Pyroelectricity of water ice

Water ice usually is thought to have zero pyroelectricity by symmetry. However, biasing it with ions breaks the symmetry because of the induced partial dipole alignment. This unmasks a large pyroelectricity. Ions were soft-landed upon 1 mum films of water ice at temperatures greater than 160 K. When cooled below 140-150 K, the dipole alignment locks in. Work function measurements of these films then show high and reversible pyroelectric activity from 30 to 150 K. For an initial approximately 10 V induced by the deposited ions at 160 K, the observed bias below 150 K varies approximately as 10 Vx(T/150 K)2. This implies that water has pyroelectric coefficients as large as that of many commercial pyroelectrics, such as lead zirconate titanate (PZT). The pyroelectricity of water ice, not previously reported, is in reasonable agreement with that predicted using harmonic analysis of a model system of SPC ice. The pyroelectricity is observed in crystalline and compact amorphous ice, deuterated or not. This implies that for water ice between 0 and 150 K (such as astrophysical ices), temperature changes can induce strong electric fields (approximately 10 MV/m) that can influence their chemistry, ion trajectories, or binding.     

A new form of spontaneously polarized material

We report here the discovery of a new form of spontaneously polarized material. Examples of this material, in the form of films, demonstrate the property that they spontaneously harbour electric fields which may exceed 10(8) Vm(-1), achieving potentials of tens of volts on the film surface. The molecules presently identified form a diverse group, thus far of six species, with gas phase dipoles lying between 0.08 D and 0.5 D: propane (0.08 D), isopentane (0.13 D), nitrous oxide (0.167 D), isoprene (0.25 D), toluene (0.385 D) and CF(3)Cl (Freon-13; 0.5 D). Here we concentrate on an understanding of the nature of the interactions which give rise to the spontaneously polarized state, using the measured temperature dependence of the electric field in N(2)O as a diagnostic. We show that the polarized state can arise through a mechanism of non-linear dipole alignment in a single domain in which dipole alignment generates the electric field within the film and the field generates dipole alignment. Non-local interactions take place over the dimension of the thickness of the film and permeate the entire medium through the agency of the electric field. This new type of material may have wide ranging applications in devices and in nanotechnology.     

Dielectrophoresis of cellulose nanocrystals and alignment in ultrathin films by electric field-assisted shear assembly

Ultrathin films of cellulose nanocrystals (CNCs) are obtained by using a convective assembly setup coupled with a low-strength external AC electric field. The orientation and degree of alignment of the rod-like nanoparticles are controlled by the applied field strength and frequency used during film formation. Calculated dipole moments and Clausius-Mossotti factors allowed the determination of the critical frequencies, the peak dielectrophoresis as well as the principal orientation of the CNCs in the ultrathin films. As a result of the combination of shear forces and low electric field highly ultrathin films with controlled, unprecedented CNC alignment are achieved.     

Electro-nanopatterning of surface relief gratings on azobenzene layer-by-layer ultrathin films by current-sensing atomic force microscopy

The electro-nanopatterning and mechanism of pattern formation in azobenzene-containing layer-by-layer (LbL) ultrathin films is described using surface probe microscopy techniques. First, arrays of nanodots were patterned on these films to investigate applied time at constant voltage bias dependence in electro-nanopatterning. The anisotropic mass transport and polar alignment of the azobenzene-containing films were observed after applying the electric field and heating the sample locally with the cantilever tip. On the basis of this novel phenomenon, small-sized surface relief gratings (SRG)s and their alignment were fabricated and observed by current-sensing atomic force microscopy. The rate of mass transport for the polymer is mainly controlled by the applied time at constant voltage bias between the cantilever and the electrode/substrate.     

Synchrotron FTIR spectroscopy of weak torsional bands: A case study of cis-methyl formate

The far infrared spectrum of cis-methyl formate has been recorded on the AILES beamline of the synchrotron SOLEIL using a Fourier transform infrared spectrometer coupled to a long path cell. The very weak fundamental band associated with the methyl-top torsion mode (ν(18)) was observed. The frequency analysis was performed using the "rho axis method", and the microwave and millimeter-wave data from the literature. A precise determination of the band origins (ν(18) (A) = 132.4303 cm(-1) and ν(18) (E) = 131.8445 cm(-1)) and of the barrier height [V(3) = 370.7398 (58) cm(-1)] have been obtained. The intensity of the ν(18) fundamental band was determined to be 3.4 × 10(-21) cm(-1)∕(molecule cm(-2)) at 297 K, equally shared among A-A and E-E transitions, thus leading to a dipole moment component μ(c) ((3)) equal to 0.0483 D. The results were compared with the ab initio calcula-tions of Senent et al. [Astrophys. J. 627, 567 (2005)].     

Novel alignment mechanism of liquid crystal on a hydrogenated amorphous silicon oxide

The mechanism of liquid crystal (LC) alignment has been investigated during the last few decades for inorganic materials as well as for organic materials; however, it has not been clearly confirmed for some alignment materials. Inorganic alignment materials such as amorphous silicon oxide (a-SiOx) and hydrogenated amorphous silicon oxide (a-SiOx:H) are deposited on indium tin oxide (ITO) films on glass by reactive sputtering deposition. After deposition, the inorganic alignment materials are irradiated using an Ar+ ion beam (IB) for LC alignment. On the basis of the experimental results, a-SiOx films deposited by the sputtering do not align the LC, but a-SiOx:H films treated with varying IB energies, IB incident angles, IB doses, and IB irradiation times have excellent alignment properties and electrooptical properties, identical to those of polyimide (PI). These results imply that inorganic alignment layers irradiated by IB can be adopted as an LC alignment layer instead of rubbed PI. Additionally, hydrogen plays an important role in LC alignment because of the difference in alignment properties between a-SiOx films and a-SiOx:H films. We investigate the mechanism of IB-treated inorganic alignment layers and suggest that LCs are aligned by chemical effects, such as van der Waals interaction, more than by physical effects, such as morphology effects, in the inorganic alignment layer irradiated by IB.     

Synthesis and characterization of volatile,fluorine-free beta-ketoiminate lanthanide MOCVD precursors and their implementation in low-temperature growth of epitaxial CeO(2) buffer layers for superconducting electronics

A new class of volatile, low-melting, fluorine-free lanthanide metal-organic chemical vapor deposition (MOCVD) precursors has been developed. The neutral, monomeric Ce, Nd, Gd, and Er complexes are coordinatively saturated by a versatile, multidentate ether-functionalized beta-ketoiminato ligand series, the melting point and volatility characteristics of which can be tuned by altering the alkyl substituents on the keto, imino, and ether sites of the ligand. Direct comparison with conventional lanthanide beta-diketonate complexes reveals that the present precursor class is a superior choice for lanthanide oxide MOCVD. Epitaxial CeO(2) buffer layer films can be grown on (001) YSZ substrates by MOCVD at significantly lower temperatures (450-650 degrees C) than previously possible by using one of the newly developed cerium beta-ketoiminate precursors. Films deposited at 540 degrees C have good out-of-plane (Deltaomega = 0.85 degrees ) and in-plane (Deltaphi = 1.65 degrees ) alignment and smooth surfaces (rms roughness approximately 4.3 A). The film growth rate decreases and the films tend to be smoother as the deposition temperature is increased. High-quality yttrium barium copper oxide (YBCO) films grown on these CeO(2) buffer layers by pulsed organometallic molecular beam epitaxy exhibit very good electrical transport properties (T(c) = 86.5 K, J(c) = 1.08 x 10(6) A/cm(2) at 77.4 K).     

Spatial Taming and Trapping of Molecules

Molecular beam techniques for study of collisional and spectroscopic processes have recently been enhanced by use of static electric or magnetic fields to orient or align molecules with permanent dipole moments. A more general method is now in prospect, applicable both to alignment and to spatial trapping of molecules. This exploits the anisotropic interaction of the electric field vector of intense laser radiation with the dipole moment induced in a polarizable molecule by the laser field. The interaction creates directional superpositions of field-free states that correspond to oblate spheroidal wavefunctions, with eigenenergies that decrease with increasing field strength. We suggest that this polarizability interaction produces the marked alignment found in laser-induced dissociative ionization of CO by the Saclay group. We also present calculations illustrating the feasibility of spattal trapping. In combination with supermirror focussing and buffer-gas cooling, an intense infrared laser can typically confine molecules for long-times (-hours) within a small (-picoliter) and cold (?1°K) “pocket of light.”     

A bilayer model of the double hysteresis loop in antiferroelectric liquid crystals

We investigate, both analytically and numerically, a simple model of the field induced double hysteresis loop in AFLC materials. This bilayer model of the bulk of an AFLC describes the free energy in terms of polar and non-polar interactions due to surface alignment, the electric field/dipole interaction in each layer and the dipole/dipole interaction between the layers. The static hysteresis loop is found analytically and the stability of each analytic solution is investigated. The dynamic switching characteristics are found numerically and then investigated as the system parameters and electric field characteristics are changed.     

含对硝基偶氮苯胺生色团的键合型有机/无机复合材料的合成及其二阶非线性光学特性

以γ 缩水甘油氧丙基三甲氧基硅烷 (KH5 6 0 )作中间体 ,用溶胶 凝胶 (Sol Gel)法合成了含对硝基偶氮苯胺 (DO3)生色团的新型键合型有机 /无机复合非线性光学 (NLO)材料 ,在这种有机生色团与无机玻璃键合形成的交联网络结构中 ,无机玻璃的刚性三维结构和优良的高温稳定性能有效抑制NLO生色团的极化松弛 .二次谐波信号 (SHG)测量表明 ,合成的键合型聚合物膜的二阶非线性光学系数 (d33)值达 5 79× 10 -7esu ,NLO稳定性也较好 ;在室温下放置 90天后 ,其d33 值能维持初始值的 93 5 % ;在 10 0℃下放置 30 0min后 ,其d33 值仍能维持初始值的 6 0 %     

Thermally induced polarizabilities and dipole moments of small tin clusters

We study the influence of thermal excitation on the electric susceptibilities for Sn(6) and Sn(7) clusters by molecular beam electric deflection and Monte-Carlo simulations in conjunction with quantum-chemical calculations. At low temperatures (40 K), no field-induced broadening of the Sn(6) and Sn(7) cluster beams are observed, in agreement with vanishing permanent electric dipole moments due to their centro-symmetrical ground states. The electric polarizabilities of Sn(6) and Sn(7), as inferred from the field-induced molecular beam deflection, are in good agreement with the quantum-chemical predictions. At elevated temperatures of 50-100 K, increased polarizabilities of about 2-3 ?(3) are obtained. Also, we found indications of a field-induced beam broadening which points to the existence of permanent dipole moments of about 0.01-0.02 D per atom at higher temperatures. These results cannot be explained by thermal excitations within a harmonic oscillator model, which would yield a temperature-independent polarizability and fluxional, but not permanent, dipole moments. We analyze this behavior by Monte-Carlo simulations in order to compute average temperature-induced electric dipole moments. For that purpose, we developed a novel technique for predicting observables sampled on the quantum-chemical potential energy surface by an umbrella sampling correction of Monte-Carlo results obtained from simulations utilizing an empirical potential. The calculated, fluxional dipole moments are in tune with the observed beam broadenings. The cluster dynamics underlying the polarizability appear to be intermediate between rigid and floppy molecules which leads to the conclusion that the rotational, not the vibrational temperature seems to be the key parameter that determines the temperature dependence of the polarizability.     

Domain manipulation of ferroelectric BaTiO3 thin films: application to the local reorientation of liquid crystal

A method is reported for local alignment of nematic liquid crystal (NLC) molecules. It consists in the poling of small areas of ferroelectric thin films using scanning probe microscopy. A liquid crystal deposited onto such a surface is aligned via a dipole-dipole interaction. The ferroelectric films are first characterized using X ray diffraction, atomic force microscopy and ellipsometry. The domain manipulation and local poling of the film are achieved and characterized using an electrostatic microscopy type set-up. A hybrid nematic liquid crystal cell (NLC-OFC: nematic liquid crystal - oxide ferroelectric cell) is then constructed and its alignment inspected using polarizing microscopy (in reflection mode). The reorientation is explained by invoking a simple interaction between the dipole moment of the LC and the surface electric field generated by the poled area. In addition, a complimentary experiment is performed to determine the depth to which the poled area affects the liquid crystal alignment. This consists of measuring the deflection of a collimated beam (optical soliton) propagating across the poled area.     

Alignment of liquid crystals on ultrathin organized molecular films

Liquid crystal (LC) alignment techniques based on various kinds of ultrathin organized molecular films are reviewed. The mechanisms of LC alignment on the organized films are discussed. For the homeotropic alignment of LCs the main anchoring mechanism is due to the dipole–dipole interaction between polar groups of an aligning agent and LC molecules while the homogeneous alignment is mainly attributed to the orientation of polymer chains or polymer aggregates. An experimental system for an anchoring transition induced by a conformation change of aligning molecules is introduced. Finally the AFM experimental observations on the rubbed polymer films and its mechanisms are summarized.     

Giant Hysteretic Single‐Molecule Electric Polarisation Switching above Room Temperature

Continual progress has been achieved in information technology through unrelenting miniaturisation of the single memory bit in integrated ferromagnetic, ferroelectric, optical, and related circuits. However, as miniaturisation approaches its theoretical limit, new memory materials are being sought. Herein, we report a unique material exhibiting single‐molecule electric polarisation switching that can operate above room temperature. The phenomenon occurs in a Preyssler‐type polyoxometalate (POM) cluster we call a single‐molecule electret (SME). It exhibits all the characteristics of ferroelectricity but without long‐range dipole ordering. The SME affords bi‐stability as a result of the two potential positions of localisation of a Tb³⁺ ion trapped in the POM, resulting in extremely slow relaxation of the polarisation and electric hysteresis with high spontaneous polarisation and coercive electric fields. Our findings suggest that SMEs can potentially be applied to ultrahigh‐density memory 1 and other molecular‐level electronic devices operating above room temperature. 2     

Directed electrodeposition of polymer films using spatially controllable electric field gradients

We report a method for the directed electrodeposition of polymer films in various patterns using spatially controllable electric field gradients. One- and two- dimensional surface electric field gradients were produced by applying different potential values at spatially distinct locations on an electrode surface. Variations in the resulting local electrochemical potentials were used to spatially manipulate the rate of electrodeposition of several polymers. By controlling the electric field gradient in the presence of sequentially varying deposition solutions, complex polymer patterns could be produced. One-dimensional structures consisting of alternating bands of polyaniline and either poly(phenylene) oxide or poly(aminophenylene) oxide were produced, as well as more complex two-dimensional structures. Film characterization was achieved through optical imaging, UV-vis spectroscopy, and ellipsometry. Results indicate that this directed deposition technique is a simple strategy to create complex, millimeter-sized surface patterns of electrodeposited materials.     

Crystallographic and morphological characterization of thin pentacene films on polycrystalline copper surfaces

The degree of crystallinity, the structure and orientation of crystallites, and the morphology of thin pentacene films grown by vapor deposition in an ultrahigh vacuum environment on polycrystalline copper substrates have been investigated by x-ray diffraction and tapping-mode scanning force microscopy (TM-SFM). Depending on the substrate temperature during deposition, very different results are obtained: While at 77 K a long-range order is missing, the films become crystalline at elevated temperatures. From a high-resolution x-ray-diffraction profile analysis, the volume-weighted size of the crystallites perpendicular to the film surface could be determined. This size of the crystallites increases strongly upon changing temperature between room temperature and 333 K, at which point the size of individual crystallites typically exceeds 100 nm. In this temperature region, three different polymorphs are identified. The vast majority of crystallites have a fiber texture with the (001) net planes parallel to the substrate. In this geometry, the molecules are oriented standing up on the substrate (end-on arrangement). This alignment is remarkably different from that on single-crystalline metal surfaces, indicating that the growth is not epitaxial. Additionally, TM-SFM images show needlelike structures which suggest the presence of at least one additional orientation of crystallites (flat-on or edge-on). These results indicate that properties of thin crystalline pentacene films prepared on technologically relevant polycrystalline metal substrates for fast electronic applications may be compromised by the simultaneous presence of different local molecular aggregation states at all temperatures.     

Nanocrystalline Diamond Thin Films Synthesis on Curved Surface

Thin films of curved surface nanocrystalline diamond (CS-NCD) are a category of important materials. However, the development of such materials is still a highly challenging task. Here we present a novel approach to synthesizing CS-NCD thin films deposited on non-spherical surfaces of molybdenum substrate using direct current plasma jet chemical vapor deposition. A special cooling system was designed and applied to ensure uniform substrate temperature. It is demonstrated from simulation and experimental results that this system is favorable for the production of thin films. The results show that the quality of CS-NCD thin films depends on the selection of optimal values of parameters including CH₄ concentration, substrate temperature, and chamber pressure. If the CH₄ concentration and/or the substrate temperature is too high or low, it results in non-diamond phase or micron-crystalline diamond thin films. Synthetic CS-NCD thin films using the proposed method have a smooth surface and uniform thickness. The average grain size and the mean surface roughness are approximately 30 and 4.3 nm respectively. Characteristics of CS-NCD thin film spectra comprised of the full width at half maximum with broad Raman peaks around 1,140 and 1,480 cm^?1, confirming the presence of the NCD phase.     

Mechanism of nematic molecular alignment based on friction charges and surface topology by rubbing

A new and simple electric charge interaction mechanism has been proposed to explain the behaviour of the tilt angle of liquid crystals by rubbing. The mechanism of the molecular alignment is elucidated based on the effect of a static electric charge on a substrate surface treated by rubbing. An electric field which is dependent on the topology of a substrate surface allows a planar orientation of molecules with positive dielectric anisotropy. With increasing rubbing strength, the tilt angle varies slowly. The director of molecules with negative dielectric anisotropy is uniform and has a tilt angle determined by the molecular permanent dipole direction. The air-liquid crystal interface case is also considered. This model enables us to give a unified picture of the molecular alignment mechanism.     

Trapping of DNA by dielectrophoresis

Under suitable conditions, a DNA molecule in solution will develop a strong electric dipole moment. This induced dipole allows the molecule to be manipulated with field gradients, in a phenomenon known as dielectrophoresis (DEP). Pure dielectrophoretic motion of DNA requires alternate current (AC) electric fields to suppress the electrophoretic effect of the molecules net charge. In this paper, we present two methods for measuring the efficiency of DEP for trapping DNA molecules as well as a set of quantitative measurements of the effects of strand length, buffer composition, and frequency of the applied electric field. A simple configuration of electrodes in combination with a microfluidic flow chamber is shown to increase the concentration of DNA in solution by at least 60-fold. These results should prove useful in designing practical microfluidic devices employing this phenomenon either for separation or concentration of DNA.     

Micro-thermal analysis of NiTi shape memory alloy thin films

A novel technique of micro-thermal analysis (micro-TA) has been used to investigate martensitic to austenitic transformations of near equi-atomic NiTi shape memory alloy (SMA) thin films deposited on silicon wafer by a plasma assisted sputter deposition technique. The results demonstrate that both power and sensor deflection signal of the technique, equivalent to micro-differential thermal analysis (μDTA) and micro-thermomechanical analysis (μTMA), respectively, have a capability of locally characterising transformation temperatures of the SMA films. The phase transition temperatures can be identified as an abrupt deviation of power and thermal expansion from linearity. The change in probe deflection reveals a sample contraction of 0.44% following the martensite to austenitic transformation. This dimension change is consistent with the difference in the unit cell volumes of the different phases. The individual films investigated here show a spatial variation on the micron-scale in the martensite to austenite transition temperatures as the surface is probed. A possible reason for this may lie in the inhomogeneous distribution of Ti and Ni in the film structure as the transition temperature is very sensitive to composition, showing typically a 100 K temperature change between 50 and 51 at.% Ni in Ti. Conventional bulk DSC experiments were carried out on the same materials and the results were compared with those from the micro-TA.