High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope.
ABSTRACT: Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.
Project description:Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g).
Project description:The time-resolved photoconductance of amorphous and crystalline LaAlO3/SrTiO3 interfaces, both hosting an interfacial 2-dimensional electron gas, is investigated under irradiation by variable-wavelengths, visible or ultraviolet photons. Unlike bare SrTiO3 single crystals, showing relatively small photoconductance effects, both kinds of interfaces exhibit an intense and highly persistent photoconductance with extraordinarily long characteristic times. The temporal behaviour of the extra photoinduced conductance persisting after light irradiation shows a complex dependence on interface type (whether amorphous or crystalline), sample history and irradiation wavelength. The experimental results indicate that different mechanisms of photoexcitation are responsible for the photoconductance of crystalline and amorphous LaAlO3/SrTiO3 interfaces under visible light. We propose that the response of crystalline samples is mainly due to the promotion of electrons from the valence bands of both SrTiO3 and LaAlO3. This second channel is less relevant in amorphous LaAlO3/SrTiO3, where the higher density of point defects plays instead a major role.
Project description:A modern trend in traumatology, orthopedics, and implantology is the development of materials and coatings with an amorphous-crystalline structure that exhibits excellent biocopatibility. The structure and physico-chemical and biological properties of calcium phosphate (CaP) coatings deposited on Ti plates using the micro-arc oxidation (MAO) method under different voltages (200, 250, and 300 V) were studied. Amorphous, nanocrystalline, and microcrystalline statesof CaHPO<sub>4</sub> and β-Ca<sub>2</sub>P<sub>2</sub>O<sub>7</sub> were observed in the coatings using TEM and XRD. The increase in MAO voltage resulted in augmentation of the surface roughness <i>R</i><sub>a</sub> from 2.5 to 6.5 µm, mass from 10 to 25 mg, thickness from 50 to 105 µm, and Ca/P ratio from 0.3 to 0.6. The electrical potential (EP) of the CaP coatings changed from -456 to -535 mV, while the zeta potential (ZP) decreased from -53 to -40 mV following an increase in the values of the MAO voltage. Numerous correlations of physical and chemical indices of CaP coatings were estimated. A decrease in the ZP magnitudes of CaP coatings deposited at 200-250 V was strongly associated with elevated <i>hTERT</i> expression in tumor-derived Jurkat T cells preliminarily activated with anti-CD2/CD3/CD28 antibodies and then contacted in vitro with CaP-coated samples for 14 days. In turn, in vitro survival of CD4<sup>+</sup> subsets was enhanced, with proinflammatory cytokine secretion of activated Jurkat T cells. Thus, the applied MAO voltage allowed the regulation of the physicochemical properties of amorphous-crystalline CaP-coatings on Ti substrates to a certain extent. This method may be used as a technological mechanism to trigger the behavior of cells through contact with micro-arc CaP coatings. The possible role of negative ZP and Ca<sup>2</sup><sup>+</sup> as effectors of the biological effects of amorphous-crystalline CaP coatings is discussed. Micro-arc CaP coatings should be carefully tested to determine their suitability for use in patients with chronic lymphoid malignancies.
Project description:Calcium phosphate (CaP) is the principal inorganic constituent of bone and teeth in vertebrates and has various applications in biomedical areas. Among various types of CaPs, amorphous calcium phosphate (ACP) is considered to have superior bioactivity and biodegradability. With regard to the instability of ACP, the phosphorus-containing molecules are usually adopted to solve this issue, but the specific roles of the molecules in the formation of nano-sized CaP have not been clearly clarified yet. Herein, alendronate, cyclophosphamide, zoledronate, and foscarnet are selected as the model molecules, and theoretical calculations were performed to elucidate the interaction between calcium ions and different model molecules. Subsequently, CaPs were prepared with the addition of the phosphorus-containing molecules. It is found that cyclophosphamide has limited influence on the generation of CaPs due to their weak interaction. During the co-precipitation process of Ca<sup>2+</sup> and PO<sub>4</sub> <sup>3-</sup>, the competitive relation among alendronate, zoledronate, and foscarnet plays critical roles in the produced inorganic-organic complex. Moreover, the biocompatibility of CaPs was also systematically evaluated. The DFT calculation provides a convincing strategy for predicting the structure of CaPs with various additives. This work is promising for designing CaP-based multifunctional drug delivery systems and tissue engineering materials.
Project description:While numerous studies have been carried out to characterize heat transport behaviours in various crystalline silicon nanostructures, the corresponding characteristics of amorphous one-dimension system have not been well understood. In this study, we amorphize crystalline silicon by means of helium-ion irradiation, enabling the formation of a completely amorphous region of well-defined length along a single silicon nanowire. Heat conduction across both amorphous region and its crystalline/amorphous interface is characterized by an electron beam heating technique with high measurement spatial resolution. The measured thermal conductivity of the amorphous silicon nanowire appears length-independence with length ranging from ~30?nm to few hundreds nm, revealing the fully diffusons governed heat conduction. Moreover, unlike the size-dependent interfacial thermal conductance at the interface between two one-dimensional crystalline materials, here for the first time, we observe that the interface thermal conductance across the amorphous/crystalline silicon interface is nearly independent of the length of the amorphous region. This unusual independence is further supported by molecular dynamics (MD) simulation in our work. Our results provide experimental and theoretical insight into the nature of interaction between heat carriers in crystalline and amorphous nano-structures and shed new light to design innovative silicon nanowire based devices.
Project description:The integration of III-V semiconductors with silicon is a key issue for photonics, microelectronics and photovoltaics. With the standard approach, namely the epitaxial growth of III-V on silicon, thick and complex buffer layers are required to limit the crystalline defects caused by the interface polarity issues, the thermal expansion, and lattice mismatches. To overcome these problems, we have developed a reverse and innovative approach to combine III-V and silicon: the straightforward epitaxial growth of silicon on GaAs at low temperature by plasma enhanced CVD (PECVD). Indeed we show that both GaAs surface cleaning by SiF4 plasma and subsequent epitaxial growth from SiH4/H2 precursors can be achieved at 175 °C. The GaAs native oxide etching is monitored with in-situ spectroscopic ellipsometry and Raman spectroscopy is used to assess the epitaxial silicon quality. We found that SiH4 dilution in hydrogen during deposition controls the layer structure: the epitaxial growth happens for deposition conditions at the transition between the microcrystalline and amorphous growth regimes. SIMS and STEM-HAADF bring evidences for the interface chemical sharpness. Together, TEM and XRD analysis demonstrate that PECVD enables the growth of high quality relaxed single crystal silicon on GaAs.
Project description:We investigated the effect of film thickness (geometrical confinement) on the structural evolution of sputtered indium-zinc-tin oxide (IZTO) films as high mobility n-channel semiconducting layers during post-treatment at different annealing temperatures ranging from 350 to 700 °C. Different thicknesses result in IZTO films containing versatile phases, such as amorphous, low-, and high-crystalline structures even after annealing at 700 °C. A 19-nm-thick IZTO film clearly showed a phase transformation from initially amorphous to polycrystalline bixbyite structures, while the ultra-thin film (5 nm) still maintained an amorphous phase. Transistors including amorphous and low crystalline IZTO films fabricated at 350 and 700 °C show reasonable carrier mobility (µ<sub>FE</sub>) and on/off current ratio (I<sub>ON/OFF</sub>) values of 22.4-35.9 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> and 1.0-4.0?×?10<sup>8</sup>, respectively. However, their device instabilities against positive/negative gate bias stresses (PBS/NBS) are unacceptable, originating from unsaturated bonding and disordered sites in the metal oxide films. In contrast, the 19-nm-thick annealed IZTO films included highly-crystalline, 2D spherulitic crystallites and fewer grain boundaries. These films show the highest µ<sub>FE</sub> value of 39.2 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> in the transistor as well as an excellent I<sub>ON/OFF</sub> value of 9.7?×?10<sup>8</sup>. Simultaneously, the PBS/NBS stability of the resulting transistor is significantly improved under the same stress condition. This promising superior performance is attributed to the crystallization-induced lattice ordering, as determined by highly-crystalline structures and the associated formation of discrete donor levels (~?0.31 eV) below the conduction band edge.
Project description:Phase-change materials are functionally important materials that can be thermally interconverted between metallic (crystalline) and semiconducting (amorphous) phases on a very short time scale. Although the interconversion appears to involve a change in local atomic coordination numbers, the electronic basis for this process is still unclear. Here, we demonstrate that in a nearly vacancy-free binary GeSb system where we can drive the phase change both thermally and, as we discover, by pressure, the transformation into the amorphous phase is electronic in origin. Correlations between conductivity, total system energy, and local atomic coordination revealed by experiments and long time ab initio simulations show that the structural reorganization into the amorphous state is driven by opening of an energy gap in the electronic density of states. The electronic driving force behind the phase change has the potential to change the interconversion paradigm in this material class.
Project description:The constantly growing need for advanced bone regeneration materials has motivated the development of calcium phosphates (CaPs) composites with a different metal or metal-oxide nanomaterials and their economical and environmentally friendly production. Here, two procedures for the synthesis of CaPs composites with TiO<sub>2</sub> nanoplates (TiNPl) and nanowires (TiNWs) were tested, with the immersion of TiO<sub>2</sub> nanomaterials (TiNMs) in corrected simulated body fluid (c-SBF) and precipitation of CaP in the presence of TiNMs. The materials obtained were analyzed by powder X-ray diffraction, spectroscopic and microscopic techniques, Brunauer-Emmett-Teller surface area analysis, thermogravimetric analysis, dynamic and electrophoretic light scattering, and their hemocompatibility and ability to induce reactive oxygen species were evaluated. After 28 days of immersion in c-SBF, no significant CaP coating was formed on TiNMs. However, the composites with calcium-deficient apatite (CaDHA) were obtained after one hour in the spontaneous precipitation system. In the absence of TiNMs, CaDHA was also formed, indicating that control of the CaP phase formed can be accomplished by fine-tuning conditions in the precipitation system. Although the morphology and size of crystalline domains of CaDHA obtained on the different nanomaterials differed, no significant difference was detected in their local structure. Composites showed low reactive oxygen species (ROS) production and did not induce hemolysis. The results obtained indicate that precipitation is a suitable and fast method for the preparation of CaPs/TiNMs nanocomposites which shows great potential for biomedical applications.
Project description:Owing to their combined open-framework structures and semiconducting properties, two-dimensional thio-stannates show great potential for catalytic and sensing applications. One such class of crystalline materials consists of porous polymeric [Sn<sub>3</sub>S<sub>7</sub> <sup>2-</sup>] <i><sub>n</sub></i> sheets with molecular cations embedded in-between. The compounds are denoted <i>R</i>-SnS-1, where <i>R</i> is the cation. Dependent on the cation, some <i>R</i>-SnS-1 thio-stannates transition into amorphous phases upon dispersion in water. Knowledge about the fundamental chemical properties of the thio-stannates, including their water stability and the nature of the amorphous products, has not yet been established. This paper presents a time-resolved study of the transition from the crystalline to the amorphous phase of two violet-light absorbing thio-stannates, <i>i.e.</i> AEPz-SnS-1 [AEPz = 1-(2-amino-ethyl)-piperazine] and trenH-SnS-1 [tren = tris-(2-amino-ethyl)-amine]. X-ray total scattering data and pair distribution function analysis reveal no change in the local intralayer coordination during the amorphization. However, a rapid decrease in the crystalline domain sizes upon suspension in water is demonstrated. Although scanning electron microscopy shows no significant decrease of the micrometre-sized particles, transmission electron microscopy reveals the formation of small particles (?200-400?nm) in addition to the larger particles. The amorphization is associated with disorder of the thio-stannate nanosheet stacking. For example, an average decrease in the interlayer distance (from 19.0 to 15.6?Å) is connected to the substantial loss of the organic components as shown by elemental analysis and X-ray photoelectron spectroscopy. Despite the structural changes, the light absorption properties of the amorphisized <i>R</i>-SnS-1 compounds remain intact, which is encouraging for future water-based applications of such materials.