Fast piezoresistive sensor and UV photodetector based on Mn‐doped ZnO nanorods

A low cost hydrothermal synthesis method to synthesize Mn‐doped ZnO nanorods (NRs) with controllable morphology and structure has been developed. Ammonia is used to tailor the ammonium hydroxide concentration, which provides a source of OH^– for hydrolysis and precipitation during the growth instead of HMT. The morphological, chemical composition, structural, and electronic structure studies of the Mn‐doped ZnO NRs show that the Mn‐doped ZnO NRs have a hexagonal wurtzite ZnO structure along the c‐axis and the Mn ions replace the Zn sites in the ZnO NRs matrix without any secondary phase of metallic manganese element and manganese oxides observed. The fabricated PEDOT:PSS/Zn_0.85Mn_0.15O Schottky diode based piezoresistive sensor and UV photodetector shows that the piezoresistive sensor has pressure sensitivity of 0.00617 kPa^–1 for the pressure range from 1 kPa to 20 kP and 0.000180 kPa^–1for the pressure range from 20 kPa to 320 kPa with relatively fast response time of 0.03 s and the UV photodetector has both relatively high responsivity and fast response time of 0.065 A/W and 2.75 s, respectively. The fabricated Schottky diode can be utilized as a very useful human‐friendly interactive electronic device for mass/force sensor or UV photodetector in everyday living life. This developed device is very promising for small‐size, low‐cost and easy‐to‐customize application‐specific requirements. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Drop‐cast and dye‐sensitized ZnO nanorod‐based visible‐light photodetectors

We report the facile fabrication of metal–semiconductor–metal (MSM) photodetectors with dye‐sensitized ZnO nanorods (NRs) operating at wavelengths of ～405–638 nm by a simple drop casting method. The ZnO NRs were synthesized by the hydrothermal synthesis method at 75 °C. The droplet of ethanol solution containing ZnO NRs was dropped between two metal electrodes and dried at 65 °C, which allows the ZnO NRs to be adhered and contacted to both metal electrodes. When a violet light of 405 nm was illuminated into the MSM ZnO NRs‐based photodetector, the photocurrent gain was obtained as ～3.9 × 10³ at the applied bias voltage of 5 V. By increasing the bias voltage from 10 V to 15 V, the device exhibited good recovery performance with a largely reduced reset time from 85.68 s to 2.47 s and an increased on–off ratio from 17.9 to 77.4. To extend the photodetection range towards the long visible spectral region, the ZnO NRs were sensitized by the N719 dye and then drop‐cast. The dye‐sensitized ZnO NRs‐based photodetector also exhibited good photocurrent switching under 638 nm of light illumination. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved performance of silicon‐nanoparticle film‐coated dye‐sensitized solar cells

Silicon (Si) nanoparticles with average size of 13 nm and orange–red luminescence under UV absorption were synthesized using electrochemical etching of silicon wafers. A film of Si nanoparticles with thickness of 0.75 µm to 2.6 µm was coated on the glass (TiO₂ side) of a dye‐sensitized solar cell (DSSC). The cell exhibited nearly 9% enhancement in power conversion efficiency (η) at film thickness of ～2.4 µm under solar irradiation of 100 mW/cm² (AM 1.5) with improved fill factor and short‐circuit current density. This study revealed for the first time that the Si‐nanoparticle film converting UV into visible light and helping in homogeneous irradiation, can be utilized for improving the efficiency of the DSSCs. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High‐gain Zn1–xMgx O‐based ultraviolet photodetectors on Al2O3 and LiGaO2 substrates

We report the fabrication and characterization of highly responsive ZnMgO‐based ultraviolet (UV) photodetectors in the metal–semiconductor–metal (MSM) configuration for solar‐blind/visible‐blind optoelectronic application. MSM devices were fabricated from wurtzite Zn_1–xMg_x O/ZnO (x ～ 0.44) thin‐film heterostructures grown on sapphire (α‐Al₂O₃) substrates and w‐Zn_1–xMg_x O (x ～ 0.08), grown on nearly lattice‐matched lithium gallate (LiGaO₂) substrates, both by radio‐frequency plasma‐assisted molecular beam epitaxy (PAMBE). Thin film properties were studied by AFM, XRD, and optical transmission spectra, while MSM device performance was analyzed by spectral photoresponse and current–voltage techniques. Under biased conditions, α‐Al₂O₃ grown devices exhibit peak responsivity of ～7.6 A/W at 280 nm while LiGaO₂ grown samples demonstrate peak performance of ～119.3 A/W, albeit in the UV‐A regime (～324 nm). High photoconductive gains (76, 525) and spectral rejection ratios (～10³, ～10⁴) were obtained for devices grown on α‐Al₂O₃ and LiGaO₂, respectively. Exemplary device performance was ascribed to high material quality and in the case of lattice‐matched LiGaO₂ films, decreased photocarrier trapping probability, presumably due to low‐density of dislocation defects. To the best of our knowledge, these results represent the highest performing ZnO‐based photodetectors on LiGaO₂ yet fabricated, and demonstrate both the feasibility and substantial enhancement of photodetector device performance via growth on lattice‐matched substrates. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Large‐area Ag nanorod array substrates for SERS: AAO template‐assisted fabrication,functionalization, and application in detection PCBs

Highly ordered arrays of thiolated β‐cyclodextrin (HS‐β‐CD) functionalized Ag‐nanorods (Ag‐NRs) with plasmonic antennae enhancement of electrical field have been achieved for encapsulation and rapid detection of polychlorinated biphenyls (PCBs). The large‐area ordered arrays of rigid Ag‐NRs supported on copper base were fabricated via porous anodic aluminum oxide (AAO) template‐assisted electrochemical deposition. The inter‐nanorod gaps between the neighboring Ag‐NRs were tuned to sub‐10 nm by thinning the pore‐wall thickness of the AAO template using diluted H₃PO₄. The nearly perfect large‐area ordered arrays of Ag‐NRs supported on copper base render these systems excellent in surface‐enhanced Raman scattering (SERS) performance with uniform electric field enhancement, as testified by the SERS spectra and Raman mappings of rhodamine 6 G. Furthermore, the Ag‐NRs were functionalized with HS‐β‐CD molecules so as to capture the apolar PCB molecules in the hydrophobic cavity of the CD. Compared to the ordinary undecorated SERS substrates, the HS‐β‐CD modified Ag‐NR arrays exhibit better capture ability and higher sensitivity in rapid detection of PCBs. Copyright © 2012 John Wiley & Sons, Ltd.     

Asymmetry in electrical properties of Al‐doped TiO2 film with respect to bias voltage

The energy diagram of RuO₂/Al‐doped TiO₂/RuO₂ structures was estimated from the capacitance–voltage and leakage current density–voltage curves. The Al‐doping profile in TiO₂ film was varied by changing position of the atomic layer deposition cycle of Al₂O₃ during the atomic layer deposition of 9 nm‐thick TiO₂ film. The interface between the TiO₂ film and the RuO₂ electrode containing Al‐doping layer showed a higher Schottky barrier by 0.1 eV compared with the opposite interface without the doping layer. The evolution of various leakage current profiles upon increasing the bias with opposite polarity could be well explained by the asymmetric Schottky barrier. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

TiO2 Nanotube Array/Monolayer Graphene Film Schottky Junction Ultraviolet Light Photodetectors

Schottky junctions made from a titanium dioxide nanotube (TiO₂NT) array in contact with a monolayer graphene (MLG) film are fabricated and utilized for UV light detection. The TiO₂NT array is synthesized by the anodization and the MLG through a simple chemical vapor deposition process. Photoconductive analysis shows that the fabricated Schottky junction photodetector (PD) is sensitive to UV light illumination with good stability and reproducibility. The corresponding responsivity (R), photoconductive gain (G), and detectivity (D*) are calculated to be 15 A W^?1, 51, and 1.5 × 10¹² cm Hz^1/2 W^?1, respectively. It is observed that the fabricated PD exhibits spectral sensitivity and a simple power‐law dependence on light intensity. Moreover, the height of the Schottky junction diode is derived to be 0.59 V by using a low temperature I–V measurement. Finally, the working mechanism of the TiO₂NT array/MLG film Schottky junction PD is elucidated.     

Rapid synthesis and characterization of ultra‐thin shell Au@SiO2 nanorods with tunable SPR for shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS)

The recently reported shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) is considered as the next generation of advanced spectroscopy for its surface and molecular generality. With the aim to utilize the virtues of shell‐isolated strategy and advance the SHINERS technique, we introduce a silane‐based rapid synthesis method of silica‐coating Au nanorods (Au@SiO₂ NRs) with manoeuvrable ultra‐thin shell and tunable SPR. The results demonstrate that the SPR of Au NRs could be optimized to obtain large Raman enhancement using either 633 nm or 785 nm laser. Differing from previously reported Au@SiO₂ NRs synthesis method, we can tune the silica shell thickness within several nanometers to maximize the Raman signal while effectively eliminating the exterior interference. And this advanced synthesis method has also significantly reduced the silica‐coating time from one day to ca. 1 h. This method as a new development of SHINERS technique has successfully got enhanced signal in solution Raman tests of malachite green, giving a great potential to be extended to in‐situ measurement for daily life detection. Copyright © 2013 John Wiley & Sons, Ltd.     

High‐temperature stability of Au/p‐type diamond Schottky diode

Rectification properties of Au Schottky diodes were investigated in high‐temperature operation. These diodes were fabricated on a p‐type diamond single crystal using the vacuum‐ultraviolet light/ozone treatment. The ideality factor n of the Schottky diodes decreased monotonically with increasing measurement temperature whereas the Schottky barrier height ?_b increased, and ?_b reached 2.6 eV at 550 K with n of 1.1. Through high temperature heating at 870 K, the mean value of ?_b at 300 K changed permanently from 2.2 eV to 1.1 eV. Decrease of ?_b might originate from a dissolution of oxygen termination at the Au/diamond interface. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silver microgrid transparent conductive electrode based on bulk plasmon effect for ultraviolet wavelength application

Silver microgrid/TiO₂/ITO (indium tin oxide glass) sandwich‐structure photodetectors with various pore sizes are fabricated by a microsphere lithography strategy. This ultraviolet (UV) detector possesses ohmic contact characteristics. The high UV transmittance results from an enhanced bulk plasmon effect of the silver microgrid electrode. Photoelectric properties of the sandwich structure with various pore sizes are discussed. The short transport distance of carriers and the low blocking of incoming UV light are the main reasons of the high activity for silver microgrid/TiO₂/ITO sandwich‐structure photodetectors. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electroluminescence enhancement in ultraviolet organic light‐emitting diode with graded hole‐injection and ‐transporting structure

Electroluminescent intensity and external quantum efficiency (EQE) in ultraviolet organic light‐emitting diodes (UV OLEDs) have been remarkably enhanced by using a graded hole‐injection and ‐transporting (HIT) structure of MoO₃/N,N ′‐bis(naphthalen‐1‐yl)‐N,N ′‐bis(phenyl)‐benzidine/MoO₃/4,4′‐bis(carbazol‐9‐yl)biphenyl (CBP). The graded‐HIT based UV OLED shows superior short‐wavelength emis‐ sion with spectral peak of ～410 nm, maximum electroluminescent intensity of 2.2 mW/cm² at 215 mA/cm² and an EQE of 0.72% at 5.5 mA/cm². Impedance spectroscopy is employed to clarify the enhanced hole‐injection and ‐transporting capacity of the graded‐HIT structure. Our results provide a simple and effective approach for constructing efficient UV OLEDs. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Amplification of Solar Energy Conversion in Quantum‐Confined CdSe‐Sensitized TiO2 Photonic Crystals by Trapping Light

Photonic effects amplifying solar energy conversion are reported in titania inverse opals sensitized with quantum‐confined CdSe films. TiO₂ inverse opals (i‐TiO₂‐o) and unstructured nanocrystalline TiO₂ (nc‐TiO₂) films are sensitized with CdSe deposited via successive ionic layer adsorption and reaction (SILAR) by generating Se^2? in situ under inert atmosphere, and the film absorbance is tuned by the number of SILAR cycles. Photonic effects are investigated while varying the i‐TiO₂‐o stop band position relative to CdSe films’ absorbance. i‐TiO₂‐o films with stop band at 700 and 560 nm are sensitized with CdSe having absorption edges at 600 and 650 nm thus tuning absorbance to the red and the blue of the stop band. Significant amplification in photon‐to‐current conversion efficiency is measured when CdSe films prepared via two cycles are adsorbed on i‐TiO₂‐o with a stop band at 700 nm, with a maximum average enhancement factor equal to 6.7 ± 1.6 at 640 nm, 60 nm to the blue of the stop band center, relative to nc‐TiO₂ sensitized with comparable CdSe amounts. The gain is observed over a wide frequency range to the blue of the stop band and is greatest when film absorbance was low. The photocurrent gain is not a result of differences in the rates of charge separation or charge transport, and occurs in the same frequency range where absorbance amplification is measured to the blue of the 700‐i‐TiO₂‐o stop band, and is thus attributed to slow light effects enhancing absorbance in the photonic crystal environment.     

Surface enhanced Raman scattering of nano diamond using visible‐light‐activated TiO2 as a catalyst to photo‐reduce nano‐structured silver from AgNO3 as SERS‐active substrate

In this work, we demonstrate nano‐structured silver particles photo‐reduced from silver nitride (AgNO₃) solution using visible‐light‐activated titanium dioxide (TiO₂), which can be a convenient and effective substrate for surface enhanced Raman spectroscopy (SERS) observation. Visible‐light‐activated carbon‐containing TiO₂ nanoparticles are applied to photo‐reduce and form nano‐structured silver from AgNO₃ upon visible‐light illumination. Photo‐reduced nano‐structured silver is used as an active substrate for SERS studies of TiO₂ as well as nano diamond and TiO₂. The photo reduction of AgNO₃ and SERS observation can be obtained by simultaneously using the same visible laser excitation. The coexistence of the anatase phase with small admixture of the rutile phase in the TiO₂ can be observed using SERS. The carbon structure in the carbon‐containing TiO₂ was determined to be sp² type carbon bonding by SERS. Copyright © 2009 John Wiley & Sons, Ltd.     

Adsorption study of 4‐MBA on TiO2 nanoparticles by surface‐enhanced Raman spectroscopy

In this paper, the adsorption of 4‐mercaptobenzoic acid (4‐MBA) on TiO₂ nanoparticles was studied mostly by surface‐enhanced Raman spectroscopy (SERS) and UV‐vis spectroscopy, at different pH values as well as under different temperatures and concentrations. The results show that the 4‐MBA molecules are bonded to the TiO₂ surface both through the sulfur atoms and COO⁻ groups at neutral or alkaline pH, but only through the sulfur atom at acidic pH. Furthermore, the 4‐MBA molecules possess high adsorptive stability on TiO₂ at a comparatively high temperature (150 °C). Concentration‐dependent SERS experiments show that the saturation concentration for 4‐MBA adsorbed on TiO₂ is about 10⁻³ M in natural case (pH = 6). Copyright © 2009 John Wiley & Sons, Ltd.     

Improved surface‐enhanced Raman scattering properties of TiO2 nanoparticles by Zn dopant

In this paper, pure and Zn‐doped TiO₂ nanoparticles (NPs) with various content of Zn were prepared by a sol–hydrothermal method and were employed as active substrates for surface‐enhanced Raman scattering (SERS). On the 3% Zn‐doped TiO₂ substrate, 4‐mercaptobenzoic acid(4‐MBA) molecules exhibit a higher SERS intensity by a factor of 6, as compared with the native enhancement of 4‐MBA adsorbed on undoped TiO₂ NPs. Moreover, the higher SERS activity was still observed on the 3% Zn‐doped TiO₂ NPs at temperature even up to 125 °C. These results indicate that an appropriate amount of Zn doping can improve the SERS performances of TiO₂ SERS‐active substrates. The introduction of Zn dopant can enrich the surface states (defects) of TiO₂ and improve the separation efficiency of photo‐generated charge carriers (electrons and holes) in TiO₂, according to measurements of X‐ray diffraction, UV‐visible diffuse reflectance spectroscopy, and photoluminescence, which are responsible for the influence of Zn dopant on the improved SERS performances of TiO₂ NPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics and mechanism for acid‐catalyzed disproportionation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl

Disproportionation of cyclic nitroxyl radicals (NRs) in acid solutions is of key importance for the chemistry of these compounds. Meanwhile, the data reported on the mechanism of this reaction in dilute acids are inconsistent with those on the stability of NRs in concentrated acids. Here we have examined the kinetics and stoichiometry for the disproportionation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl ( 1 ) in aqueous H₂SO₄ (1.0–99.3 wt%) and found that (1) the disproportionation of 1 proceeds by the same mechanism over the entire range of acid concentrations, (2) the effective rate constant of the process exhibits a bell‐shaped dependence on the excess acidity function X peaked at X = ?pK _1H+ = 5.8 ± 0.3, (3) a key step of the process involves the oxidation of 1 with its protonated counterpart 1H ⁺ yielding oxopiperidinium cation 2 and hydroxypiperidine 3 at a rate constant of (1.4 ± 0.8) × 10⁵ M^?1 · s^?1, and (4) the reaction is reversible and, upon neutralization of acid, disproportionation products 2 and 3H ⁺ comproportionate to starting 1 . In highly acidic media, the protonated form 1H ⁺ is relatively stable due to a low disproportionation rate. Based on the known and newly obtained values of equilibrium constants, both the standard redox potential for the 1H ⁺ / 3 pair (955 ± 15 mV) and the pH‐dependences have been calculated for the reduction potentials of 1 and 2 to hydroxylamine 3 that is in equilibrium with its protonated 3H ⁺ and deprotonated 3 ^? forms. The data obtained provide a deeper insight into the mechanism of nitroxyl‐involving reactions in chemical and biological systems. Copyright © 2008 John Wiley & Sons, Ltd.     

All‐Dielectric Meta‐Reflectarray for Efficient Control of Visible Light

Wide‐bandgap material based all‐dielectric metasurfaces have been ideal platforms for the realization of arbitrary phase control in visible spectrum. While TiO₂ metasurfaces are very promising in broadband and high‐efficiency anomalous transmission, meta‐hologram, and meta‐lenses et al., the current realizations are strongly dependent on the sophisticated fabrication technique to fabricate TiO₂ nano‐pillars with aspect ratio > 10. Herein we experimentally demonstrate a much simpler approach to realize efficient phase control of visible light. By exploiting TiO₂ nano‐blocks as meta‐atoms on a ground metal plane, we find that TiO₂ metasurface with aspect ratio around 1‐1.5 is good enough to produce phase changes covering ‐π to π and high reflection efficiency simultaneously. Based on the phase control of the meta‐reflectarray, anomalous reflection with a ratio between anomalous reflection and normal reflection ～ 74/26 have been experimentally realized using a combination of typical electron‐beam lithography, electron‐beam evaporation, and a simple lift‐off process. Similarly, high performance TiO₂ metasurface in form of hologram has also been demonstrated for red (633 nm), green (520 nm), and blue (445 nm) wavelengths. We believe this research shall route a new way to cost‐effective all‐dielectric metasurfaces and advance their applications in encryption, anti‐counterfeiting, and wearable displays.     

Titanium local structure in tektite probed by X‐ray absorption fine structure spectroscopy

The local structure of titanium in tektites from six strewn fields was studied by Ti K‐edge X‐ray absorption near edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti—O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high‐temperature TiO₂–SiO₂ glass and TiO₂ anatase. All samples showed that the valence of Ti is 4+. Based on the Ti—O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four‐coordinated tetrahedral site with Ti—O distances of 1.84–1.79 Å; type II, Ti occupies a five‐coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti—O distances of 1.92–1.89 Å; type III, Ti occupies a six‐coordinated octahedral site with Ti—O distances of 2.00–1.96 Å. Although Ti occupies the TiO₆ octahedral site in most titanium minerals under ambient conditions, some tektites have four‐ and five‐coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages.     

Ag‐doped TiO2 enhanced photocatalytic oxidation of 1,2‐cyclohexanediol

The superiority of silver‐doped titania for photocatalytic oxidation (PCO) of organic compounds inspired us to investigate PCO of 1,2‐cyclohexanediol. Ag/TiO₂ was prepared, characterized (nanosize 19–24 nm) and used for oxidation of 1,2‐cyclohexanediol (1) in acetonitrile. The photolysate was analyzed using GC and GC/MS techniques. The PCO products are 2‐hydroxylcyclohexanone (2), 1,2‐cyclohexandione (3), 2‐cyclohexenone(4), cyclohexanone (5), and adipic acid (6).The formation of electron–hole pair at the surface of the catalyst followed by oxidation reactions was the suggested mechanism. Kinetic studies revealed first‐order mechanism for PCO of 1 and rate constant (k) = ?0.145 h^–1. Copyright © 2012 John Wiley & Sons, Ltd.     

Resonance Raman spectroscopic study for radial vibrational modes in ultra‐thin walled TiO2 nanotubes

The study reports the observation of radial vibrational modes in ultra‐thin walled anatase TiO₂ nanotube powders grown by rapid breakdown anodization technique using resonant Raman spectroscopic study. The as‐grown tubes in the anatase phase are around 2–5 nm in wall thickness, 15–18 nm in diameter and few microns in length. The E_{g(ν1,ν5,ν6)} phonon modes with molecular vibrations in the radial direction are predominant in the resonance Raman spectroscopy using 325 nm He–Cd excitation. Multi‐phonons including overtones and combinational modes of E_{g(ν1,ν5,ν6)} are abundantly observed. Fröhlich interaction owing to electron–phonon coupling in the resonance Raman spectroscopy of ultra‐thin wall nanotubes is responsible for the observation of radial vibrational modes. Finite size with large surface energy in these nanotubes energetically favor only one mode, B_1g(ν4) with unidirectional molecular vibrations in the parallel configuration out of the three Raman modes with molecular vibration normal to the radial modes. Enhanced specific heat with increasing temperatures in these nanotubes as compared to that reported for nanoparticles of similar diameter may possibly be related to the presence of the prominent radial mode along with other energetic phonon mode. The findings elucidate the understanding of total energy landscape for TiO₂ nanotubes. Copyright © 2015 John Wiley & Sons, Ltd.