From Crystalline to Amorphous Germania Bilayer Films at the Atomic Scale: Preparation and Characterization

A new two‐dimensional (2D) germanium dioxide film has been prepared. The film consists of interconnected germania tetrahedral units forming a bilayer structure, weakly coupled to the supporting Pt(111) metal‐substrate. Density functional theory calculations predict a stable structure of 558‐membered rings for germania films, while for silica films 6‐membered rings are preferred. By varying the preparation conditions the degree of order in the germania films is tuned. Crystalline, intermediate ordered and purely amorphous film structures are resolved by analysing scanning tunnelling microscopy images.     

Crystalline ice growth on Pt(111) and Pd(111): nonwetting growth on a hydrophobic water monolayer

The growth of crystalline ice films on Pt(111) and Pd(111) is investigated using temperature programed desorption of the water films and of rare gases adsorbed on the water films. The water monolayer wets both Pt(111) and Pd(111) at all temperatures investigated [e.g., 20-155 K for Pt(111)]. However, crystalline ice films grown at higher temperatures (e.g., T>135 K) do not wet the monolayer. Similar results are obtained for crystalline ice films of D2O and H2O. Amorphous water films, which initially wet the surface, crystallize and dewet, exposing the water monolayer when they are annealed at higher temperatures. Thinner films crystallize and dewet at lower temperatures than thicker films. For samples sputtered with energetic Xe atoms to prepare ice crystallites surrounded by bare Pt(111), subsequent annealing of the films causes water molecules to diffuse off the ice crystallites to reform the water monolayer. A simple model suggests that, for crystalline films grown at high temperatures, the ice crystallites are initially widely separated with typical distances between crystallites of approximately 14 nm or more. The experimental results are consistent with recent theory and experiments suggesting that the molecules in the water monolayer form a surface with no dangling OH bonds or lone pair electrons, giving rise to a hydrophobic water monolayer on both Pt(111) and Pd(111).     

Layer-by-layer growth of thin amorphous solid water films on Pt(111) and Pd(111)

The growth of amorphous solid water (ASW) films on Pt(111) is investigated using rare gas (e.g., Kr) physisorption. Temperature programmed desorption of Kr is sensitive to the structure of thin water films and can be used to assess the growth modes of these films. At all temperatures that are experimentally accessible (20-155 K), the first layer of water wets Pt(111). Over a wide temperature range (20-120 K), ASW films wet the substrate and grow approximately layer by layer for at least the first three layers. In contrast to the ASW films, crystalline ice films do not wet the water monolayer on Pt(111). Virtually identical results were obtained for ASW films on epitaxial Pd(111) films grown on Pt(111). The desorption rates of thin ASW and crystalline ice films suggest that the relative free energies of the films are responsible for the different growth modes. However, at low temperatures, surface relaxation or "transient mobility" is primarily responsible for the relative smoothness of the films. A simple model of the surface relaxation semiquantitatively accounts for the observations.     

Thin silica films on Ru(0001): monolayer, bilayer and three-dimensional networks of [SiO4] tetrahedra

The atomic structure of thin silica films grown over a Ru(0001) substrate was studied by X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, low energy electron diffraction, helium ion scattering spectroscopy, CO temperature programmed desorption, and scanning tunneling microscopy in combination with density functional theory calculations. The films were prepared by Si vapor deposition and subsequent oxidation at high temperatures. The silica film first grows as a monolayer of corner-sharing [SiO(4)] tetrahedra strongly bonded to the Ru(0001) surface through the Si-O-Ru linkages. At increasing amounts of Si, the film forms a bilayer of corner-sharing [SiO(4)] tetrahedra which is weakly bonded to Ru(0001). The bilayer film can be grown in either the crystalline or vitreous state, or both coexisting. Further increasing the film thickness leads to the formation of vitreous silica exhibiting a three-dimensional network of [SiO(4)]. The principal structure of the films can be monitored by infrared spectroscopy, as each structure shows a characteristic vibrational band, i.e., ～1135 cm(-1) for a monolayer film, ～1300 cm(-1) for the bilayer structures, and ～1250 cm(-1) for the bulk-like vitreous silica.     

Coating process regimes in particulate film production by forced-convection-assisted drag-out

Operating conditions for the deposition of monolayer and bilayer particulate coatings from aqueous 20-nm-diameter silica dispersions are identified in the context of a drag-out operation assisted by forced convection. The dry film thickness, uniformity, and morphology are assessed within an operating window parametrized by the capillary number and silica dispersion weight fraction. Three film deposition regimes with respect to the capillary number are observed: convective film deposition at low process rates, film entrainment at moderate process rates, and a thin-film transition regime at intermediate process rates. Locally ordered particulate films of variable layering thickness, including (i) a discontinuous submonolayer or (ii) a mixed submonolayer and monolayer, (iii) a mixed monolayer and bilayer, and (iv) multilayers, are dominant under convective deposition conditions. A map of morphologies is presented within the capillary number-weight fraction operating window, where monolayer and mixed monolayer-bilayer films are demonstrated in the thin-film transition regime at an intermediate dispersion weight fraction. A complementary map of the morphologies formed by the drag-out of 110 nm silica dispersions reveals a broader applicability to this type of operability diagram. These operating maps are constructed using model silica dispersions and are therefore relevant to particulate coatings of other inorganic materials.     

Particle zips: vertical emulsion films with particle monolayers at their surfaces

Vertical emulsion films with particle monolayers at their surfaces have been studied by direct microscope observations. The effects of particle wettability and surface coverage on the structure and stability of water films in octane and octane films in water have been investigated. Monodisperse silica particles (3 microm in diameter) hydrophobized to different extents have been used. It is found that the structure and stability of emulsion films strongly depend on the film type (water-in-oil or oil-in-water), the particle contact angle, the interactions between particles from the same and the opposite monolayer, and the monolayer density. Stable films are observed only when the particle wettability fulfills the condition for stable particle bridges--in agreement with the concept that hydrophilic particles can give stable oil-in-water emulsions, whereas hydrophobic ones give water-in-oil emulsions. In the case of water films with dilute disordered monolayers at their surfaces, the hydrophilic particles are expelled from the film center toward its periphery, giving a dimple surrounded by a ring of particles bridging the film surfaces. In contrast, the thinning of octane films with dilute ordered monolayers at their surfaces finally leads to the spontaneous formation of a dense crystalline monolayer of hydrophobic particles bridging both surfaces at the center of the film. The behaviors of water and octane films with dense close-packed particle monolayers at their surfaces are very similar. In both cases, a transition from bilayer to bridging monolayer is observed at rather low capillary pressures. The implications of the above finding for particle stabilized emulsions are discussed.     

Fabrication of hollow and mesoporous germania microspheres by templating against plasma-treated polystyrene microspheres

The surfaces of monodisperse polystyrene (PS) colloids have been modified with hydroxyl groups by means of plasma treatment technique. By templating against these surface-modified PS colloids, the germania coating PS composite microspheres were prepared via a sol–gel process. After removal of PS cores, the resulting composite microspheres converted into hollow germania microspheres with mesoporous structure. The shell thickness of these hollow spheres can be controlled by varying the concentration of germania precursor. BET results indicated that the hollow germania microspheres shell exhibits slightly broader pore size distribution than that of corresponding composite one owing to the swelling effects of the PS core during the etching process. In addition, the as-prepared germania exhibits amorphous phase which can be converted into crystalline phase by calcination treatment. It is worthy to noting that this fabrication protocol demonstrated a facile, low-cost and environment-benign way for fabricating hollow germania structures by templating method. Moreover, this protocol is not limit to germania; it also could be used to create the other hollow inorganic oxides spheres.     

氧化锌有序结构在Au(111)和Cu(111)上的生长

利用NO₂或O₂作为氧化剂,研究了氧化锌在Au(111)和Cu(111)上的生长和结构。NO₂表现了更好的氧化性能,有利于有序氧化锌纳米结构或薄膜的生长。在Au(111)和Cu(111)这两个表面上,化学计量比氧化锌都形成非极性的平面化ZnO(0001)的表面结构。在Au(111)上,NO₂气氛下室温沉积锌倾向于形成双层氧化锌纳米结构;而在更高的沉积温度下,在NO₂气氛中沉积锌则可同时观测到单层和双层氧化锌纳米结构。O₂作为氧化剂时可导致形成亚化学计量比的ZnO_x结构。由于铜和锌之间的强相互作用会促进锌的体相扩散,并且铜表面可以被氧化形成表面氧化物,整层氧化锌在Cu(111)上的生长相当困难。我们通过使用NO₂作为氧化剂解决了这个问题,生长出了覆盖Cu(111)表面的满层有序氧化锌薄膜。这些有序氧化锌薄膜表面显示出莫尔条纹,表明存在一个ZnO和Cu(111)之间的莫尔超晶格。实验上观察到的超晶格结构与最近理论计算提出的Cu(111)上的氧化锌薄膜结构相符,具有最小应力。我们的研究表明,氧化锌薄膜的表界面结构可能会随氧化程度或氧化剂的不同而变化,而Cu(111)的表面氧化也可能影响氧化锌的生长。当Cu(111)表面被预氧化成铜表面氧化物时,ZnO_x的生长模式会发生变化,锌原子会受到铜氧化物晶格的限域形成单位点锌。我们的研究表明了氧化锌的生长需要抑制锌向金属基底的扩散,并阻止亚化学计量比ZnO_x的形成。因此,使用原子氧源有利于在Au(111)和Cu(111)表面上生长有序氧化锌薄膜。     

Surface structure and properties of poly-(ethylene terephthalate) hydrolyzed by alkali and cutinase

This study was aimed at comparatively investigating the hydrolysis of crystalline and amorphous poly-(ethylene terephthalate) films by alkali and cutinase. Changes of surface properties were investigated by FTIR spectroscopy (ATR mode). The A₁₃₄₁/A₁₄₁₀ and I₁₁₂₀/I₁₁₀₀ absorbance ratios, and the full width at half maximum of the carbonyl stretching band (FWHM₁₇₁₅) were used to evaluate the polymer crystallinity and its changes upon hydrolysis. The effect of different treatments on chain orientation was evaluated by calculating R ratios of appropriate bands. The spectroscopic indexes showed that both alkali and enzyme treatments induced structural and conformational rearrangements with a consequent increase in crystallinity in both amorphous and crystalline films. The crystalline PET film was modified more strongly by alkali than by cutinase, while the opposite occurred for the amorphous one. The trend of the water contact angle (WCA) clearly indicates that alkali is more effective than cutinase in enhancing hydrophilicity of PET films and that the effect is stronger on amorphous than on crystalline films. The values of WCA correlate well with the FTIR indexes calculated from the spectra of hydrolyzed crystalline PET films. The mechanism of the surface hydrolysis of PET by alkali and cutinase is discussed.     

Phase diagram of water between hydrophobic surfaces

Molecular dynamics simulations demonstrate that there are at least two classes of quasi-two-dimensional solid water into which liquid water confined between hydrophobic surfaces freezes spontaneously and whose hydrogen-bond networks are as fully connected as those of bulk ice. One of them is the monolayer ice and the other is the bilayer solid which takes either a crystalline or an amorphous form. Here we present the phase transformations among liquid, bilayer amorphous (or crystalline) ice, and monolayer ice phases at various thermodynamic conditions, then determine curves of melting, freezing, and solid-solid structural change on the isostress planes where temperature and intersurface distance are variable, and finally we propose a phase diagram of the confined water in the temperature-pressure-distance space.     

IR Spectroscopic Investigations of Gasochromic and Electrochromic Sol-Gel—Derived Peroxotungstic Acid/Ormosil Composite and Crystalline WO3 Films

We studied the gasochromic effect of amorphous peroxopolytungstic acid (W-PTA), W-PTA (ormosil) and crystalline WO₃ films. These latter films were prepared after a heat treatment of W-PTA/ormosil films at 450°C. The ormosil served as a template, providing the monoclinic WO₃ films with adequate porosity. The spill-over effect was attained by impregnating the porous WO₃ crystalline films with H₂PtCl₆ followed by a heat treatment at 380°C. The amorphous films became gasochromic with the addition of PdCl₂ to the corresponding W-PTA and W-PTA/ormosil sols.Structural features of all the films were studied with the help of infrared (IR) spectroscopy and transmission electron microscopy (TEM). In situ IR spectra of the films, performed in the presence of reducing (H₂/Ar) and oxidising (O₂/Ar) gases, revealed a reversible transformation of the monoclinic to the tetragonal H _x WO₃ phase. At the same time the coloration (reduction) of the amorphous films was accompanied by the formation of coordinated water molecules and increased numbers of W=O bonds. Gasochromic colouring/bleaching changes and the corresponding kinetics were assessed from in situ UV-visible transmission measurements on the films.     

The structure and crystallization of thin water films on Pt(111)

When water is adsorbed on Pt(111) above 135 K several different ice structures crystallize, depending on the thickness of the ice layer. At low coverage water forms extended islands of ice with a (square root(37) x square root(37))R25(o) unit cell, which compresses as the monolayer saturates to form a (square root(39) x square root(39))R16(o) structure. The square root(39) low-energy electron diffraction (LEED) pattern becomes more intense as the second layer grows, remaining bright for films up of 10-15 layers and then fading and disappearing for films more than ca. 40 layers thick. The ice multilayer consists of an ordered square root(39) wetting layer, on which ice grows as a crystalline film which progressively loses its registry to the wetting layer. Ice films more than ca. 50 layers thick develop a hexagonal LEED pattern, the entire film and wetting layer reorienting to form an incommensurate bulk ice. These changes are reflected in the vibrational spectra which show changes in line shape and intensity associated with the different ice structures. Thin amorphous solid water films crystallize to form the same phases observed during growth, implying that these structures are thermodynamically stable and not kinetic phases formed during growth. The change from a square root(39) registry to incommensurate bulk ice at ca. 50 layers is associated with a change in crystallization kinetics from nucleation at the Pt(111) interface in thin films to nucleation of incommensurate bulk ice in amorphous solid water films more than 50 layers thick.     

Reactions of NO2 with BaO/Pt(111) model catalysts: the effects of BaO film thickness and NO2 pressure on the formation of Ba(NOx)2 species

The adsorption and reaction of NO(2) on BaO (<1, ～3, and >20 monolayer equivalent (MLE))/Pt(111) model systems were studied with temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRAS) under ultra-high vacuum (UHV) as well as elevated pressure conditions. NO(2) reacts with sub-monolayer BaO (<1 MLE) to form nitrites only, whereas the reaction of NO(2) with BaO (～3 MLE)/Pt(111) produces mainly nitrites and a small amount of nitrates under UHV conditions (P(NO(2))≈ 1.0 × 10(-9) Torr) at 300 K. In contrast, a thick BaO (>20 MLE) layer on Pt(111) reacts with NO(2) to form nitrite-nitrate ion pairs under the same conditions. At elevated NO(2) pressures (≥1.0 × 10(-5) Torr), however, BaO layers at all these three coverages convert to amorphous barium nitrates at 300 K. Upon annealing to 500 K, these amorphous barium nitrate layers transform into crystalline phases. The thermal decomposition of the thus-formed Ba(NO(x))(2) species is also influenced by the coverage of BaO on the Pt(111) substrate: at low BaO coverages, these species decompose at significantly lower temperatures in comparison with those formed on thick BaO films due to the presence of a Ba(NO(x))(2)/Pt interface where the decomposition can proceed at lower temperatures. However, the thermal decomposition of the thick Ba(NO(3))(2) films follows that of bulk nitrates. Results obtained from these BaO/Pt(111) model systems under UHV and elevated pressure conditions clearly demonstrate that both the BaO film thickness and the applied NO(2) pressure are critical in the Ba(NO(x))(2) formation and subsequent thermal decomposition processes.     

Photoluminescence properties of BaMoO4 amorphous thin films

BaMoO₄ amorphous and crystalline thin films were prepared from polymeric precursors. The BaMoO₄ was deposited onto Si wafers by means of the spinning technique. The structure and optical properties of the resulting films were characterized by FTIR reflectance spectra, X-ray diffraction (XRD), atomic force microscopy (AFM) and optical reflectance. The bond Mo-O present in BaMoO₄ was confirmed by FTIR reflectance spectra. XRD characterization showed that thin films heat-treated at 600 and 200 °C presented the scheelite-type crystalline phase and amorphous, respectively. AFM analyses showed a considerable variation in surface morphology by comparing samples heat-treated at 200 and 600 °C. The reflectivity spectra showed two bands, positioned at 3.38 and 4.37 eV that were attributed to the excitonic state of Ba²⁺ and electronic transitions within MoO²⁻₄, respectively. The optical band gaps of BaMoO₄ were 3.38 and 2.19 eV, for crystalline (600 °C/2 h) and amorphous (200 °C/8 h) films, respectively. The room-temperature luminescence spectra revealed an intense single-emission band in the visible region. The PL intensity of these materials was increased upon heat-treatment. The excellent optical properties observed for BaMoO₄ amorphous thin films suggested that this material is a highly promising candidate for photoluminescent applications.     

Oriented SrFe12O19 thin films prepared by chemical solution deposition

Thin films of SrFe₁₂O₁₉ (SrM) were prepared from a solution of iron and strontium alkoxides through the chemical solution deposition method on both amorphous (glassy SiO₂), and single crystal substrates (Si(100), Si(111), Ag(111), Al₂O₃(001), MgO(111), MgAl₂O₄(111), SrTiO₃(111)) substrates. The process of crystallization was investigated by means of powder diffraction, atomic force microscopy and scanning electron microscopy. Magnetization measurements, ferromagnetic and nuclear magnetic resonance were used for evaluation of anisotropy in the films. Whilst amorphous substrates enabled growth of randomly oriented SrM phase, use of single crystal substrates resulted in samples with different degree of oriented growth. The most pronounced oriented growth was observed on SrTiO₃(111). A detailed inspection revealed that growth of SrM phase starts through the breakup of initially continuous film into isolated grains with expressive shape anisotropy and hexagonal habit. A continuous film with epitaxial relations to the substrate was produced by repeating recoating and annealing.     

Influence of submonolayer sodium adsorption on the photoemission of the Cu(111)/water ice surface

Photoemission from an ice film deposited on Cu(111) as a function of thickness has been observed in the presence and absence of sodium atoms at the surface-vacuum interface. For either adsorbate alone and photon energies below 4 eV, two-photon photoemission from the Cu(111) substrate dominates. The Cu(111) photoelectron spectrum is perturbed by low coverages of Na, and its intensity is strongly attenuated by a few monolayers of ice. For a low density amorphous ice film, strong charging effects are observed. For ice films annealed to yield either the dense amorphous or crystalline phase, this effect is absent. Deposition of only 0.02 monolayer of Na leads to a dramatic decrease in the threshold for photoemission to 2.3+/-0.2 eV. Thus, photoelectrons are generated by visible radiation in a one-photon process with a cross section that exceeds 10(-18) cm(2). The initial state for the photoemission is identified as a metastable surface trapped electron, which decays thermally with an activation energy of 10+/-2 kJ mol(-1). Quantum calculations are described which support this model and show that the Na atom is accommodated in the first layer of the ice surface.     

Enhanced selectivity towards O(2) and H(2) dissociation on ultrathin Cu films on Ru(0001)

The reactivity of Cu monolayer (ML) and bilayer films grown on Ru(0001) towards O(2) and H(2) has been investigated. O(2) initial sticking coefficients were determined using the King and Wells method in the incident energy range 40-450 meV, and compared to the corresponding values measured on clean Ru(0001) and Cu(111) surfaces. A relative large O(2) sticking coefficient (～0.5-0.8) was measured for 1 ML Cu and even 2 ML Cu/Ru(0001). At low incident energies, this is one order of magnitude larger than the value observed on Cu(111). In contrast, the corresponding reactivity to H(2) was near zero on both Cu monolayer and bilayer films, for incident energies up to 175 meV. Water adsorption on 2 ML Cu/Ru(0001) was found to behave quite differently than on the Ru(0001) and Cu(111) surfaces. Our study shows that Cu/Ru(0001) is a highly selective system, which presents a quite different chemical reactivity towards different species in the same range of collision energies.     

High-temperature solvent stability of sol–gel germania triblock polymer coatings in capillary microextraction on-line coupled to high-performance liquid chromatography

Germania-based sol–gel organic–inorganic hybrid coatings were prepared for on-line coupling of capillary microextraction with high-performance liquid chromatography. For this, a germania-based sol–gel precursor, tetra-n-butoxygermane and a hydroxy-terminated triblock copolymer, poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) were used. These sol–gel germania triblock polymer coatings were chemically anchored to the inner walls of a fused silica capillary (0.25 mm I.D.) in course of its evolution from the sol solution. Scanning electron microscopy images of the sol–gel germania triblock polymer coating were obtained to estimate the coating thickness. For the first time, the analyte distribution constants between a sol–gel germania organic–inorganic hybrid coating and the samples (K_cs) were determined. For a variety of analytes from different chemical classes, including polycyclic aromatic hydrocarbons (PAHs), ketones, alcohols, phenols and amines, the K_cs values ranged from 8.1 × 10¹ to 5.6 × 10⁴. Also, for the first time, the stability of the sol–gel germania-based coating in high-temperature reversed-phase solvent environment was evaluated. The sol–gel germania triblock polymer coatings were capable of surviving exposure to high-temperature solvent conditions (200 °C) with little change in extraction capabilities. This demonstrates that sol–gel germania triblock polymer hybrid materials might be suitable for further applications in high-temperature HPLC. The reproducibility of the method for preparation of the sol–gel germania triblock polymer coatings was also evaluated, and the capillary-to-capillary RSD values ranged from 5.3 to 6.5%. The use of higher flow rates in extraction was found to significantly reduce the time required (from 30–40 to 10–15 min) to reach equilibrium between the sol–gel germania triblock polymer coating and the analytes in the sample solution.     

Composite Water Sorbents of the Salt in Silica Gel Pores Type: The Effect of the Interaction between the Salt and the Silica Gel Surface on the Chemical and Phase Compositions and Sorption Properties

The influence of the inorganic salt-silica gel surface interaction on the chemical and phase compositions and sorption properties of composites of the salt in silica gel pores type is studied. Two possible interaction mechanisms are considered: (1) the ion-exchange adsorption of metal cations on the silica gel surface from a solution of a salt (CaCl₂, CuSO₄, MgSO₄, Na₂SO₄, and LiBr) and (2) the solid-phase spreading of a salt (CaCl₂) over the silica gel surface. The adsorption of metal cations on the silica gel surface in the impregnation step affords ≡Si-OM ⁿ⁺¹ surface complexes in the composites. As a result, two salt phases are formed in silica gel pores at the composite drying stage, namely, an amorphous phase on the surface and a crystalline phase in the bulk. The sorption equilibrium between the CaCl₂/SiO₂ system and water vapor depends on the ratio of the crystalline phase to the amorphous phase in the composite.     

Aerosol-Gel Deposition of Optically Active Thin Films in the System Y2Ti2O7-Er2Ti2O7

Optically active thin films in the system Y₂Ti₂O₇-Er₂Ti₂O₇ (YETO) have been deposited using the Aerosol-gel process. Depending on the heat-treatment temperature, amorphous or crystalline films could be prepared in the range 600–950°C. The study shows that dilution of erbium ions within a Y₂Ti₂O₇ (YTO) matrix allows to prevent short range distance interactions between those ions and to promote good photoluminescence properties of YETO films. These properties are discussed and compared with those of sol-gel derived silica films doped with erbium.