AES and LEED studies of xenon adsorption on (100)NaCl

The thermal and electro impact behaviour of NO adsorbed on Pt(111) and Pt(110) have been studied by LEED, Auger spectroscopy, and thermal desorption. NO was found to adsorb non-dissociatively and with very similar low coverage adsorption enthalpies on the two surfaces at 300 K. In both cases, heating the adlayer resulted in partial dissociation and led to the appearance of N₂ and O₂ in the desorption spectra. The (111) surface was found to be significantly more active in inducing the thermal dissociation of NO, and on this surface the molecule was also rapidly desorbed and dissociated under electron impact. Cross sections for these processes were obtained, together with the desorption cross section for atomically bound N formed by dissociation of adsorbed NO. Electron impact effects were found to be much less important on the (110) surface. The results are considered in relation to those already obtained by Ertl et al. for NO adsorption on Ni(111) and Pd(111), and in particular, the unusual desorption kinetics of N₂ production are considered explicitly. Where appropriate, comparisons are made with the behaviour of CO on Pt(111) and Pt(110), and the adsorption kinetics of NO on the (110) surface have been examined.     

the determination of monolayer structure by infrared spectroscopy: CO2 on NaCl(100)

Infrared spectra of a ¹²C¹⁶O₂ monolayer on NaCl(100) are reported for the first time. The polarization and coverage dependence of spectroscopic signals indicate that there is only one kind of adsorption site, in which the molecular axis is tilted 68° from the surface normal. The adsorbate layer grows in the form of constant-density islands. Plane group symmetry analysis reveals a unique structure: there are two tilted molecules per layer unit cell, arranged in herringbone fashion. This structure is in quantitative agreement with the photometric observations. Splitting of the molecular v₃ band is interpreted by a vibration-vibration coupling mechanism.     

Na2O overlayers epitaxially prepared on Pd(100) and structure-sensitive CO2 adsorption

Sodium oxide overlayers prepared on Pd(100) were examined with AES, LEED and XPS. The oxides were grown by cycles of Na deposition followed by oxidation, maintaining the composition of Na₂O. The surface structure of the deposited oxide was sensitive to the annealing temperature after oxidation. The Na₂O/Pd(100) surfaces gave rise to a (3 × 3) LEED pattern when annealed at 600 K under vacuum. A model based on Na₂O(100) was proposed for the (3 × 3) overlayers, where the oxide was epitaxially aligned in a square periodicity on the substrate. Multilayered Na₂O was prepared maintaining the (3 × 3) pattern, by repeated cycles of preparation. Annealing at 700 K caused a c(4 × 6) pattern, for which a model based on Na₂O(110) was proposed. CO₂ was adsorbed on the (3 × 3) oxide of various thickness to form carbonate at 350 K, whereas the c(4 × 6) oxide was inert. The relationship of structure and reactivity is discussed in relation to the microscopic design of metal-oxide surfaces for base-catalysis.     

Decomposition of CO2 on (100) W

The binding states and condensation kinetics of CO₂ and its decomposition products CO and O₂ on (100) W are examined by flash desorption mass spectrometry. Carbon dioxide desorbs almost entirely as CO and oxygen at all coverages. At saturation there are three major states of CO. These correspond to the high temperature states of CO alone although all peaks are shifted and amounts are altered slightly.     

Model calculation of infrared absorption by a monolayer of CO2 on NaCl(100)

We calculate the absorbance for a proposed model of CO₂ monolayer adsorption on the (100) surface of NaCl. The fitted results near the asymmetric stretch frequency agree quite well with recent experimental data. Implications for further measurements are discussed.     

Modification of ferroelectric hysteresis in Pb(Nb,Zr,Ti)O3 thin films induced by CO2 adsorption

We report on the modification of ferroelectric hysteresis in Pb(Nb,Zr,Ti)O₃ thin films under the adsorption of CO₂ gas. The samples were exposed to the gas in ultra high vacuum while different voltages between the top (Ag) and bottom (Pt) electrodes were applied. After dosing, the samples were heated from room temperature at 1.8 K/s, and a mass spectrometer was used to detect the desorbed molecules. The effective molecular sticking was demonstrated by the appearance of the carbon Auger peak in the surface of the sample and by the presence of CO₂ in the desorption curves. After +(−) 9.9 V were applied to the bottom electrode during dosing, we found a shift of −0.52 (+0.58) μC/cm² in the remnant polarization. These evidences suggest the existence of a depolarizing field induced by molecular adsorption at the surface of the top electrode, and contribute to highlight the potential use of ferroelectric thin films as gas sensors.     

TDS and LEED studies of H2O adsorption on GaAs(110)

The UHV cleaved (110) face has been exposed to water in the range from 10 L to 2 × 10⁴ L. The main TDS peak in H₂O desorption appears at 350 K, independent of coverage. The low desorption energy of 0.7 eV (16 kcal/mol) is reasonable for oxygen atoms bound via the lone pair orbital to As as was earlier derived from UPS measurements. A broad spur between 450 and 600 K may be related to O-Ga bonds. The sticking probability shows values below 10^-4; only near 4.8 × 10³ L (6 × 10¹⁵ cm^-2 s^-1 H₂O molecules for 300 s) corresponding to a coverage of about 0.4 monolayes a steep maximum appears. At about one monolayer saturation is observed. Exposures to more than 10⁴ L of water quench the intensity of the (10) LEED spot considerably stronger than the intensity of the (11) spot. A comparison of the I(E) curves with existing model calculations suggests that the observed behaviour of the LEED spots is caused by a change in surface structure towards the unrelaxed configuration. The higher sticking coefficient observed near 0.4 monolayers may be connected with this rearrangement of surface atoms.     

TbMnO3 epitaxial thin films by pulsed-laser deposition

Epitaxial TbMnO₃ films have been fabricated on SrTiO₃(001) and LaAlO₃(001) substrates by pulsed laser deposition (PLD), the structure and surface morphology of the films were characterized by X-ray diffraction with Cu K_α radiation and atomic force microscopy. The electrical transport and magnetic properties of the TbMnO₃ films and bulk were examined, the resistivity and the forbidden band width E_g change with epitaxial orientation, semiconductor transport properties are found in the films and bulk, the average of the E_g of the films on SrTiO₃ and on LaAlO₃ is equal to the E_g of the bulk. The two TMO films have different magnetization mode, the magnetization of the film on SrTiO₃ have an analogy to that of TbMnO₃ single crystal.     

Ferromagnetism in epitaxial orthorhombic YMnO3 thin films

Epitaxial orthorhombic YMnO₃ thin films, (0 0 1) oriented, have been grown by pulsed laser deposition on (0 0 1)SrTiO₃ substrates. Their crystal structure and magnetic response have been studied in detail. Although bulk o-YMnO₃ is antiferromagnetic, our magnetic measurements reveal intriguing thermal hysteresis between the zero-field-cooled and field-cooled curves below the onset of the antiferromagnetic ordering temperature, thus signaling a more complex magnetic structure with net ferromagnetic moments. We discuss on the possible origin of this net magnetization and we have found a correlation of the magnetic response with the strain state of the films. We propose that substrate-induced strain modifies the subtle competition of magnetic interactions and leads to a non-collinear magnetic state that can thus be tuned by strain engineering.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Influences of CO2 laser annealing on mechanical and laser-induced damage properties of ZrO2 thin films

Zirconium dioxide (ZrO₂) thin films were deposited on BK7 glass substrates by the electron beam evaporation method. A continuous wave CO₂ laser was used to anneal the ZrO₂ thin films to investigate whether beneficial changes could be produced. After annealing at different laser scanning speeds by CO₂ laser, weak absorption of the coatings was measured by the surface thermal lensing (STL) technique, and then laser-induced damage threshold (LIDT) was also determined. It was found that the weak absorption decreased first, while the laser scanning speed is below some value, then increased. The LIDT of the ZrO₂ coatings decreased greatly when the laser scanning speeds were below some value. A Nomarski microscope was employed to map the damage morphology, and it was found that the damage behavior was defect-initiated both for annealed and as-deposited samples. The influences of post-deposition CO₂ laser annealing on the structural and mechanical properties of the films have also been investigated by X-ray diffraction and ZYGO interferometer. It was found that the microstructure of the ZrO₂ films did not change. The residual stress in ZrO₂ films showed a tendency from tensile to compressive after CO₂ laser annealing, and the variation quantity of the residual stress increased with decreasing laser scanning speed. The residual stress may be mitigated to some extent at proper treatment parameters.     

LEED and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 and C) chemisorbed on the stepped rhodium (755) and (331) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₂, C₂H₄ and C has been studied on the clean stepped Rh(755) and (331) surfaces. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) were used to determine the size and orientation of the unit cells, desorption temperatures and decomposition characteristics for each adsorbate. All of the molecules studied readily chemisorbed on both stepped surfaces and several ordered surface structures were observed. The LEED patterns seen on the (755) surface were due to the formation of surface structures on the (111) terraces, while on the (331) surface the step periodicity played an important role in the determination of the unit cells of the observed structures. When heated in O₂ or C₂H₄ the (331) surface was more stable than the (755) surface which readily formed (111) and (100) facets. In the CO and CO₂ TDS spectra a peak due to dissociated CO was observed on both surfaces. NO adsorption was dissociative at low exposures and associative at high exposures. C₂H₄ and C₂H₂ had similar adsorption and desorption properties and it is likely that the same adsorbed species was formed by both molecules.     

High Curie temperature in B-site ordered Sr2CrWO6 epitaxial thin films

Epitaxial and c-axis oriented double perovskite Sr₂CrWO₆ thin films were prepared on SrTiO₃ (100) and LaAlO₃ (100) substrates by pulsed-laser deposition. Structural, magnetic and transport properties were found to be sensitive to the gas conditions employed during the deposition. A small amount of oxygen along with Ar during the deposition was found to be essential for B-site ordering; such films displayed lattice parameters close to the bulk value and display ferromagnetic metallic behavior. The Curie temperature observed above 500 K in these films is higher than bulk Sr₂CrWO₆ samples. Films grown without oxygen were observed to have long c-parameter and no B-site ordering; they were non-magnetic and semiconducting.     

利用脉冲激光沉积技术在双轴织构的Ni基带上外延CeO2薄膜

利用脉冲激光沉积技术在氢还原气氛下成功地在双轴织构的Ni基带上外延了高质量的CeO₂薄膜. x射线衍射θ—２θ扫描和ω扫描结果表明，CeO₂薄膜在Ni基带上呈c轴方向生长，存在很强的平面外织构；极图和φ扫描显示它具有良好的平面内织构. Ni基片上织构的CeO₂薄膜为进一步在其上外延高质量的YBa₂Cu₃O_7-x超导薄膜提供了很好的模板. 关键词： 双轴织构的Ni基带 2薄膜')" href="#">CeO₂薄膜 脉冲激光沉积     

Growth and thermal stability of epitaxial BiFeO3 thin films

We have investigated the oxygen pressure and the temperature dependence on BiFeO₃ thin films deposited on SrTiO₃ substrates by pulsed laser deposition. Reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM) and X-ray diffraction measurements indicate that high-quality epitaxial thin films are obtained for and T=650 °C. Outside of this pressure-temperature window, parasitic peaks attributed to β-Bi₂O₃ appear. We find an increase of the out-of-plane lattice parameter with oxygen pressure that we ascribe to Bi-deficiency due to its high volatility at low pressure. Ex-situ anneals have been performed and results show that as-grown single-phase BiFeO₃ thin films degrade after annealing, whereas as-grown BiFeO₃ containing impurity phases evolve toward a single-phase structure. These experiments demonstrate that parasitic phases can stabilize compounds which are usually unstable in air at elevated temperatures.     

Sims studies of the adsorption of O2, CO and CO2 on titanium using low primary energies

The influence of the adsorption of O₂, CO and CO₂ on secondary ion yields from titanium has been examined using 500 eV primary argon ions. Secondary ion energy distributions were also measured. Electron-induced desorption was used as an auxiliary technique. For oxygen adsorption there is agreement with measurements using other techniques and the adsorption process is shown to occur in two stages, an initial rapid chemisorption regime followed by an oxide regime. For carbon monoxide adsorption, the measurements suggest that dissociation does not occur significantly at room temperature. For CO₂, the results are more complex. Complete dissociation seems unlikely but there may be partial dissociation. Some tentative generalizations are made concenrning the influence of adsorption on secondary ion yields.     

High-quality epitaxial LaNiO3 thin films on SrTiO3(100) and LaAlO3(100)

LaNiO₃ thin films have been deposited by pulsed laser deposition on SrTiO₃(100) and LaAlO₃(100) substrates. The processing conditions have been investigated in order to optimize electrical resistivity, crystal quality, and surface morphology. Excellent properties are achieved at moderate substrate temperature and relatively low oxygen pressure, without the need for annealing. Thickness exerts an important influence on electrical transport, as the electrical resistivity increases quickly in films thicker than a few tens of nanometer. The surface of the films on LaAlO₃ is very flat in all the studied thickness range, but the films on SrTiO₃ develop a pattern of boundaries and even cracks as the thickness is higher. Below the critical thickness, high-quality epitaxial films with very smooth surface and low electrical resistivity are obtained under the optimum conditions of substrate temperature and oxygen pressure. The optimum processing conditions are different depending on the substrate, and control is especially critical in films deposited on SrTiO₃.