Determination of preferential molecular orientation in porphyrin-fullerene dyad ZnDHD6ee monolayers by the X-ray standing-wave method and X-ray reflectometry

Monolayers of porphyrin-fullerene dyad molecules with zinc atoms incorporated into the porphyrin ring (ZnDHD6ee) on the surface of aqueous subphase and on Si substrates have been investigated by the X-ray standing-wave method and X-ray reflectometry. The experiments have been performed under laboratory conditions and on synchrotron radiation sources (KMC-2 station of BESSY II (Berlin) and Langmuir station at the National Research Centre “Kurchatov Institute”). Depth distributions of Zn atoms and electron density in the monolayer film are calculated. On the basis of the analysis of these distributions, it is concluded that ZnDHD6ee dyad molecules in monolayers have preferential orientation. The data obtained indicate that the molecules in monolayer film retain their orientation when the monolayer is transferred from a liquid subphase surface onto a solid substrate.     

Study of the supramolecular structure formation of comb-like polyimide precursor Langmuir-Blodgett films

The Langmuir monolayers and Langmuir-Blodgett films of a comb-like polyimide prepolymer (the rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine) were studied. The supramolecular structures of the monolayers and Langmuir-Blodgett films of polyamic acid salts were characterized and a way for the surpamolecular structure to form was proposed based on an analysis of the surface pressure-area isotherms of monolayers on the water surface, investigations of the conditions of monolayer deposition onto solid substrates, and studies of the structures and surface morphology of Langmuir-Blodgett films.     

Formation of Langmuir-Blodgett films in solutions of comblike polymers

The structures have been analyzed of the monolayers of comblike precursor polymers of polyimides and mixed cellulose esters formed at the water/air interface and of the Langmuir-Blodgett films obtained by transfer of these condensed monolayers onto solid substrates. The important factors that ensure the structure control and supramolecular organization of these monolayers and films are established.     

Structure of porphyrin-fullerene dyad monolayer on the water surface and solid substrate

Monolayers of porphyrin-fullerene dyad TBD6a were formed on the surface of a water subphase and then transported on a solid substrate by the Langmuir-Schaefer method. A simulation was performed for the structure of a single molecule and for a molecular monolayer, according to the area per molecule in the monolayer formed, which was calculated based on an analysis of the π-A isotherm. A unit cell was chosen for the proposed molecular packing (a = 1.54 nm, b = 1.50 nm, c = 1.75 nm, α = 80.0°, β = 90.0°, and γ = 90.0°), and the atomic coordinates were calculated. A comparison of the interplanar spacings and diffraction peak intensities in the experimental and calculated (for the unit cell proposed) diffraction patterns indicates that a platelike texture is formed in the monolayer and that the crystal structure of the domains corresponds to the model chosen.     

Influence of ensembles of gold nanoparticles on the growth of ZnO on the sapphire (0001) surface

Gold is deposited on sapphire (0001) substrates by vacuum sputtering to form an ensemble of nanoparticles on the surface. Then the substrates are transferred to a magnetron sputtering chamber to be heated to 650°C and coated by a ZnO layer. The resulting layers are investigated by scanning electron microscopy, atomic force microscopy, electron diffraction, and photoluminescence. It is established that the Au sublayer ensures a higher quality of the ZnO structure and enhances photoluminescence. The differences in the morphology of ZnO structures is explained by the Au aggregation during substrate heating before ZnO deposition.     

Growth of nanofibrous barium carbonate on calcium carbonate seeds

Fibrous barium carbonate (BaCO₃/witherite) crystals 50–100 nm in diameter and several microns in length were grown on calcium carbonate (CaCO₃) seeds at temperatures as low as 4 °C. The BaCO₃ fibers were deposited onto calcite rhombs or CaCO₃ films using the polymer-induced liquid-precursor (PILP) process, which was induced with the sodium salt of polyacrylic acid (PAA). The structure and morphology of the resultant fibers were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and polarized light microscopy (PLM). Fibers were successfully grown on calcite seeds of various morphologies, with a range of barium concentrations, and PAA molecular weight and concentration. Two categories of fibers were grown: straight and twisted. Both types of fibers displayed single-crystalline SAED diffraction patterns, but after examining high-resolution TEM lattice images, it was revealed that the fibers were in fact made up of nanocrystalline domains. We postulate that these nanocrystalline domains are well aligned due to a singular nucleation event (i.e., each fiber propagates from a single nucleation event on the seed crystal) with the nanocrystalline domains resulting from stresses caused by dehydration during crystallization of the highly hydrated precursor phase. These BaCO₃ fibers grown on calcite substrates further illustrate the robustness and non-specificity of the PILP process.     

GaSb薄膜生长的RHEED研究

采用分子束外延技术,在GaAs衬底上生长GaSb薄膜时,利用反射式高能电子衍射仪(RHEED)对衬底表面清洁状况、外延层厚度等进行在线监控.通过RHEED讨论低温缓冲层对GaSb薄膜表面结构和生长机制的作用,可以估算衬底温度,并能计算出薄膜的生长速率.实验测量GaSb的生长周期为1.96s,每秒沉积0.51单分子层.低温缓冲层提高了在GaAs衬底上外延GaSb薄膜的生长质量.     

Precise thickness measurement within a few monolayers by X-ray diffraction from InGaAs/GaAs strained-layer superlattices

We propose a technique to measure the thickness of a GaAs layer with a precision of a few monolayers (MLs) by high-resolution X-ray diffraction (HRXRD) from InGaAs/GaAs strained-layer superlattices (SLSs) on GaAs substrates. Using this technique to monitor the GaAs growth rate, we have successfully controlled the Ga beam flux within ±1% in molecular beam epitaxy (MBE) growth for continuous 40 runs during four days by increasing the Ga cell temperature to compensate the decrease of the Ga beam flux caused by the consumption of the Ga source. Precise thickness measurements are also demonstrated in the growth on InP substrates by using InAlGaAs/InGaAs SLSs and InAlGaAs/InAlAs SLSs.     

Planned Multilayer Assemblies by Adsorption

Adsorption at liquid solid interfaces is employed to construct organized multilayer structures on polar solid substrates. We have recently demonstrated that oriented compact monolayers of good quality can be obtained under suitable conditions either by physisorption or by chemisorption, using either pure compounds as adsorbates or mixtures of several components, and even using mixtures of both physisorbed and chemisorbed species.¹ Monolayer formation by adsorption offers certain important advantages as compared with the Lanmuir-Blodgett method; adsorption is a spontaneous process leading to thermodynamically equilibrated film structures, there is no mechanical manipulation of the films, water is not indispensable for monolayer formation, monolayer composition and structure are usually dependent on the chemical nature and microscopic organization of the solid surface, covalent binding to the substrate and intralayer polymerization may take place simultaneously with the monolayer formation process, there are no restrictions regarding the macroscopic shape and size of the substrate. However, the adsorption method has been so far shown to be suitable only for formation of single mono-layers,¹ which limited severely its usefulness in the construction of multilayer assemblies.     

Correlation of ordering formation and surface structure in (GaIn)P using modulated MOVPE

Modulated metalorganic vapour phase epitaxial growth (MOVPE) is used to clarify the role of the surface conditions on the ordering behaviour in ternary (GaIn)P layers. The alternating deposition of GaP and InP layers with individual thicknesses of up to one monolayer is successfully used for the growth of (GaIn)P bulk layers lattice matched to (100) GaAs substrates with various off-orientations. The layer quality and the degree of ordering are investigated using high-resolution X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL), respectively. The application of modulated growth conditions for the deposition of (GaIn)P bulk layers has a strong influence on the degree of ordering achieved in the intermediate growth temperature regime where the highest degree of ordering occurs under continuous MOVPE. Beside a new boundary structure observed in layers grown under modulated flux conditions, the successful growth of highly ordered (GaIn)P layers grown using the modulated MOVPE technique support the model that up to 2 monolayers of the (GaIn)P growth surface are involved in the ordering formation process.     

Effects of alloy composition on the As desorption from and adsorption on strained InxGa1−xAs surfaces

The specular reflectivity of strained In_xGa_1−xAs surfaces grown by molecular beam epitaxy on InAs (100) substrates is measured with reflection high-energy electron diffraction (RHEED). A discontinuous change in the surface reflectivity is observed as the substrate temperature is increased above the transition point where As desorbs from the surface. A clear hysteresis loop is revealed as the substrate temperature is decreased. The substrate temperature required for desorption of surface As increases with Ga composition. A comparison between experimental results and theoretical calculations based on a Monte Carlo simulation shows that the average vertical interaction is increasing with Ga fraction. Fluctuations in alloy composition across the surface result in In-rich domains from which As is preferentially desorbed. The sudden loss of As, corresponding to a first order phase transition, occurs when the As desorbed domains attain a critical size. The metastability of the phase transition is shown to be a minimum for In_0.5Ga_0.5As layers.     

Transmission electron microscopic evaluation of InGaAs/InAlAs in-plane superlattices grown on slightly misoriented (110)InP substrates by molecular beam epitaxy

InGaAs/InAlAs in-plane superlattices (IPSLs) consisting of InAs/GaAs and InAs/AlAs monolayer superlattices grown on slightly misoriented (110)InP substrates by molecular beam epitaxy have been structurally evaluated by transmission electron microscopy. We used (110)InP 3° tilted toward the [00 ] direction. The ISPLs were fabricated by an alternative growth of half monolayers of AlAs and GaAs and one monolayer of InAs while maintaining regular arrays of one monolayer steps on the growth surface. In electron diffraction patterns from the ( 10) cross-section, two types of superstructure spots double-positioned in the 001 direction are observed, consistent with the existence of the IPSLs. Dark-field imaging from the superstructure spots reveal a periodic diffraction contrast with an average lateral periodicity of about 4 nm, i.e., one terrace width. However, meandering of the vertical interface and partial disordering in the IPSLs are often observed. From high resolution ( 10) cross-sectional TEM images, the presence of IPSLs was also confirmed with an atomic scale resolution, although their vertical interface are meandering. In electron diffraction patterns from the (110) plan-view, extra-spots similar to those observed in the ( 10) cross-section were seen. Dark-field images from the superstructure spots indicated that the IPSLs were formed almost exactly along the 110 direction, suggesting that the steps on the growth surface are very straight along the 110 direction.     

Two-dimensional crystallization of proteins on lipid monolayers at the air–water interface and transfer to an electron microscopy grid

The two-dimensional (2-D) crystallization of proteins on lipid monolayers at the air–water interface is a well established method for crystallizing soluble proteins. The transfer of 2-D crystals from the air–water interface to an electron microscopy (EM) grid constitutes a critical and ill-controlled step in the whole procedure, which is likely to be responsible for the high variability of results obtained with this method. In this paper, we address the following questions: (1) does the material observed on EM grids constitute a true representation of the material present at the air–water interface? (2) is there an optimal method of transfer to obtain well-ordered protein 2-D crystals? To answer these questions, we combine data obtained on three different protein systems, annexin V, streptavidin and cholera toxin, using two types of EM grids, coated with either holey carbon films or continuous carbon films. These combined observations help us draw a coherent picture of the state of the interfacial films at the air–water surface and provide new insight into the perturbing influence of the transfer step. The main conclusions are: (1) both annexin V and streptavidin form crystalline monolayers at the air–water interface, which are well preserved when transfer is performed by means of holey carbon films; (2) a major reorganization of the material present at the water surface accompanies transfer with continuous carbon films; the basal monolayer is extensively damaged, transforming into domains and vesicular structures, which do not pre-exist at the water surface; with the three protein systems studied here, these domains are often crystalline; (3) the most striking structural reorganization induced by transfer with continuous carbon films is observed with annexin V, for which the native p6 crystalline assembly is transformed into another crystal form more ordered, with p3 symmetry. It is most probable that these conclusions also apply to other protein 2-D crystals formed by the lipid monolayer method. The recent in situ observation of 2-D crystals of annexin V formed on solid-supported bilayers, by atomic force microscopy, supports our interpretation that monolayers transferred with holey carbon films represent the genuine material pre-exisiting at the air–water interface.     

Growth Mechanism in Atomic Layer Epitaxy (II). A Model of the Growth Process of CdTe on CdTe (111) Substrates

A realistic model of CdTe growth by atomic layer epitaxy (ALE) has been proposed. This model is based on experimental studies concerning the isothermal re-evaporation rates of elemental Cd and Te deposits on the (lll)A and (lll)B surfaces of CdTe substrates, on a study of surface morphology and crystal structure of CdTe single crystal overlayers grown by ALE on CdTe(lll)B substrates under various crystallization conditions as well as on the existing theories related to the interaction of thermally activated atoms or molecules with hot solid surfaces. This model includes: (i) an existence of transition layers of both Cd and Te₂ species, intermediate between a chemisorbed and a bulk-like film, which create reaction zones 3–4 monolayers thick near the substrate surface, and (ii) partial re-evaporation of the first, chemisorbed monolayer of the deposited constituent elements.     

Growth of vertical and defect free InP nanowires on SrTiO3(001) substrate and comparison with growth on silicon

We present a study of the molecular beam epitaxy of InP nanowires (NWs) on (001) oriented SrTiO₃ (STO) substrates using vapor liquid solid mechanism and gold–indium as metal catalyst. The growth direction of InP NWs grown on STO(001) is compared with NWs grown on (001) and (111) oriented silicon substrates. Gold–indium dewetting under a flux of indium results in the majority of InP NWs growing vertically from the surface of STO(001). With the growth parameters we have used the NWs have a pure wurtzite structure and are free of stacking faults and cubic segments. The structural quality of the NWs is confirmed by micro-photoluminescence measurements showing a narrow peak linewidth of 6.5 meV.     

X-ray diffraction study on amorphous gallium

Amorphous films of some μm in thickness, prepared by low temperature condensation in an ultra-high vacuum onto liquid helium cooled substrates, have been studied in situ by using an X-ray diffractometer operating in a symmetrical reflection mode. The structure factor of gallium has been obtained over the wavevector range 1.3 to 16.1 Å⁻ by means of two wavelengths, Cr_K and Mo_K, monochromatized by balanced filters. The average number of nearest neighbours deduced from the well-resolved first maximum in the radial distribution function is equal to 9.3 atoms. The results are compared to those previously found by electron diffraction measurements on thin films and also to the structure of supercooled liquid.     

Domain structure of Na1 − x LixNbO3 crystals

The domain structure of single-crystal and ceramic samples of Na_{1 ? x} Li_xNbO₃ solid solutions (at x ≤ 0.14) in the orthorhombic ferroelectric and antiferroelectric phases at room temperature is investigated by optical and electron microscopies and X-ray diffraction. The characteristic feature of the domain structure is the formation of 90° complexes consisting of laminar domains with a specific orientation relative to the lattice of the initial cubic phase. Consideration is given to the specific features in packing of these complexes and typical configurations of domains in the crystals. Observations revealed that the domain structure can involve 90°, 60°, 120°, and 180° boundaries, as well as (hhl) boundaries of the S type whose orientation depends on the cell distortion and changes with a variation in _x. The indices of these boundaries are determined. The density of 180° boundaries in the ferroelectric phase is very low compared to that of non-90° boundaries.     

X-ray diffraction study of fluorene, 9-fluorenone, and 9-dicyanomethylenefluorene derivatives

The results of a single-crystal X-ray diffraction analysis of fluorene, 9-fluorenone, and 9-dicyanomethylenefluorene derivatives as individual compounds, as well as their crystal solvates, molecular complexes, and charge-transfer complexes, are generalized. The most interesting features of the molecular geometry and conformation and the molecular packing in the crystals are discussed. The structural formula of 95 compounds and the R factors for X-ray diffraction analysis, which characterize the reliability of determining the structure, are summarized in three tables.     

3-叔丁基-1-(3-羟基苯基)脲的晶体结构及密度泛函理论研究

脲类及其衍生物在化学、农业、医学等多个领域有重要用途。而芳基脲类化合物是一类重要的医药化工中间体,本文经酰化和氧化两步反应制备3-叔丁基-1-(3-羟基苯基)脲,并于室温下经溶剂挥发法获得其单晶体,对晶体的堆积及分子间作用模式进行了分析。其结构经核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、核磁共振碳谱(¹³C NMR)、质谱MS和X射线单晶衍射等方法确证,在B3LYP/6-311+G(2d, p)模式下使用密度泛函理论(DFT)进行了最优结构以及前沿轨道能量计算,对比了晶体与理论计算的分子结构。结果表明,经DFT优化的分子结构与X-射线单晶衍射确定的晶体结构基本一致,该化合物为单斜方P2₁/n空间群,晶胞参数为a=1.181 42(6) nm,b=1.762 00(8) nm,c=1.179 02(5) nm,Z=8。     

3-Aryloxypropiononitriles Intermediates: Crystal and Molecular Structure of 2- and 4-(2-Bromoethoxy)diphenylmethanes

The crystal structure of 2- and 4-(2-bromoethoxy)diphenylmethanes ( I and II respectively), intermediates in a novel synthesis of substituted 3-aryloxypropiononitriles, have been determined by single crystal X-ray diffraction at room temperature (r.t.) and at 150K. No significant changes in the crystal structure of I and II have been observed in going from r.t. to 150K. In both compounds the bromoethoxy group presents a gauche conformation and shows a short Br.O intramolecular interaction that allows to explain the very good reaction yields obtained in the novel synthesis. The three-dimensional structure of I is stabilized by two intermolecular hydrogen bonds and that of II by six. This difference in the crystal packing of I and II explains the variation in the m.p. The analysis of ¹H and ¹³C NMR spectra suggests that the molecular conformations in solution are similar to those found in solid state.