Thermal desorption of hydrogen from carbon nanosheets

Carbon nanosheets are a unique nanostructure that, at their thinnest configuration, approach a single freestanding graphene sheet. Temperature desorption spectroscopy (TDS) has shown that the hydrogen adsorption and incorporation during growth of the nanosheets by radio frequency plasma-enhanced chemical vapor deposition are significant. A numerical peak fitting to the desorption spectra (300-1273 K) via the Polanyi-Wigner equation showed that desorption followed a second order process, presumably by the Langmuir-Hinshelwood mechanism. Six peaks provide the best fit to the TDS spectra. Surface desorption activation energies were determined to be 0.59, 0.63, and 0.65 eV for the external graphite surface layers and 0.85, 1.15, and 1.73 eV for desorption and diffusion from the bulk. In contrast to TDS data from previously studied a-C:H films [Schenk et al. J. Appl. Phys. 77, 2462 (1995)], a greater amount of hydrogen bound as sp(2) hybridized carbon was observed. A previous x-ray diffraction study of these films has shown a significant graphitic character with a crystallite dimension of L(a)=10.7 nm. This result is consistent with experimental results by Raman spectroscopy that show as-grown carbon nanosheets to be crystalline as commercial graphite with a crystallite size of L(a)=11 nm. Following TDS, Raman data indicate that the average crystallite increased in size to L(a)=15 nm.     

LEED, STM, and TDS studies of ordered thin films of the rhombus-shaped polycondensed aromatic hydrocarbon C54H22, on MoS2, GeS, and graphite

Low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and thermal desorption spectroscopy (TDS) are used to study vacuum vapor-deposited molecular thin films of the rhombus-shaped polycondensed aromatic hydrocarbon "rhombus-C54", C54H22, on MoS2 and graphite (0001) and on GeS (010) substrates. It is found that this compound forms well-ordered incommensurate superstructures of the closest packed flat-lying molecules in well-defined azimuthal orientations to the substrate. These films are thermally remarkably stable. By TDS, a monolayer binding energy on graphite of 2.3 eV was derived, whereas the molecules in the second layer were found to be less strongly bound (1.9 eV). This difference allows the preparation of monolayers by desorbing multilayers at the appropriate temperature. Apparently, this molecule is a promising candidate for further studies aiming at applications in organic electronics such as organic field effect transistors or light emitting displays.     

乙醇在Mn薄膜／Rh（100）上吸附和分解的研究

应用高分辨电子能量损失谱（HREELS）和热脱附谱（TDS）,研究了Mn薄膜／Rh(100)上乙醇的吸附和分解,提出了表面吸附和分解的反应工,在300K时,蒸镀的Mn在清洁Rh(100)表面上以层层模式生长;在130－300K间,在25mLMn/Rh(100)表面上吸附20L乙醇的TDS结果与乙醇在Rh(100)表面上的结果一致在155K处,脱附出多层凝聚态吸附的乙醇;升温到255K,脱附出H2和CH4,继续升温,出现了与乙醇在R (100)表面上不一致的现象,在470K,同时出现了第2个H2和CH4的脱附峰,在500K,脱附极少量的CO;在950K附近,脱附出大量CO。     

Evolution of water vapor from indium-tin-oxide thin films fabricated by various deposition processes

Tin-doped In₂O₃ (indium-tin-oxide) transparent conducting films are widely used as electrodes of liquid crystal displays and low-E windows. In the present study, a systematic TDS study was undertaken for ITO films fabricated by various deposition processes; such as PVD, dip coating and spray deposition. Water vapor was the main gas evolved from the films; gas evolution from the silicon substrate was negligible. The evolution proceeded via two steps at approximately 373 and 473-623 K. The amount of the evolved water was in the order: (dip-coated film)>(PVD films)> (spray-deposited film). This order was identical to that of the film's resistivities. This revised version was published online in August 2006 with corrections to the Cover Date.     

Analysis of sputter deposited and evaporated tantalum oxide layers on SiO2 by SNMS, XPS, TDS and TRFA

Summary Tantalum oxide films with a thickness of 100 nm for the application in high power laser systems have been prepared on SiO₂-substrates by ion beam sputtering or electron beam evaporation. Comparative analysis of both groups of dielectric films has been performed with the separate bombardment mode of secondary neutral mass spectrometry SNMS, X-ray induced photoelectron spectroscopy XPS, thermal desorption spectroscopy TDS and total reflection X-ray fluorescence analysis TRFA.

---

Analyse von aufgesputterten und aufgedampften Tantaloxid-Schichten auf SiO₂ mit Hilfe von SNMS, XPS, TDS und TRFA

     

Structural evolution of perfluoro-pentacene films on Ag(111): transition from 2D to 3D growth

The structural evolution and thermal stability of perfluoro-pentacene (PF-PEN) thin films on Ag(111) have been studied by means of low-temperature scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). Well-defined monolayer films can be prepared by utilizing the different adsorption energy of mono- and multilayer films and selectively desorbing multilayers upon careful heating at 380 K, whereas at temperatures above 400 K, a dissociation occurs. In the first monolayer, the molecules adopt a planar adsorption geometry and form a well-ordered commensurate (6 × 3) superstructure where molecules are uniformly oriented with their long axis along the <110> azimuth. This molecular orientation is also maintained in the second layer, where molecules exhibit a staggered packing motif, whereas further deposition leads to the formation of isolated, tall islands. Moreover, on smooth silver surfaces with extended terraces, growth of PF-PEN onto beforehand prepared long-range ordered monolayer films at elevated temperature leads to needle-like islands that are uniformly aligned at substrate steps along <110> azimuth directions.     

Oxidation of Reduced Ceria by Incorporation of Hydrogen

The interaction of hydrogen with reduced ceria (CeO_2?x) powders and CeO_2?x(111) thin films was studied using several characterization techniques including TEM, XRD, LEED, XPS, RPES, EELS, ESR, and TDS. The results clearly indicate that both in reduced ceria powders as well as in reduced single crystal ceria films hydrogen may form hydroxyls at the surface and hydride species below the surface. The formation of hydrides is clearly linked to the presence of oxygen vacancies and is accompanied by the transfer of an electron from a Ce³⁺ species to hydrogen, which results in the formation of Ce⁴⁺, and thus in oxidation of ceria.     

In vitro percutaneous absorption of thiamine disulfide through rat skin from a mixture of propylene glycol and fatty acid or its analog.

Percutaneous absorption of thiamine disulfide, (TDS), a lipophilic derivative of thiamine, from a mixture of propylene glycol (PG) and fatty acid (FA) or its analog through rat skin was tested in vitro. Lauric acid (12:0) enhanced the absorption depending on its concentration in PG and showed a maximal enhancement at 10% w/w. At 10% w/v, lauryl alcohol also enhanced the absorption, but less than 12:0, which lauric acid methyl ester suppressed the absorption. The flux of TDS did not depend on the solubility of TDS in the vehicle, but on the permeability coefficient. From these results, it is suggested that FA increases the permeability coefficient not only because FA increases TDS diffusion by disrupting lipid packing in the stratum corneum but also, FA increases TDS partition to lipid phase by interacting with TDS.     

Studies on the emission behavior of polypropylene by gas chromatography/mass spectrometry with static headspace or thermodesorption

Emissions from polypropylene (PP) may cause undesired smell, be harmful, or lead to so-called fogging which prohibits its use for car interiors. Thus, qualitative as well as quantitative emission studies are necessary. Thermodesorption (TDS) and static headspace (sHS) with subsequent GC-MS analysis are two powerful tools for analyzing the emission behavior of polymers with a minimum of sample handling. In this work we investigated the emission behavior of PP with TDS and sHS coupled to GC-MS paying special attention to quantitative considerations and to the relevance of emitted substances for fogging phenomena. After extraction for 30min and incubation for 2h, TDS-GC-MS and sHS-GC-MS results were satisfyingly repeatable (with relative standard deviations up to 5%). TDS allowed to introduce substances up to higher boiling points into the GC-MS system, but required to control sample geometry, as emission depended rather on sample surface than on sample mass. In sHS, emission was governed by partitioning between the gas and the sample phase rather than by full evaporation of the analytes. Above a certain analyte-dependent amount, peak area became independent of the sample amount. However, if the sample amount was kept constant, peak areas of emitted substances showed a linear dependence upon concentration of volatiles. Therefore, accurate quantitation was still possible. Typically alkanes, alkenes and dialkenes dominate TDS-GC-MS and sHS-GC-MS chromatograms of PP. They only contributed to fogging if they had a chain length higher than C16. These substances were only detectable when TDS was used for sample introduction, but not with sHS. sHS-GC-MS is thus not useful for judging fogging behavior.     

Growth kinetics, structure, and morphology of para-quaterphenyl thin films on gold(111)

The adsorption, desorption, and growth kinetics as well as the thin film morphology and crystal structure of p-quaterphenyl (4P) grown under ultrahigh vacuum conditions on single crystalline Au(111) have been investigated. Thermal desorption spectroscopy (TDS) reveals two distinct first-order peaks attributed to monolayer desorption followed by a zero-order multilayer desorption. The saturation coverage of the full 4P monolayer has been quantitatively measured with a quartz microbalance to be 8 x 10(13) molecules/cm2. Using low energy electron diffraction the structures of the 0.5 and 1 ML (monolayer) adsorbates have been studied, showing highly regular arrangements of the 4P molecules, which are affected by the (111) surface structure. At the transition from 0.5 to 1 ML a structural compression of the overlayer has been observed. The behavior of thicker 4P films has been investigated by combined TDS-XPS (XPS-x-ray photoelectron spectroscopy). A temperature-induced recrystallization process at about 270 K has been observed for a 7 nm thick 4P film grown at 93 K, corresponding to a transition from a disordered layerlike growth to a crystalline island growth. Ex situ optical microscopy and atomic-force microscopy investigations have revealed needle-shaped 4P islands. Applying x-ray diffraction the crystalline order and epitaxial relationship of the 4P films with 30 nm and 200 nm mean thicknesses have been determined.     

Analysis of cigarette smoke by an online thermal desorption system and multidimensional GC-MS

Single puffs of cigarette smoke with a wide continuous range of volatility are directly analyzed using a new system. The system consists of a smoking machine, an online thermal desorption system (TDS), and a multidimensional gas chromatograph-mass spectrometer (MDGC-MS) system. The online TDS with the smoking machine collects the single-puff cigarette smoke with glass beads as the cryogenic adsorbent. The MDGC is composed of three capillary columns, Poraplot Q, and DB-WAX for separation and a deactivated capillary column for pressure balance, which enables simultaneous separation of the two different phases. The smoke desorbed from the TDS is divided into vapor and semivolatile phases and analyzed individually with each column by the MDGC. Thus, the system enables the overall analysis of the two phases simultaneously, including acetaldehyde and 1,4-benzenediol. This system also provides more appropriate analysis for compounds crossing the two phases such as toluene and pyridine. For the approach of introducing internal standards, a gas mixture of toluene-d(8) and o-xylene-d(10) is applied and the compounds are detected in the vapor and semivolatile phases, respectively.     

On the method of reflection and short in dielectric time domain spectroscopy

The method of reflection against a sample and short in dielectric time domain spectroscopy (TDS) is discussed. It is shown how, by a proper choice of sample lengths, the method can be used to reach even the high-frequency end of the spectrum accessible by TDS. Results for test measurements on benzyl alcohol and chlorobenzene are given.     

Evolution of water vapor from indium-tin-oxide transparent conducting films fabricated by dip coating process

Tin-doped indium oxide In₂O₃ (indium-tin-oxide) transparent conducting films were fabricated on silicon substrates by a dip coating process. The thermal analysis of the ITO films was executed by temperature-programmed desorption (TPD) or thermal desorption spectroscopy (TDS) in high vacuum. Gas evolution from the ITO film mainly consisted of water vapor. The total amount of evolved water vapor increased on increasing the film thickness from approx. 25 to 250 nm and decreased by increasing the preparation temperature from 365 to 600°C and by annealing at the same temperature for extra 10 h. The evolution occurred via two steps; the peak temperatures for 250 nm thick films were approx. 100-120 and 205-215°C. The 25 nm thick films evolved water vapor at much higher temperatures; a shoulder at approx. 150-165°C and a peak at approx. 242°C were observed. The evolution temperatures increased by increasing the preparation and the annealing temperatures except in case of the second peak of the 25 nm thick films. The evolution of water vapor at high temperature was tentatively attributed to thermal decomposition of indium hydroxide, In(OH)₃, formed on the surface of the nm-sized ITO particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Time domain dielectric spectroscopy. A new effective tool for physical chemistry investigation

The general principles of time domain dielectric spectroscopy (TDS) are summarized. The methods of data treatment and presentation, and different TDS methods which enable one to obtain the permanent spectrum of ^* () in the frequency range of 10⁵–10¹⁰ are given. The examples of TDS application for the investigation of dielectric properties in samples of different nature and structure are considered in this review.     

Adsorption of CO on the copper-precovered ZnO(0001) surface: a molecular-beam scattering study

Auger electron spectroscopy (AES), thermal-desorption spectroscopy (TDS), and, in particular, molecular-beam scattering techniques have been combined to address particle size effects in the adsorption of CO on Cu-on-ZnO(0001). AES and TDS lead to a Cu coverage, theta(Cu), calibration. The TDS curves, as a function of theta(Cu) and CO exposure, revealed three structures at 150, 220, and 260-280 K, in agreement with prior studies. However, a unique assignment of the TDS structures to a particular Cu face was not possible. An enhancement of the initial adsorption probability, S0, with respect to the support indicates the effect of the Cu nanoparticles. Despite that the shape of S0 versus impact energy curves was independent of theta(Cu) and agreed with Cu single-crystal reference systems, distinct particle size effects were present with regard to the adsorption mechanism. It was possible to observe a crossover from Langmuir-type adsorption dynamics to more precursor-assisted adsorption dynamics with increasing theta(Cu). Thus, a dynamic structure-activity relationship was evident, i.e., the energy-transfer mechanism depends on the Cu morphology.     

A Glycosidic-Bond-Based Mass-Spectrometry-Cleavable Cross-linker Enables In Vivo Cross-linking for Protein Complex Analysis

Chemical cross-linking mass spectrometry (CXMS) has emerged as a powerful technology to analyze protein complexes. However, the progress of in vivo CXMS studies has been limited by cross-linking biocompatibility and data analysis. Herein, a glycosidic bond-based MS-cleavable cross-linker of trehalose disuccinimidyl ester (TDS) was designed and synthesized, which was fragmented in MS under CID/HCD to simplify the cross-linked peptides into conventional single peptides via selective cleavage between glycosidic and peptide bonds under individual MS collision energy. Consequently, the cross-linking identification accuracy and throughput were significantly enhanced, and the popular MS mode of stepped HCD was allowed. In addition, TDS showed proper cell-penetrating properties while being highly water-soluble, making it non-DMSO dependent during solubilization. Collectively, TDS provides a promising toolkit for CXMS characterization of living systems with high biocompatibility and accuracy.     

Adsorption of water on JSC‐1A (simulated moon dust samples)—a surface science study

JSC‐1a (a simulated lunar dust sample) supported on a silica wafer (SiO₂/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x‐ray (EDX) spectroscopy, and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and in addition by collecting isothermal adsorption transients. Blind experiments on the silica support have been performed as well. JSC‐1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg, as characterized in detail in prior studies, for example, at NASA. The particle sizes span the range from a few micrometers up to 100 µm. At small exposures, H₂O TDS is characterized by broad (100–450) K structures; at large exposures, distinct TDS peaks emerge, which are assigned to amorphous solid water (ASW) (145 K) and crystalline ice (CI) (165 K). Water dissociates on JSC‐1a at small exposures but not on the bare silica support. Coadsorption TDS data (alkane–water mixtures) indicate that rather porous condensed ice layers form at large exposures, with the mineral particles acting most likely as nucleation sites. At thermal impact energies, the initial adsorption probability amounts to 0.92 ± 0.05. It is evident that the drop‐and‐dry technique, developed in studies about nanoparticles/tubes, can be extended to obtain samples for surface science studies based on powders consisting of particles with rather large diameters. Copyright © 2008 John Wiley & Sons, Ltd.     

Analysis of organic contaminations on Si(100) by thermal desorption spectroscopy

Summary Temperature and chemical state selective analysis of organic contaminants on Si(100) present after storage in air can be performed using thermal desorption spectroscopy (TDS). Samples stored for different times in air were characterized by XPS and then subjected to TDS. Hydrocarbon fragments were observed as well as a significant partial pressure of formaldehyde occurring as a decomposition product from higher molecular contaminants. Effects of treatment with HF and heating under reduced pressures of molecular oxygen were studied. The paper describes also some general analytical features of the technique.     

Numerical study of a drug release profile in the transdermal drug delivery system

Drug release by diffusion from an unstressed thin polymer film with a dissolved crystallizable component was simulated using a kinetic Monte Carlo model. This model was used previously to study Ostwald ripening in a high crystallizable component regime and was shown to correctly simulate solvation, diffusion, and precipitation. In this study, the same model with modifications was applied to the drug transportation and release in the low concentration regime of interest to the transdermal drug delivery system (TDS) community. We demonstrate the model's utility by simulating diffusion, crystal precipitation, growth and shrinkage during storage, and drug release from the thin TDS to a surface under different conditions. The simulation results provide a first approximation for the drug release profile occurring from TDS to skin. It has been reported that growth of drug crystals in TDS occurs mainly in the middle third of the polymer layer at relatively higher temperatures. The results from the simulations showed that the release rate and concentration profile of a TDS depend on the dissolution process of the crystal. At low storage temperature, the drug precipitates to form small evenly distributed crystals throughout the thickness of the TDS patch. The release rate of these small, evenly distributed crystals most closely matched that of a completely dissolved drug.     

Fluorescent humic substances–arsenic complex in well water in areas where blackfoot disease is endemic in Taiwan

The relationship between the four components, (1) fluorescence intensity, (2) arsenic concentration, (3) pH and (4) total dissolved solids, (TDS) measured in well waters from areas in Taiwan where blackfoot disease (BFD) is endemic was studied, as well as the relationships between the four degrees of BFD and each of the above four symptomatic components, in order to evaluate the etiological factors of BFD more progressively. The following 95% confidence intervals were obtained in well water samples (n = 1189): fluorescence intensity, 26.837–32.570; arsenic concentration, 0.103–0.127 mg dm^?3; pH, 7.466–7.519; and TDS 733.063–801.647 mg dm^?3. Fluorescence intensities of the four degrees of BFD were not all the same (F = 64.54, P < 0.001), and nor were arsenic concentrations (F = 72.03, P < 0.001), pH values (F = 7.30, P < 0.001), nor TDS values (F = 10.76, P < 0.001). In addition, multiple comparisons indicate that the higher the epidemical degree, the higher the fluorescence intensities, arsenic concentrations and pH values become; however, such a relationship is not found for TDS values. Moreover, the fluorescence intensities have positive linear correlations with arsenic concentrations (r = 0.49, P < 0.001), pH (r = 0.25, P < 0.001), and TDS (r = 0.18, P < 0.001), as do the arsenic concentrations with pH (r = 0.22, P < 0.001). Of the four epidemical degree groups, pairs are not significantly different from one another in correlation coefficients between fluorescence intensity and arsenic concentration, which implies a steady relationship between fluorescent compounds and arsenic. We conclude that fluorescent compounds in well water, as possible etiological factors of BFD, are closely related to arsenic along with pH and TDS values in the areas where BFD is endemic. In addition, we infer that a complex is formed by fluorescent compounds, arsenic and other metals.