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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Synthesis of TiO{sub 2} thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO{sub 2} thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, (TIP, Ti(O{sup i}Pr){sub 4}) and Bis(dimethylamido)titanium diisopropoxide, (BTDIP, (Me{sub 2}N){sub 2}Ti(O{sup i}Pr){sub 2}) were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO{sub 2} polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO{sub 2} thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO{sub 2} thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO{sub 2} film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO{sub 2} film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO{sub 2} film synthesized with BTDIP precursor to apply dye-sensitized solar cell.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Characterizing Density and Spatial Distribution of Trap States in Ta 3 N 5 Thin Films for Rational Defect Passivation

Tantalum nitride (Ta 3 N 5 ) has gained significant attention as a potential photoanode material, yet it has been challenged by material quality issues. Defect-induced trap states are detrimental to the performance of any semiconductor material. Beyond influencing the performance of Ta 3 N 5 films, defects can also accelerate the degradation in water during desired electrochemical applications. Defect passivation has provided an enormous boost to the development of many semiconductor materials but is currently in its infancy for Ta 3 N 5 . This is in part due to a lack of experimental understanding regarding the spatial and energetic distribution of trap states throughout Ta 3 N 5 thin films. Here, we employ drive-level capacitance profiling (DLCP) to experimentally resolve the spatial and energetic distribution of trap states throughout Ta 3 N 5 thin films. The density of deeper energetic traps is found to reach ∼2.5 to 6 × 10 22 cm –3 at the interfaces of neat Ta 3 N 5 thin films, over an order of magnitude greater than the bulk. In addition to the spatial profile of deep trap states, we report neat Ta 3 N 5 thin films to be highly n-type in nature, owning a free carrier density of ∼9.74 × 10 17 cm –3 . This information, coupled with the present understanding of native oxide layers on Ta 3 N 5 , has facilitated the rational design of a targeted passivation strategy that simultaneously provides a means for catalyst immobilization. Loading catalyst via silatrane moieties suppresses the density of defects at the surface of Ta 3 N 5 thin films by two orders of magnitude, while also reducing the free carrier density of films by over one order of magnitude, effectively dedoping the films to ∼2.40 × 10 16 cm –3 . The surface passivation of Ta 3 N 5 films translates to suppressed defect-induced trapping and recombination of photoexcited carriers, as determined through absorption, photoluminescence, and transient photovoltage. Here, this illustrates how developing a deeper understanding of the distribution and influence of defects in Ta 3 N 5 thin films has the potential to guide future works and ultimately accelerate the integration and development of high-performance Ta 3 N 5 thin film devices.

defect passivation↗
DOE OSTI2012

Atmospheric-pressure plasma-enhanced chemical vapor deposition of a-SiCN:H films: Role of precursors on the film growth and properties

Atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using Surfx Atomflow TM 250D APPJ was utilized to synthesize amorphous silicon carbonitride coatings using tetramethyldisilizane (TMDZ) and hexamethyldisilizane (HMDZ) as the single source precursors. The effect of precursor chemistry and the substrate temperature (T s ) on the properties of a-SiCN:H films were evaluated, while nitrogen was used as the reactive gas. Surface morphology of the films was evaluated using atomic force microscopy (AFM); chemical properties were determined using Fourier transform infrared spectroscopy (FTIR); thickness and optical properties were determined using spectroscopic ellipsometry and mechanical properties were determined using nano-indentation. In general films deposited at substrate temperature (T s ) <200 °C contained organic moieties, while the films deposited at T s >200 oC depicted strong Si-N and Si-CN absorption. Refractive indices (n) of the thin films showed values between 1.5 -2.0 depending on the deposition parameters. Mechanical properties of the films determined using nano-indentation revealed that these films have hardness between 0.5 GPa to 15 GPa depending on the Ts. AFM evaluation of the films showed high roughness (R a ) values of 2-3 nm for the films grown at low T s (< 250 °C), while the films grown at T s ≥ 300 °C exhibited atomically smooth surface with R a of ~ 0.5 nm. Furthermore, based on the gas phase (plasma) chemistry, precursor chemistry and the other experimental observations, a possible growth model that prevails in the AP-PECVD of a-SiCN:H thin films is proposed.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Structure and properties of nanocrystalline ZrN{sub x}O{sub y} thin films: Effect of the oxygen content and film thickness

The main objective of this study was to investigate the structure and properties of ZrN{sub x}O{sub y} thin films associated with oxygen content and film thickness. ZrN{sub x}O{sub y} thin films were deposited using hollow cathode discharge ion plating on Si (100) substrate. The thickness of ZrN{sub x}O{sub y} films increased with increasing oxygen flow rate, ranging from 143 to 894 nm. Phase separation from ZrN{sub x}O{sub y} to ZrN and monoclinic ZrO{sub 2} (m-ZrO{sub 2}) was observed by x-ray diffraction (XRD). The electrical and mechanical properties were influenced by the film thickness and the amount of separated phase, m-ZrO{sub 2}. ZrN{sub x}O{sub y} thin films with smaller thickness or deposited at higher O{sub 2} flow rate were found to have higher electrical resistivity. Hardness of the ZrN{sub x}O{sub y} thin films increased with increasing thickness, which could be related to microstructure change of the thin films. Residual stress of the ZrN phase in the ZrN{sub x}O{sub y} thin films, measured using the modified sin{sup 2} {psi} XRD method, decreased with increasing oxygen flow rate. The thickness dependence of the residual stress in ZrN was different with different oxygen flow rates. The average residual stress of the ZrN{sub x}O{sub y} thin films also decreased with increasing oxygen flow rate and the stress did not showed significant dependence on the film thickness.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Thickness-dependent metal-insulator transition in epitaxial SrRuO{sub 3} ultrathin films

Transport characteristics of ultrathin SrRuO{sub 3} films, deposited epitaxially on TiO{sub 2}-terminated SrTiO{sub 3} (001) single-crystal substrates, were studied as a function of film thickness. Evolution from a metallic to an insulating behavior is observed as the film thickness decreases from 20 to 4 unit cells. In films thicker than 4 unit cells, the transport behavior obeys the Drude low temperature conductivity with quantum corrections, which can be attributed to weak localization. Fitting the data with 2-dimensional localization model indicates that electron-phonon collisions are the main inelastic relaxation mechanism. In the film of 4 unit cells in thickness, the transport behavior follows variable range hopping model, indicating a strongly localized state. Magnetoresistance measurements reveal a likely magnetic anisotropy with the magnetic easy axis along the out-of-plane direction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopic ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10 –14 cm 2 /s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electrical bending actuation of gold-films with nanotextured surfaces

An actuating material system comprising a gold-film with nanotextured surface was fabricated. Using electroless gold plating onto a substrate of porous anodized aluminum oxide, a thin film of gold with a high density of short gold nanofibers on its surface was made. When one end of such a film was connected to an ion generator, bending was achieved upon electrical charging in air. Experiments showed that the free end of an 8 mm film could be displaced by more than 1.6 mm with a bending strain of 0.08%. In contrast with other types of thin-film artificial muscle materials, the present Au-film did not require any electrolyte to function. With the relatively easy fabrication method, this nanotextured film shows promising actuation behavior in air. Actuation systems based on a number of mechanisms have been developed in the last few decades, including electric, ionic, photonic, pneumatic, and thermal. As discussed in detail in Madden et al. and Brochu and Pei,11 the weaknesses of these materials include bulkiness, low stress or strain generation, low strain rate, long response time, short cycle life, and low energy efficiency. Recent developments have involved the possibilities to use the unique properties of nanostructures to produce actuation, such as in nanostructured carbon, nanoporous gold or platinum, V 2 O 5 nanofibre sheet, electroactive nanostructured polymers, hybrid carbon nanotube yarn, niobium nanowire yarn, and anodized aluminum oxide (AAO). Here, we introduce a nanostructured material system comprising a gold film with a high density of short gold-nanofibers attached to one side, which can bend to produce a large displacement (~1.6 mm) upon electrical charging through an ion generator. In addition to the displacement, the functionality without the need of an electrolyte is another advantage for using this material system as actuators. We discuss the fabrication and characterization methods, the morphology, and the actuating properties of this system here. To achieve a metal film with a nanotextured surface, electroless gold-plating was performed on substrates of AAO with a characteristic nano-honeycomb structure consisting of >10 10 pores per cm 2 . The fabrication of the AAO substrates followed the procedures described in Cheng and Ngan. The anodization condition for the AAO was 40 V against graphite electrode in saturated oxalic acid at 18 °C for 2 h. The pore diameter observed was 50 ± 5 nm. By using an electroless gold-plating method described by Kohli et al.,22 gold in short nanofiber form was deposited into the pores of the AAO template. As shown in Figs. 1(a) and 1(b), in addition to partially filling the pores with gold, the top surface of the AAO template was coated with a thin gold film (~100 nm) of Au. A ~30 μm layer of lacquer was then painted on the top of the thin gold film to serve as a supporting layer.

42 ENGINEERING↗
DOE OSTI2022

Enhancing and Extinguishing the Different Emission Features of 2D (EA(1-)(x)FA(x))(4)Pb3Br10 Perovskite Films

2D hybrid perovskites are attractive for optoelectronic devices. In thin films, the color of optical emission and the texture of crystalline domains are often difficult to control. Here, a method for extinguishing or enhancing different emission features is demonstrated for the family of 2D Ruddlesden-Popper perovskites (EA(1-)(x)FA(x))(4)Pb3Br10 (EA = ethylammonium, FA = formamidinium). When grown from aqueous hydrobromic acid, crystals of (EA(1-)(x)FA(x))(4)Pb3Br10 retain all the emission features of their parent compound, (EA)(4)Pb3Br10. Surprisingly, when grown from dimethylformamide (DMF), an emission feature, likely self-trapped exciton (STE), near 2.7 eV is missing. Extinction of this feature is correlated with DMF being incorporated between the 2D Pb-Br sheets, forming (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y). Without FA, films grown from DMF form (EA)(4)Pb3Br10, retain little solvent, and have strong emission near 2.7 eV. Slowing the kinetics of film growth strengthens a different emission feature, likely a different type of STE, which is much broader and present in all compositions. Films of (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y) have large, micron-sized domains and homogeneous orientation of the semiconducting sheets, resulting in low electronic disorder near the absorption edge. The ability to selectively strengthen or extinguish different emission features in films of (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y) reveals a pathway to tune the emission color in these compounds.

2D halide perovskites↗
DOE OSTI2023

Alkali element (Li, Na, K, and Rb) doping of Cu 2 BaGe 1– x Sn x Se 4 films

Cu 2 BaGe 1–x Sn x Se 4 (CBGTSe) represents an exemplary system within the I 2 –II–IV–X 4 (I = Ag, Cu; II = Sr, Ba; IV = Ge, Sn; X = S, Se) family, which has been introduced to target suppressing the formation of anti-site defects and associated defect clusters within the analogous kesterite Cu 2 ZnSn(S,Se) 4 . Previous studies on CBGTSe films showed relatively low hole carrier densities (<10 13 cm –3 ), which may limit their corresponding application as active layers within photovoltaic, thermoelectric, and optoelectronic devices. In the current study, we explore the incorporation of alkali elements (Li, Na, K, and Rb) into CBGTSe films as prospective dopants to address the low hole carrier density and to allow for property tunability. First, incorporation of Na-, K-, and Rb-dopants noticeably increases the average grain sizes for CBGTSe films, while the Li-dopant has relatively limited impact. In addition, the alkali-dopants lead to a 1 to 3 orders of magnitude increase in hole carrier density (up to 10 15 cm –3 is achieved using K doping, corresponding to the alkali element yielding the highest doping efficiency). Here, the alkali-doped films show slightly lower minority carrier lifetimes and carrier mobility values than the non-doped samples, and these values are found to follow an approximate universal dependence with carrier density (also considering data derived from other previously explored vacuum-deposited I 2 –II–IV–X 4 chalcogenide films). As alkali-doping can significantly increase carrier densities, alkali elements can be considered useful p-type dopants for CBGTSe, as well as prospectively for other analogous I 2 –II–IV–X 4 systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Synthesis and characterization of titanium-alloyed hematite thin films for photoelectrochemical water splitting

We have synthesized pure and Ti-alloyed hematite thin films on F doped SnO{sub 2} coated glass substrates by radio frequency magnetron co-sputtering of iron oxide and titanium targets in mixed Ar/O{sub 2} and mixed N{sub 2}/O{sub 2} ambient. We found that the hematite films deposited in the N{sub 2}/O{sub 2} ambient exhibit much poorer crystallinity than the films deposited in the Ar/O{sub 2} ambient. We determined that Ti alloying leads to increased electron carrier concentration and crystallinity, and reduced bandgaps. Moreover, Ti-alloyed hematite thin films exhibited improved photoelectrochemical performance as compared with the pure hematite films: The photocurrents were enhanced and the photocurrent onset shifted to less positive potentials.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Ion irradiation of Fe-Fe oxide core-shell nanocluster films: Effect of interface on stability of magnetic properties

A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NCs) of Fe core-Fe{sub 3}O{sub 4} shell or fully oxidized Fe{sub 3}O{sub 4}. Films of these NC on Si(100) or MgO(100)/Fe{sub 3}O{sub 4}(100) were irradiated to 10{sup 16} Si{sup 2+}/cm{sup 2} near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. In all cases, the particle sizes increased due to ion irradiation, and when a core of Fe is present, irradiation reduces the oxide shells to lower valent Fe species. These results show that ion irradiated behavior of the NC films depends strongly on the initial nanostructure and chemistry, but in general saturation magnetization decreases slightly.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Doping-tunable thermal emission from plasmon polaritons in semiconductor epsilon-near-zero thin films

We utilize the unique dispersion properties of leaky plasmon polaritons in epsilon-near-zero (ENZ) thin films to demonstrate thermal radiation control. Owing to its highly flat dispersion above the light line, a thermally excited leaky wave at the ENZ frequency out-couples into free space without any scattering structures, resulting in a narrowband, wide-angle, p-polarized thermal emission spectrum. We demonstrate this idea by measuring angle- and polarization-resolved thermal emission spectra from a single layer of unpatterned, doped semiconductors with deep-subwavelength film thickness (d/λ{sub 0} ∼ 6×10{sup −3}, where d is the film thickness and λ{sub 0} is the free space wavelength). We show that this semiconductor ENZ film effectively works as a leaky wave thermal radiation antenna, which generates far-field radiation from a thermally excited mode. The use of semiconductors makes the radiation frequency highly tunable by controlling doping densities and also facilitates device integration with other components. Therefore, this leaky plasmon polariton emission from semiconductor ENZ films provides an avenue for on-chip control of thermal radiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film was prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance, due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as-prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder-free electrode effectively reduces electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provides a high specific surface area to improve electron transport, enhancing rapid ion transport and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/micro-size electronic devices.

holey film↗
DOE OSTI2025

Accelerating Discovery of Solid‐State Thin‐Film Metal Dealloying for 3D Nanoarchitecture Materials Design through Laser Thermal Gradient Treatment

Thin‐film solid‐state metal dealloying (thin‐film SSMD) is a promising method for fabricating nanostructures with controlled morphology and efficiency, offering advantages over conventional bulk materials processing methods for integration into practical applications. Although machine learning (ML) has facilitated the design of dealloying systems, the selection of key thermal treatment parameters for nanostructure formation remains largely unknown and dependent on experimental trial and error. To overcome this challenge, a workflow enabling high‐throughput characterization of thermal treatment parameters is demonstrated using a laser‐based thermal treatment to create temperature gradients on single thin‐film samples of Nb‐Al/Sc and Nb‐Al/Cu. This continuous thermal space enables observation of dealloying transitions and the resulting nanostructures of interest. Through synchrotron X‐ray multimodal and high‐throughput characterization, critical transitions and nanostructures can be rapidly captured and subsequently verified using electron microscopy. The key temperatures driving chemical reactions and morphological evolutions are clearly identified. While the oxidation may influence nanostructure formation during thin‐film treatment, the dealloying process at the dealloying front involves interactions solely between the dealloying elements, highlighting the availability and viability of the selected systems. Further, this approach enables efficient exploration of the dealloying process and validation of ML predictions, thereby accelerating the discovery of thin‐film SSMD systems with targeted nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Optical and structural properties of sputtered CdS films for thin film solar cell applications

Graphical abstract: Photo current–voltage curves (a) and the quantum efficiency (QE) (b) for the solar cell with CdS film grown at 300 °C. - Highlights: • CdS thin films were grown by a RF magnetron sputtering method. • Influence of growth temperature on the properties of CdS films was investigated. • At higher T{sub g}, the crystallinity of the films improved and the grains enlarged. • CdS/CdTe solar cells with efficiencies of 9.41% were prepared at 300 °C. - Abstract: CdS thin films were prepared by radio frequency magnetron sputtering at various temperatures. The effects of growth temperature on crystallinity, surface morphology and optical properties of the films were characterized with X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Raman spectra, UV–visible spectrophotometry, and photoluminescence (PL) spectra. As the growth temperature was increased, the crystallinity of the sputtered CdS films was improved and the grains were enlarged. The characteristics of CdS/CdTe thin film solar cell appeared to be significantly influenced by the growth temperature of the CdS films. Thin film CdS/CdTe solar cells with efficiencies of 9.41% were prepared at a growth temperature of 300 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation

We report thickness and homopolymer molar mass dependencies in thin film blends of a compositionally symmetric 75 kg/mol lamellar polystyrene-block-poly(methyl methacrylate) diblock copolymer (PS-b-PMMA) with near-equal volume fractions of PS and PMMA homopolymers on “neutral” surfaces that promote a vertical domain orientation. PS and PMMA homopolymers with equal molar masses of 1, 3, and 22 kg/mol are blended in a 1:1 mass ratio. To efficiently explore this parameter space, we prepared combinatorial samples with gradient homopolymer concentrations using electrospray deposition (ESD) and gradient film thicknesses using flow coating; these samples were subsequently characterized by grazing-incidence small-angle X-ray scattering and scanning electron microscopy, respectively. Our results demonstrate that the added homopolymers increase or reduce domain spacings with respect to the neat (unblended) block copolymer depending on their molar masses, in line with previous reports; a simple heuristic to estimate the domain scaling in ternary blends based on the homopolymer molar mass agrees well with data for the thinnest blend films studied here. More surprisingly, we observe that the measured domain spacing in blends also depends on film thickness, with thicker films exhibiting larger domain spacings than thinner films at the same homopolymer concentration. Furthermore, thickness gradients at fixed homopolymer concentrations reveal a change in lamellae orientation from vertical to horizontal as film thickness is increased beyond the nominal lamellar domain spacing. Coarse-grained molecular dynamics simulations indicate that this change in orientation is induced by homopolymer segregation to film surfaces. Finally, tying these effects together, we hypothesize that the observed dependence of domain spacing on film thickness is a consequence of changes in the vertical homopolymer composition profile in thicker films during lamellae reorientation and the conformational asymmetry between PMMA and PS segments.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electron-stimulated reactions in layered CO/H{sub 2}O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

Low-energy (100 eV) electron-stimulated reactions in layered H{sub 2}O/CO/H{sub 2}O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H{sub 2}O and D{sub 2}O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Time-resolved terahertz dynamics in thin films of the topological insulator Bi 2 Se 3

We use optical pump–THz probe spectroscopy at low temperatures to study the hot carrier response in thin Bi 2 Se 3 films of several thicknesses, allowing us to separate the bulk from the surface transient response. We find that for thinner films the photoexcitation changes the transport scattering rate and reduces the THz conductivity, which relaxes within 10 picoseconds (ps). For thicker films, the conductivity increases upon photoexcitation and scales with increasing both the film thickness and the optical fluence, with a decay time of approximately 5 ps as well as a much higher scattering rate. Furthermore, these different dynamics are attributed to the surface and bulk electrons, respectively, and demonstrate that long-lived mobile surface photo-carriers can be accessed independently below certain film thicknesses for possible optoelectronic applications.

36 MATERIALS SCIENCE↗