Direct printing synthesis of self-organized copper oxide hollow spheres on a substrate using copper(II) complex ink: gas sensing and photoelectrochemical properties.

The direct printing synthesis of metal oxide hollow spheres in the form of film on a substrate is reported for the first time. This method offers facile, scalable, high-throughput production and device fabrication processes. The printing was carried out via a doctor-blade method using Cu(II) complex ink with controllable high viscosity based on formate-amine coupling. Following only thermal heating in air, well-defined polycrystalline copper oxide hollow spheres with a submicrometer diameter (≤1 µm) were formed spontaneously while being assembled in the form of a film with good adhesion on the substrate. This spontaneous hollowing mechanism was found to result from the Kirkendall effect during oxidation at elevated temperature. The CuO films with hollow spheres, prepared via direct printing synthesis at 500 °C, led to the creation of a superior p-type gas sensor and photocathode for photoelectrochemical water splitting with completely hollow cores, a rough/porous shell structure, a single phase, high crystallinity, and no organic/polymer residue. As a result, the CuO hollow-sphere films showed high gas responses and permissible response speeds to reducing gases and high photocurrent density compared to conventional CuO powder films and the values previously reported. These results exemplify the successful realization of a high-throughput printing fabrication method for the creation of superior nanostructured devices.

Integrating metal-oxide-decorated CNT networks with a CMOS readout in a gas sensor.

We have implemented a tin-oxide-decorated carbon nanotube (CNT) network gas sensor system on a single die. We have also demonstrated the deposition of metallic tin on the CNT network, its subsequent oxidation in air, and the improvement of the lifetime of the sensors. The fabricated array of CNT sensors contains 128 sensor cells for added redundancy and increased accuracy. The read-out integrated circuit (ROIC) was combined with coarse and fine time-to-digital converters to extend its resolution in a power-efficient way. The ROIC is fabricated using a 0.35 µm CMOS process, and the whole sensor system consumes 30 mA at 5 V. The sensor system was successfully tested in the detection of ammonia gas at elevated temperatures.

SnO(2) nanotubes fabricated using electrospinning and atomic layer deposition and their gas sensing performance.

A novel method is developed to fabricate a SnO(2) nanotube network by utilizing electrospinning and atomic layer deposition (ALD), and the network sensor is proven to exhibit excellent sensitivity to ethanol owing to its hollow, nanostructured character. The electrospun polyacrylonitrile (PAN) nanofibers of 100-200 nm diameter are used as a template after stabilization at 250 degrees C. An uniform and conformal SnO(2) coating on the nanofiber template is achieved by ALD using dibutyltindiacetate (DBTDA) as the Sn source at 100 degrees C and the wall thickness is precisely controlled by adjusting the number of ALD cycles. The calcination at 700 degrees C transforms the amorphous nanofibers into SnO(2) nanotubes composed of several nanometer-sized crystallites. The SnO(2) nanotube network sensor responds to ethanol, H(2), CO, NH(3) and NO(2) gases, but it exhibited an extremely high gas response to ethanol with a short response time (<5 s). The results demonstrate that the combination of electrospinning and ALD is a very effective and promising technique to fabricate long and uniform metal oxide nanotubes with the precise control of wall thickness, which can be applied to various applications such as gas sensors and lithium ion batteries.

H(2) sensing characteristics of SnO(2) coated single wall carbon nanotube network sensors.

SnO(2) nanoparticle coated single wall nanotube (SWNT) network sensors were fabricated by forming a SWNT network on the Pt patterned SiO(2)/Si substrate using a dip coating method and subsequently depositing SnO(2) nanoparticles on the SWNT network by rf magnetron sputtering. Their H(2) gas sensing properties were investigated. The SnO(2)-SWNT network sensors stably and reversibly responded to H(2) gas even at room temperature and could detect H(2) gas down to 100 ppm. In addition to the low temperature detection, a remarkable finding was that the gas sensing behavior of SnO(2)-SWNT network sensors was changed from p-type to n-type with increasing SnO(2) deposition time (i.e. surface coverage of SnO(2) on SWNT). A schematic model was proposed to explain the switching of sensing behavior depending on the surface coverage of SnO(2) nanoparticles on the SWNTs.

CuBi2O4 Prepared by the Polymerized Complex Method for Gas-Sensing Applications.

Multicomponent oxides can be extensively explored as alternative gas-sensing materials to binary oxides with their structural and compositional versatilities. In this work, the gas-sensing properties of CuBi2O4 have been investigated toward various reducing gases (C2H5OH, NH3, H2, CO, and H2S) and oxidizing gas (NO2) for the first time. For this, the powder synthesis has been developed using the polymerized complex method (Pechini method) to obtain a single-phase polycrystalline CuBi2O4. The defect, optical, and electronic properties in the prepared CuBi2O4 powder were modulated by varying the calcination temperature from 500 to 700 °C. Noticeably, a high concentration of Cu+-oxygen vacancy ([Formula: see text]) defect complexes and isolated Cu2+ ion clusters was found in the 500 °C-calcined CuBi2O4, where they were removed through air calcination at higher temperatures (up to 700 °C) while making the compound more stoichiometric. The change in the intrinsic defect concentration with the calcination temperature led to the variation of the electronic band gap energy and hole concentration in CuBi2O4 with the polaronic hopping conduction (activation energy = 0.43 eV). The CuBi2O4 sensor with 500 °C-calcined powder showed the highest gas responses (specifically, 10.4 toward 1000 ppm C2H5OH at the operating temperature of 400 °C) with the highest defect concentration. As a result, the gas-sensing characteristics of CuBi2O4 are found to be dominantly affected by the intrinsic defect concentration, which is controlled by the calcination temperature. Toward reducing H2S and oxidizing NO2 gases, the multiple reactions arising simultaneously on the surface of the CuBi2O4 sensor govern its response behavior, depending on the gas concentration and the operating temperature. We believe that this work can be a cornerstone for understanding the effect of chemical defect on the gas-sensing characteristics in multicomponent oxides.

Giant Electroresistive Ferroelectric Diode on 2DEG.

Manipulation of electrons in a solid through transmitting, storing, and switching is the fundamental basis for the microelectronic devices. Recently, the electroresistance effect in the ferroelectric capacitors has provided a novel way to modulate the electron transport by polarization reversal. Here, we demonstrate a giant electroresistive ferroelectric diode integrating a ferroelectric capacitor into two-dimensional electron gas (2DEG) at oxide interface. As a model system, we fabricate an epitaxial Au/Pb(Zr(0.2)Ti(0.8))O3/LaAlO3/SrTiO3 heterostructure, where 2DEG is formed at LaAlO3/SrTiO3 interface. This device functions as a two-terminal, non-volatile memory of 1 diode-1 resistor with a large I+/I- ratio (>10(8) at ± 6 V) and I(on)/I(off) ratio (>10(7)). This is attributed to not only Schottky barrier modulation at metal/ferroelectric interface by polarization reversal but also the field-effect metal-insulator transition of 2DEG. Moreover, using this heterostructure, we can demonstrate a memristive behavior for an artificial synapse memory, where the resistance can be continuously tuned by partial polarization switching, and the electrons are only unidirectionally transmitted. Beyond non-volatile memory and logic devices, our results will provide new opportunities to emerging electronic devices such as multifunctional nanoelectronics and neuromorphic electronics.

Brookite TiO2 thin film epitaxially grown on (110) YSZ substrate by atomic layer deposition.

Epitaxial brookite TiO2 (B-TiO2) film was deposited on (110) yttria-stabilized zirconia (YSZ) substrate using plasma-enhanced atomic layer deposition, and its structural, optical, and gas sensing properties were investigated. As-deposited TiO2 film was a pure brookite and (120) oriented. The determined in-plane orientation relationships were [21̅0]B-TiO2//[1̅10]YSZ and [001]B-TiO2 //[001]YSZ. The B-TiO2 film showed ∼70% transmittance and the optical band gap energy was 3.29 eV. The B-TiO2 film-based gas sensor responded to H2 gas even at room temperature and the highest magnitude of the gas response was determined to be ∼150 toward 1000 ppm of H2/air at 150 °C. In addition, B-TiO2 sensor showed a high selectivity for H2 against CO, EtOH, and NH3.

Nonvolatile resistance switching on two-dimensional electron gas.

Two-dimensional electron gas (2DEG) at the complex oxide interfaces have brought about considerable interest for the application of the next-generation multifunctional oxide electronics due to the exotic properties that do not exist in the bulk. In this study, we report the integration of 2DEG into the nonvolatile resistance switching cell as a bottom electrode, where the metal-insulator transition of 2DEG by an external field serves to significantly reduce the OFF-state leakage current while enhancing the on/off ratio. Using the Pt/Ta2O5-y/Ta2O5-x/SrTiO3 heterostructure as a model system, we demonstrate the nonvolatile resistance switching memory cell with a large on/off ratio (>10(6)) and a low leakage current at the OFF state (∼10(-13) A). Beyond exploring nonvolatile memory, our work also provides an excellent framework for exploring the fundamental understanding of novel physics in which electronic and ionic processes are coupled in the complex heterostructures.

SnO2@TiO2 double-shell nanotubes for a lithium ion battery anode with excellent high rate cyclability.

SnO2@TiO2 double-shell nanotubes have been facilely synthesized by atomic layer deposition (ALD) using electrospun PAN nanofibers as templates. The double-shell nanotubes exhibited excellent high rate cyclability for lithium ion batteries. The retention of hollow structures during cycling was demonstrated.

Non-volatile control of 2DEG conductivity at oxide interfaces.

The functionalization of two-dimensional electron gas (2DEG) at oxide interfaces can be realized integrating 2DEG with multifunctional oxide overlayers by epitaxial growth. Using a ferroelectric Pb(Zr0.2 Ti0.8 )O3 overlayer on 2DEG (LaAlO3 /SrTiO3 ), we demonstrate a model system of the functionalized 2DEG, where electrical conductivity of 2DEG can be reversibly controlled with a large on/off ratio (>1000) in a non-volatile way by ferroelectric polarization switching.