Jeffrey S. Cross

Electrochemistry at Chemically Modified Graphenes

Electrochemical applications of graphene are of great interest to many researchers as they can potentially lead to crucial technological advancements in fabrication of electrochemical devices for energy production and storage, and highly sensitive sensors. There are many routes towards fabrication of bulk quantities of chemically modified graphenes (CMG) for applications such as electrode materials. Each of them yields different graphene materials with different functionalities and structural defects. Here, we compare the electrochemical properties of five different chemically modified graphenes: graphite oxide, graphene oxide, thermally reduced graphene oxide, chemically reduced graphene oxide, and electrochemically reduced graphene oxide. We characterized these materials using transmission electron microscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, which allowed us to correlate the electrochemical properties with the structural and chemical features of the CMGs. We found that thermally reduced graphene oxide offers the most favorable electrochemical performance among the different materials studied. Our findings have a profound impact for the applications of chemically modified graphenes in electrochemical devices.

Surface plasmon resonance biosensor with high anti-fouling ability for the detection of cardiac marker troponin T

Designing a surface recognition layer with high anti-fouling ability, high affinity, and high specificity is an important issue to produce high sensitivity biosensing transducers. In this study, a self-assembled monolayer (SAM) consisting of a homogeneous mixture of oligo(ethylene glycol) (OEG)-terminated alkanethiolate and mercaptohexadecanoic acid (MHDA) on Au was employed for immobilizing troponin T antibody and applied in detecting cardiac troponin T by using surface plasmon resonance (SPR). The mixed SAM showed no phase segregation and exhibited human serum albumin resistance, particularly with an antibody-immobilized surface. X-ray photoemission spectra revealed that the chemical composition ratio of OEG to the mixed SAM was 69% and the OEG packing density was 82%. The specific binding of troponin T on the designed surface indicated a good linear correlation (R=0.991, P<0.0009) at concentrations lower than 50 μgmL(-1) with the limit of detection of 100 ngmL(-1) using a SPR measuring instrument. It is concluded that the mixed SAM functions as designed since it has high detection capability, high accuracy and reproducibility, as well as shows strong potential to be applied in rapid clinical diagnosis for label-free detection within 2 min.

Characterization of Bi and Fe co-doped PZT capacitors for FeRAM

Abstract Ferroelectric random access memory (FeRAM) has been in mass production for over 15 years. Higher polarization ferroelectric materials are needed for future devices which can operate above about 100 °C. With this goal in mind, co-doping of thin Pb(Zr40,Ti60)O3 (PZT) films with 1 at.% Bi and 1 at.% Fe was examined in order to enhance the ferroelectric properties as well as characterize the doped material. The XRD patterns of PZT-5% BiFeO3 (BF) and PZT 140-nm thick films showed (111) orientation on (111) platinized Si wafers and a 30 °C increase in the tetragonal to cubic phase transition temperature, often called the Curie temperature, from 350 to 380 °C with co-doping, indicating that Bi and Fe are substituting into the PZT lattice. Raman spectra revealed decreased band intensity with Bi and Fe co-doping of PZT compared to PZT. Polarization hysteresis loops show similar values of remanent polarization, but square-shaped voltage pulse-measured net polarization values of PZT-BF were higher and showed higher endurance to repeated cycling up to 1010 cycles. It is proposed that Bi and Fe are both in the +3 oxidation state and substituting into the perovskite A and B sites, respectively. Substitution of Bi and Fe into the PZT lattice likely creates defect dipoles, which increase the net polarization when measured by the short voltage pulse positive-up-negative-down (PUND) method.

Theoretical and experimental determination of the crystal structures of cesium–molybdenum chloride

We herein report the structure-property relationships of the octahedral molybdenum metal cluster compound, Cs2[Mo6Cl14]. Using purified samples, we attempted to determine if Cs2[Mo6Cl14] possesses crystalline polarity. Heat treatment was performed prior to characterization to remove impurities, as X-ray powder diffraction and Fourier transformation infrared spectroscopy studies suggested the unit cell of Cs2[Mo6Cl14] expanded with the insertion of water molecules and/or hydroxyl moieties. Geometry optimization and total energy calculations by density functional theory calculations were conducted to determine whether Cs2[Mo6Cl14] crystallizes in centrosymmetric () or non-centrosymmetric (P31c) space groups. Furthermore, the results of the optical studies, along with the absence of a second harmonic generation, and the observation of a strong third harmonic generation, supported the hypothesis that inversion symmetry exists in the Cs2[Mo6Cl14] lattice. The space group of Cs2[Mo6Cl14] was therefore identified as symmetry.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations

The electronic and crystal structures of Cs2[Mo6X14] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al Kα, suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Ferroelectric Properties of BaZrO3 Doped Sr0.8Bi2.2Ta2O9 Thin Films

Novel sol–gel derived Sr0.8Bi2.2Ta2O9 (SBT) doped with 5 and 7% molar ratio BaZrO3 (BZ) thin films were fabricated, characterized, and electrical properties were evaluated with Pt electrodes. X-ray diffraction (XRD) analysis showed all the characteristic peaks of the layered perovskite structure with (115) orientation and slight peak broadening by BZ doping. X-ray photoelectron spectra (XPS) showed a small shift in the Sr 3d peak with BZ substitution. Scanning electron microscopy (SEM) cross-sectional photographs of the films show smaller grain size and greater porosity with BZ addition. The remanent polarization (2Pr) was significantly reduced from ~16.4 µC/cm2 for SBT to ~2.3 µC/cm2 for SBT with 7% BZ. Capacitance–voltage measurements performed at a frequency of 1 MHz showed butterfly type hysteresis loops, which is further evidence of ferroelectricity of the modified SBT, and dielectric constant of 135 for SBT with 7% BZ. Leakage current measurements showed one order of magnitude higher leakage current for SBT with 5% BZ compared to SBT. Lower film dielectric constant leads to higher leakage current in BZ doped SBT. Although leakage mechanisms predict this general trend, it runs counter to the objective of preparing ferroelectric films with low leakage and low dielectric constants for ferroelectric gate field-effect transistor (FeFET) type memory.

Solvent-mediated purification of hexa-molybdenum cluster halide, Cs2[Mo6Cl14] for enhanced optical properties

The crystallization of a high-purity hexamolybdenum cluster chloride, Cs2[Mo6Cl14], was investigated with the aim of improving its intrinsic properties, including optical properties. In particular, we used the hydrophilicities of alcoholic solvents to purify Cs2[Mo6Cl14] by dehydration. The precursor, trigonal Cs2[Mo6Cl14] with water impurities, or monoclinic Cs2[Mo6Cl14]·H2O, was dispersed in methanol (MeOH), ethanol (EtOH), or 1-propanol (1-PrOH) to induce recrystallization during stirring. As a result, regardless of the precursor, Cs2[Mo6Cl14] crystallized from EtOH and 1-PrOH, while Cs2[Mo6Cl14]·H2O crystallized from MeOH, which indicates that EtOH and 1-PrOH behave as dehydrating agents during recrystallization. Subsequent characterization by X-ray diffraction, thermal desorption, and infrared spectroscopic techniques confirmed that the Cs2[Mo6Cl14] crystallized from EtOH or 1-PrOH, particularly 1-PrOH, is of high purity (fewer inserted water molecules) and high crystallinity. Improved luminescence efficiency following purification was evidenced by time-resolved photoluminescence measurements; the Cs2[Mo6Cl14] purified by dehydration on recrystallization clearly exhibited an increased luminescence lifetime.

Characterization of Low Temperature Chemical Vapor Deposited Gd2O3 Doped CeO2 Films

Highly oriented and polycrystalline Gd2O3 doped CeO2 thin films were prepared on α-Al2O3(0001) substrates by chemical vapor deposition, using Ce(C5H4C2H5)3 and Gd(C5H4C2H5)3 as precursors. The compositions of the films were controlled by optimizing the vaporization pressure of Gd precursor under the constant vaporization condition of Ce precursor. In-plane electrical conductivities of the films at various temperatures and oxygen partial pressures were evaluated by electrochemical impedance spectroscopy measurements. The activation energy of the film was determined as 0.94 eV, which is comparable with that of pulsed laser deposited films.

Ferroelectric Properties of Epitaxial BiFe0.97Mn0.03O3 Thin Films with Different Crystal Orientations Deposited on Buffered Si Substrates

We investigated electrical properties of epitaxial Mn doped bismuth ferrite BiFe0.97Mn0.03O3 (BFMO) thin films with different crystal orientations deposited on Si substrates with appropriate buffer layers. Epitaxial SrRuO3 (SRO) thin films with (001), (101), and (111) orientations were grown on CeO2/yttria-stabilized zirconia (YSZ)/Si(001) substrates and YSZ/Si(001), respectively, by the insertion of MgO and TiO2 atomic layers using pulsed-laser deposition (PLD). Using spin coating, we deposited BFMO thin films onto orientated SRO thin films. The BFMO orientation followed the SRO orientation. The Pr values of the BFMO were ordered as follows {111}>{110}>{100}, which is the same as that predicted by crystallographic considerations. The largest Pr value of the {111} orientation is 76 μC/cm2 at 100 kHz, 25°C.

Ferroelectricity of BiFeO3 Thin Films by Pulsed Laser Deposition and Effect of Atmosphere

In this study, BiFeO3 (BFO) epitaxial film was deposited on SrRuO3 (100)/SrTiO3 (100) substrates using pulsed laser deposition (PLD). Phase pure BFO thin film was obtained. Introducing a mask between the target and substrate in PLD improved the surface roughness from 47.8 nm (RMS, without mask) to 7.7 nm (RMS, with mask). The composition and electrical properties of BFO thin film were assessed after annealing for 1 h in Ar, N2, or O2 atmosphere at 600°C. The P-E hysteresis properties improved only in the O2 atmosphere. After annealing under O2 atmosphere, the leakage current decreased from 6.1 × 10-2 A/cm to 2.9 × 10-2 A/cm at 200 kV/cm, as in the other annealing atmospheres, but 2Pr increased from 35 BC/cm2 to 50 BC/cm2.