped with oxygen vacancies and Nb⁺⁵ decreased from 3.8 × 10⁻¹ to 4.1 × 10⁻³ Ω cm when the weight percent of rutile in anatase-rutile phase mixture decreases from 52.8% to 32%. Furthermore, the lowest resistivity value of 2.37 × 10⁻³ Ω cm was obtained for the doped TiO₂ films having single phase anatase structure. The physical processes responsible for the diverse electrical properties are discussed and are associated with the growth conditions. Our result indicates that highly conductive doped-TiO₂ film can be obtained by controlling the anatase phase formation via the growth temperature. The obtained results can significantly contribute to the development of transparent electrodes by RF sputtering, a suitable technique for coating large area substrates.     

2D Titanium Carbide (MXene) Based Films: Expanding the Frontier of Functional Film Materials

2D titanium carbide (Ti₃C₂T_x) MXene films, with their well-defined microstructures and chemical functionality, provide a macroscale use of nano-sized Ti₃C₂T_x flakes. Ti₃C₂T_x films have attractive physicochemical properties favorable for device design, such as high electrical conductivity (up to 20 000 S cm^–1), impressive volumetric capacitance (1500 F cm^–3), strong in-plane mechanical strength (up to 570 MPa), and a high degree of flexibility. Here, the appealing features of Ti₃C₂T_x-based films enabled by the layer-to-layer arrangement of nanosheets are reviewed. We devote attention to the key strategies for actualizing desirable characteristics in Ti₃C₂T_x-based functional films, such as high and tunable electrical conductivity, outstanding mechanical properties, enhanced oxidation-resistance and shelf life, hydrophilicity/hydrophobicity, adjustable porosity, and convenient processability. This review further discusses fundamental aspects and advances in the applications of Ti₃C₂T_x-based films with a focus on illuminating the relationship between the structural features and the resulting performances for target applications. Finally, the challenges and opportunities in terms of future research, development, and applications of Ti₃C₂T_x-based films are suggested. A comprehensive understanding of these competitive features and challenges shall provide guidelines and inspiration for the further development of Ti₃C₂T_x-based functional films, and contribute to the advances in MXene technology.     

Synthesis of thin p-type rutile films

The structure and electrical and optical properties of heterostructures formed on the surface of single-crystal silicon wafers as a result of the heat treatment and pulsed photon treatment of Ti films in oxygen, air, and nitrogen are investigated. It is shown that a TiO₂/Ti₅Si₃/p-Si heterostructure is formed upon heat treatment in air, whereas a TiO₂/TiSi₂/p-Si heterostructure is formed upon photon treatment. It is established that rutile films with pronounced n-type conductivity are formed as a result of the heat treatment of Ni-doped Ti films in oxygen. Rutile films with p-type conductivity are formed upon the thermal annealing of Ti films in air with subsequent photon treatment in nitrogen.     

Improving carrier mobility with vanadium doping of transparent conducting CdO

Cadmium oxide (CdO) is a transparent conducting oxide (TCO) with versatile applications, many of which are linked to its transparency in the Vis/NIR spectral range in addition to its unique electrical conductivity. Its optoelectronic properties can be controlled in order to bring them into a desired choice by doping method. Usually resistivity of TCO could be reduced by increasing N_el, which, in turns, reduces the transparency (especially in the NIR region) of TCO. Therefore, it is important to seek ways to reduce ρ by increasing of μ_el (rather than N_el) that also reduces the absorption.In the present work, CdO thin films doped with different amounts of vanadium (V) ions were deposited on glass and silicon wafer substrates by physical vapour deposition method. The films were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), optical absorption spectroscopy, and dc-electrical measurements. The obtained results show significant improvements in the conductivity (σ), mobility (μ), and carrier concentration (N_el) of host CdO. The measured utmost enhancement in conductivity by 420%, mobility by 766%, and carrier concentration by 201% for CdO films doped with 4–5 wt% V. This suggests the possibility of using V-doped CdO films in different TCO applications.     

Conductivity in transparent anatase TiO2 films epitaxially grown by reactive sputtering deposition

The synthesis of semiconducting TiO₂ thin films deposited by reactive sputtering is discussed. In particular, defect doping of the anatase polymorph that is epitaxial stabilized on (0 0 1) LaAlO₃ was explored using either oxygen or water vapor as the oxidizing species. For films grown in oxygen, a transition from insulating to metallic conductivity of the films is observed as the O₂ pressure is reduced. X-ray diffraction measurements show the presence of the Ti_nO_2n−1 phase when the oxygen pressure is reduced sufficiently to induce conductive behavior. Hall measurements indicate that these materials are p-type. In contrast, the use of water vapor as the oxidizing species enabled the formation of n-type semiconducting TiO₂ with carrier density on the order of 10¹⁸ cm⁻³ and mobility of 10–15 cm²/V s.     

Zr‐Doped Indium Oxide (IZRO) Transparent Electrodes for Perovskite‐Based Tandem Solar Cells

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm² V^?1 s^?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □^?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In₂O₃) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm^?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.     

Pristine Titanium Carbide MXene Films with Environmentally Stable Conductivity and Superior Mechanical Strength

2D titanium carbide (Ti₃C₂T_x MXene) has potential application in flexible/transparent conductors because of its metallic conductivity and solution processability. However, solution‐processed Ti₃C₂T_x films suffer from poor hydration stability and mechanical performance that stem from the presence of intercalants, which are unavoidably introduced during the preparation of Ti₃C₂T_x suspension. A proton acid colloidal processing approach is developed to remove the extrinsic intercalants in Ti₃C₂T_x film materials, producing pristine Ti₃C₂T_x films with significantly enhanced conductivity, mechanical strength, and environmental stability. Typically, pristine Ti₃C₂T_x films show more than twofold higher conductivity (10 400 S cm^?1 vs 4620 S cm^?1) and up to 11‐ and 32‐times higher strength and strain energy at failure (112 MPa, 1,480 kJ m^?3, vs 10 MPa, 45 kJ m^?3) than films prepared without proton acid processing. Simultaneously, the conductivity and mechanical integrity of pristine films are also largely retained during the long‐term storage in H₂O/O₂ environment. The improvement in mechanical performance and conductivity is originated from the intrinsic strong interaction between Ti₃C₂T_x layers, and the absence of extrinsic intercalants makes pristine Ti₃C₂T_x films stable in humidity by blocking the intercalation of H₂O/O₂. This method makes the material more competitive for real‐world applications such as electromagnetic interference shielding.     

Effects of Nb Content on the Ferroelectric and Dielectric Properties of Nb/Nd-Co-doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films

Nd/Nb-co-substituted Bi_3.15Nd_0.85Ti_3?x Nb _x O₁₂ (BNTN _x , x = 0.01, 0.03, 0.05 and 0.07) thin films were grown on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition. The effects of Nb content on the micro-structural, dielectric, ferroelectric, leakage current and capacitive properties of the BNTN _x thin films were investigated. A low-concentration substitution with Nb ions in BNTN _x can greatly enhance its remanent polarization (2P _r) and reduce the coercive field (2E _c) compared with those of Bi₄Ti₃O₁₂ (BIT) thin film. The highest 2P _r (71.4 μC/cm²) was observed in the BNTN_0.03 thin film when the 2E _c was 202 kV/cm. Leakage currents of all the films were on the order of 10^?6 to 10^?5 A/cm², and the BNTN_0.03 thin film has a minimum leakage current (2.1 × 10^?6 A/cm²) under the high electric field (267 kV/cm). Besides, the C–V curve of the BNTN_0.03 thin film is the most symmetrical, and the maximum tunability (21.0%) was also observed in this film. The BNTN_0.03 thin film shows the largest dielectric constant and the lowest dielectric loss and its maximum Curie temperature is 410 ± 5°C.     

Rationally Engineered Electrodes for a High‐Performance Solid‐State Cable‐Type Supercapacitor

Wire‐shaped electrodes for solid‐state cable‐type supercapacitors (SSCTS) with high device capacitance and ultrahigh rate capability are prepared by depositing poly(3,4‐ethylenedioxythiophene) onto self‐doped TiO₂ nanotubes (D‐TiO₂) aligned on Ti wire via a well‐controlled electrochemical process. The large surface area, short ion diffusion path, and high electrical conductivity of these rationally engineered electrodes all contribute to the energy storage performance of SSCTS. The cyclic voltammetric studies show the good energy storage ability of the SSCTS even at an ultrahigh scan rate of 1000 V s^?1, which reveals the excellent instantaneous power characteristics of the device. The capacitance of 1.1 V SSCTS obtained from the charge–discharge measurements is 208.36 µF cm^?1 at a discharge current of 100 µA cm^?1 and 152.36 µF cm^?1 at a discharge current of 2000 µA cm^?1, respectively, indicating the ultrahigh rate capability. Furthermore, the SSCTS shows superior cyclic stability during long‐term (20 000 cycles) cycling, and also maintains excellent performance when it is subjected to bending and succeeding straightening process.     

Design of conduction band structure of TiO2 electrode using Nb doping for highly efficient dye‐sensitized solar cells

A barrier layer of undoped TiO₂ was deposited on the Nb‐doped TiO₂ electrode to suppress the recombination at the Nb‐doped TiO₂/dye–electrolyte interface for highly efficient dye‐sensitized solar cells (DSCs). The Nb content in TiO₂ was varied in a range of 0.7–3.5 mol% to modify the TiO₂ energy‐band structure. Nb‐doped TiO₂/dye interfaces were characterized by a combination of ultraviolet photoemission spectroscopy and optical absorption spectroscopy measurements, allowing the determination of the conduction band minimum (CBM) of the TiO₂ electrode and the lowest unoccupied molecular orbital of the N719 dye. The lowering of TiO₂ CBM by Nb doping induced the increase in short‐circuit current of DSCs. However, open‐circuit voltage and fill factor are decreased, and this result was ascribed to the enhanced recombination at the Nb‐doped TiO₂/dye–electrolyte interface. The effect of doping on charge transport in DSCs was analyzed using electrochemical impedance spectroscopy. We have shown that by introducing of TiO₂ barrier layer, the Nb doping content, which results in DSC highest efficiency, can be increased because of the suppression of the dopant‐induced recombination. The energy conversion efficiency of the solar cells increased from 7.8% to 9.0% when undoped TiO₂ electrode is replaced with electrode doped with 2.7 mol% of Nb because of the improvement of the electron injection and collection efficiencies. The correlation between the electronic structure of the TiO₂ electrode, charge transfer characteristics, and photovoltaic parameters of DSCs is discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method

Polyaniline (PANI)/TiO₂ nanocomposite samples with various dopant percentages of TiO₂ were synthesized at room temperature using a chemical oxidative method. The samples were characterized by ultraviolet-visible spectrometer, Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and conductivity measurements. Incorporation of TiO₂ nanoparticles caused a slight red shift at 310 nm in the absorption spectra due to the interactions between the conjugated polymer chains and TiO₂ nanoparticles with π–π^? transition. FTIR confirmed the presence of TiO₂ in the molecular structure. In PANI/TiO₂ composites, two additional bands at 1623 cm^?1 and 1105 cm^?1 assigned to Ti–O and Ti–O^–C stretching modes were present. It can be concluded that Ti organic compounds are formed with an alignment structure of TiO₂ particles. XRD patterns revealed that, as the TiO₂ percentage was increased, the amorphous nature disappeared and the composites became more strongly oriented along the (1 1 0) direction, which showed the tetragonal structure of nanocrystalline TiO₂. SEM studies revealed the formation of uniform granular morphology with average grain size of 200 nm for (50%) PANI/TiO₂ nanocomposite samples.     

Sulfate‐Assisted Interfacial Engineering for High Yield and Efficiency of Triple Cation Perovskite Solar Cells with Alkali‐Doped TiO2 Electron‐Transporting Layers

Facile electron injection and extraction are two key attributes desired in electron transporting layers to enhance the efficiency of planar perovskite solar cells. Herein it is demonstrated that the incorporation of alkali metal dopants in mesoporous TiO₂ can effectively modulate electronic conductivity and improve the charge extraction process by counterbalancing oxygen vacancies acting as nonradiative recombination centers. Moreover, sulfate bridges (SO₄^2?) grafted on the surface of K‐doped mesoporous titania provide a seamless integration of absorber and electron‐transporting layers that accelerate overall transport kinetics. Potassium doping markedly influences the nucleation of the perovskite layer to produce highly dense films with facetted crystallites. Solar cells made from K:TiO₂ electrodes exhibit power conversion efficiencies up to 21.1% with small hysteresis despite all solution coating processes conducted under ambient air conditions (controlled humidity: 25–35%). The higher device efficiencies are attributed to intrinsically tuned electronic conductivity and chemical modification of grain boundaries enabling uniform coverage of perovskite films with large grain size.     

Low temperature TiO2 rutile phase thin film synthesis by chemical spray pyrolysis (CSP) of titanyl acetylacetonate

Rutile phase TiO₂ thin films have been synthesized using chemical spray pyrolysis of titanyl acetylacetonate TiAcAc in ethanol at 500 °C. The first part of the paper focuses on the thermal decomposition behavior of the precursor by simultaneous thermogravimetry and differential thermal analysis (TG/DTA) coupled with differential scanning calorimetry (DSC). The second part of the paper focuses on the evolution of TiO₂ thin films and their structural transformation with substrate temperature. XRD revealed amorphous TiO₂ thin film at low substrate temperatures (<350 °C) and on high substrate temperatures anatase (3.84 g/cm³) or rutile (4.25 g/cm³) crystalline structure was obtained. The lattice constant, grain size, microstrain and the dislocation density of the film were obtained from the peak width. FTIR spectra of both anatase and rutile TiO₂ revealed stretching vibration of the Ti–O bond for tetrahedral and octahedral surroundings of the titanium atom. Scanning electron micrograph showed the compactness of the rutile film.     

Room‐Temperature Synthesis of Porous Nanoparticulate TiO2 Films for Flexible Dye‐Sensitized Solar Cells

A novel room‐temperature method for the preparation of porous TiO₂ films with high performance in dye‐sensitized solar cells (DSSCs) has been developed. In this method a small amount of Ti^IV tetraisopropoxide (TTIP) is added to an ethanolic paste of TiO₂ nanoparticles, where it hydrolyzes in situ and connects the TiO₂ particles to form a homogenous and mechanically stable film of up to 10 μm thickness without crack formation. Residual organics originating from the TTIP were removed by UV–ozone treatment of the films, leading to a remarkable improvement of the cell efficiency. Intensity‐modulated photocurrent/voltage spectroscopy (IMPS/IMVS) showed that the main effect of the UV–ozone treatment is to suppress the recombination of photogenerated electrons, thereby extending their lifetime. The efficiency was further increased by preheating the TiO₂ nanoparticles before the paste preparation to remove contaminants originating from the preparation process of the particles. Solar‐to‐electric energy conversion efficiencies of 4.00 and 3.27 % have been achieved for cells with conductive glass and plastic film substrates, respectively, under illumination with AM 1.5 (100 mW cm^–2) simulated sunlight.     

Evidence of Interfacial Charge Transfer upon UV‐Light Irradiation in Novel Titanium Oxide Gel

We report on the combined magnetization and electron paramagnetic resonance characterization of a novel Ti‐O organic–inorganic gel hybrid and the related electron–hole generation process upon UV illumination. We find that electrons are injected into the conduction band of the Ti‐O framework, photoreducing Ti^IV to Ti^III. Ti^III sites are mainly located on the surface, owing to the nanometric dimensions of the inorganic component. Surprisingly, the symmetry of the TiO₆ octahedra depends on the level of illumination: in the lightly UV‐exposed samples Ti^III is sited in the weakly distorted TiO₆ octahedra to which methanoate groups are bonded, as suggested by electron spin echo envelope modulation (ESEEM) experiments. Extensive illumination causes structural rearrangements, leading to enhanced tetragonal TiO₆ distortion and shifting the Ti^III interaction towards the hydroxide groups or water. The results provide clear evidence for an interfacial charge transfer between the quantum‐size TiO lattice and coordinated species upon in situ and ex situ UV illumination at temperatures from room temperature to 5 K.