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At least 1,441 records · Page 80

Structure and physicochemical properties of thin film photosemiconductor cells based on porphine derivatives

Photosemiconductor thin films based on two organic porphine derivatives have been investigated. These compounds have different pendent groups; the film morphology, along with the specific fabrication technique, is determined to a great extent by these groups. The films have been fabricated by vacuum sputtering and using the Langmuir−Schaefer method. According to the atomic force microscopy (AFM) data, the Langmuir−Schaefer films are more homogeneous than the sputtered ones. It is shown that the sputtered films based on substituted porphine have a looser stacking than the initial analog. A spectroscopy study revealed a bathochromic shift of the Soret band in the Langmuir−Schaefer films–sputtered films series. This shift is explained by the increase in the concentration and size of molecular aggregates in sputtered films. It is shown that a polycrystalline C{sub 60} fullerene film deposited onto an amorphous substituted porphine layer improves the photoelectric characteristics of the latter. Both the time stability of the photodiode structure and its ampere‒watt sensitivity increase (by a factor of 10 in the transition regime). The steady-state current does not change. The effect of polarity reversal of the photovoltaic signal is observed in a planar C{sub 60}‒substituted metalloporphine heterostructure, which is similar to the pyroelectric effect. The polarity reversal can be explained by the contribution of the trap charge and discharge current at the interface between the amorphous photosemiconductor and crystalline photosemiconductor to the resulting photoelectric current.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The influence of substrate temperature on the structural and optical properties of ZnS thin films

Thin films of ZnS were deposited on soda lime glass substrates by a modified close-space sublimation technique. The change in optical and structural properties of the films deposited at various substrate temperatures (150-450 Degree-Sign C) was investigated. X-ray diffraction spectra showed that films were polycrystalline in nature having cubic structure oriented only along (111) plan. The crystallinity of films increased with the substrate temperature up to 250 Degree-Sign C. However, crystallinity decreased with further increase of substrate temperature and films became amorphous at 450 Degree-Sign C. The atomic force microscopy data revealed that the films become more uniform and dense with the increase of substrate temperature. Optical properties of the films were determined from the transmittance data using Swanepoel model. It was observed that the energy band gap is increased from 3.52 to 3.65 eV and refractive index of the films are decreased with the increase of substrate temperature. Moreover, considerable improvement in blue response of the films was noticed with increasing substrate temperature.

36 MATERIALS SCIENCE↗

Effect of high voltage electric field on structure and property of PEDOT:PSS film

Low electrical conductivity of PEDOT:PSS film is to some extent a limit for its wide application. To solve this problem, the high voltage electric field was used to improve the film’s electrical conductivity and its effects on the film’s structure and properties were investigated. The PEDOT:PSS film was prepared on quartz substrate with spin coating. Visible light transmittance of the prepared film was tested with UV–Visible spectroscopy and chemical structure was measured with Fourier transform Raman spectroscopy (FIRM). The surface morphology was characterized with AFM, and electrical conductivity was measured with Hall effects measurement. The results showed that with the increase of the electric field, the electrical conductivity of PEDOT:PSS film was boosted rapidly at first, and then improved slowly when the electric field was above 200 kV/m. The film’s electrical conductivity improved more than 17 times in total from 0.51 × 10{sup –3} up to 8.92 × 10{sup –3} S/m. However, the film’s visible light transmittance decreased only a little with the increase of the electric field, not more than 3%. In addition, despite little change in the chemical structure of the PEDOT:PSS film, its surface roughness increased significantly with the increase of the electric field intensity.

36 MATERIALS SCIENCE↗

Fundamental Mechanisms of Roughening and Smoothing During Thin Film Deposition

In this research program, we have explored the fundamental limits for thin film deposition in both crystalline and amorphous (i.e. non-crystalline) materials systems. For vacuum-based physical deposition processes such as sputter deposition, the background gas pressure of the inert gas (usually argon) used as the process gas has been found to be a key variable. Both a roughness transition and stress transition as a function of pressure have been linked to a common mechanism involving collisions of energetic particles from the deposition source with the process inert gas. As energetic particles collide with gas molecules in the deposition process they lose their energy rapidly if the pressure (and background gas density) is above a critical value. Both roughness and stress limit important properties of thin films for applications. In the area of epitaxial growth we have also discovered a related effect; there is a critical pressure below which highly crystalline layers grow in a layer-by-layer mode. This effect is also though to be due to energetic particle thermalization and scattering. Several other important effects such as the observation of coalescence dominated growth has been observed. This mode can be likened to the behavior of two-dimensional water droplets on the hood of a car during a rain storm; as the droplets grow and touch each other they tend to coalesce rapidly into new larger circular puddles, and this process proceeds exponentially as larger puddles overtake smaller ones and also merge with other large puddles. This discovery will enable more accurate simulations and modeling of epitaxial growth processes. We have also observed that epitaxial films undergo a roughening transition as a function of thickness, which is attributed to strain induced by the crystalline lattice mismatch with the substrate crystal. In addition, we have studied another physical deposition process called pulsed laser deposition. It differs from sputter deposition due to the pulsed nature of the deposition where particles arrive at the growth surface in an interval of a few microseconds. We have observed effects such as transient formation of two dimensional islands on elemental crystalline surfaces. Pulsed deposition may also lead to non-equilibrium phases in some cases, such as the observation anomalously high tetragonality for ferroelectric thin films. All of the results described above feature in-situ synchrotron X-ray scattering as the main experimental method, which has become an indispensable technique for observing the kinetics of structures forming in real-time. We have also investigated in-situ coherent X-ray scattering and have developed methods to characterize temporal correlations that are not possible to observe with low-coherence X-rays. A high profile result of this work is a new technique to monitor defect propagation velocities in thin films. This has practical significance since defects limit the properties of thin films and it is desirable to understand their properties and origin in order to control them for practical applications. More broadly, amorphous thin films and multilayers have applications in optical devices, including mirrors and filters. Epitaxial thin films and multilayers have applications in electronic devices such as ferroelectric multilayers for non-volatile data storage, and thermoelectric nanostructures for energy conversion. Our progress in this project points the way for improved deposition methods and for improved simulation and modeling of thin film deposition processes for nanoscale control of materials with novel applications in these areas.

36 MATERIALS SCIENCE↗

In Situ X-ray Measurements to Follow the Crystallization of BaTiO 3 Thin Films during RF-Magnetron Sputter Deposition

Here, we report on adding an important dimension to the fundamental understanding of the evolution of the thin film micro structure evolution. Thin films have gained broad attention in their applications for electro-optical devices, solar-cell technology, as well storage devices. Deep insights into fundamental functionalities can be realized via studying crystallization microstructure and formation processes of polycrystalline or epitaxial thin films. Besides the fundamental aspects, it is industrially important to minimize cost which intrinsically requires lower energy consumption at increasing performance which requires new approaches to thin film growth in general. Here, we present a state of the art sputtering technique that allows for time-resolved in situ studies of such thin film growth with a special focus on the crystallization via small angle scattering and X-ray diffraction. Focusing on the crystallization of the example material of BaTiO 3 , we demonstrate how a prototypical thin film forms and how detailed all phases of the structural evolution can be identified. The technique is shaped to enable a versatile approach for understanding and ultimately controlling a broad variety of growth processes, and more over it demonstrate how to in situ investigate the influence of single high temperature sputtering parameters on the film quality. It is shown that the whole evolution from nucleation, diffusion adsorption and grain growth to the crystallization can be observed during all stages of thin film growth as well as quantitatively as qualitatively. This can be used to optimize thin-film quality, efficiency and performance.

36 MATERIALS SCIENCE↗

Nanoimprinted Diffraction Gratings for Light Trapping in Crystal-Silicon Film Photovoltaics

Crystal-silicon (c-Si) film photovoltaics hold the promise of combining the advantages of state-of-the-art wafer-silicon technology with the scalability and the inherently much lower cost of thin-film solar technologies. In the thickness range of 2-20 μm very effective light trapping is essential to absorb sufficient red and near-infrared (NIR) light and reach targeted efficiencies of 16% 18%, as defined by the U.S. National Solar Technology Roadmap. One proposed method is diffractive light trapping, which, at least in certain wavelength ranges, can theoretically outperform light trapping through random scattering at a rough surface or interface. The goals of this project were (1) to develop a nanoimprinting process for a high-refractive-index dielectric material, (2) to fabricate diffraction gratings as back-reflectors using this material, and (3) to demonstrate for a 2c-Si film an improvement in AM1.5 photon absorption of at least 80% relative to single-pass absorption. We achieved goals (1) and (2). We developed a soft-imprint method for sol-based titanium dioxide precursor films (index range 2.3-2.4) and integrated imprinted films in thin-film silicon devices. We did not fully reach goal (3): depending on the model used for interpretation of the optical experimental data, AM1.5 photon absorption was improved by only 53% (coherent electromagnetic model) to 66% (non-coherent ray-tracing model). When compared to a metallized flat reference film (double-pass absorption), the improvement due to the grating is only 6%, if the (more conservative) electromagnetic model is used. Other important achievements from this project were: • We perfected an imprinting method for another ceramic material, aluminum oxide phosphate, which is index-matched with glass. • We tested diffractive light trapping at different incidence angles and found positive evidence for light trapping for angles up to 50°, although the light-trapping efficiency decreased with increasing incidence angle. • The extent of the trapped wavelength range scales with the refractive index of the dielectric material. The full benefit of a high refractive index, however, is only achieved if the dielectric layer underneath the grating layer (the residual layer) is sufficiently thick (several 100 nm). For a very thin residual layer, the light wave is predominantly localized in the underlying material during diffraction, and this material's refractive index then determines the trapping range. The (welcomed) consequence is that if this material is the silicon absorber layer, e.g. in a thin-film superstrate configuration, a very large trapping range can be achieved even if a low-index dielectric is used. We tested this directly through light-trapping experiments in glass plates using two different imprinted dielectric materials, titanium dioxide (index range 2.3-2.4) and aluminum oxide phosphate (index 1.5), with thick and thin residual layers. • We tested both copper and aluminum as low-cost reflector alternatives to silver on the grating back sides. In the relevant wavelength range above 650 nm, copper not only has the same high reflectance as silver, but the diffraction efficiency is also on par with silver. • A total of five scientific publications resulting from this work have either been published or are in preparation for submission (see Detailed Technical Report, below). Two conference presentations were given. In conclusion, we successfully developed nanoimprinting techniques for two ceramic precursor materials and tested diffractive light trapping in c-Si and nc-Si:H thin-film devices. The measured amount of light trapping did not fully reach our target value. The lessons learned from this project, however, both concerning experimental techniques and theoretical/modeling methods, have been extensive. Light trapping remains a central issue in thin c-Si technology, and we recommend to the US Department of Energy to increase research in this important area.

14 SOLAR ENERGY↗

Full Coverage Shaped Hole Film Cooling in an Accelerating Boundary Layer with High Free-Stream Turbulence

Full coverage shaped-hole film cooling and downstream heat transfer measurements have been acquired in the accelerating flows over a large cylindrical leading edge test surface. The shaped holes had an 8° lateral expansion angled at 30° to the surface with spanwise and streamwise spacings of 3 diameters. Measurements were conducted at four blowing ratios, two Reynolds numbers and six well documented turbulence conditions. Film cooling measurements were acquired over a four to one range in blowing ratio at the lower Reynolds number and at the two lower blowing ratios for the higher Reynolds number. The film cooling measurements were acquired at a coolant to free-stream density ratio of approximately 1.04. The flows were subjected to a low turbulence condition (Tu = 0.7%), two levels of turbulence for a smaller sized grid (Tu = 3.5%, and 7.9%), one turbulence level for a larger grid (8.1%), and two levels of turbulence generated using a mock aero-combustor (Tu = 9.3% and 13.7%). Turbulence level is shown to have a significant influence in mixing away film cooling coverage progressively as the flow develops in the streamwise direction. Effectiveness levels for the aero-combustor turbulence condition are reduced to as low as 20% of low turbulence values by the furthest downstream region. The film cooling discharge is located close to the leading edge with very thin and accelerating upstream boundary layers. Film cooling data at the lower Reynolds number, show that transitional flows have significantly improved effectiveness levels compared with turbulent flows. Downstream effectiveness levels are very similar to slot film cooling data taken at the same coolant flow rates over the same cylindrical test surface. However, slots perform significantly better in the near discharge region. These data are expected to be very useful in grounding computational predictions of full coverage shaped hole film cooling with elevated turbulence levels and acceleration. IR measurements were performed for the two lowest turbulence levels to document the spanwise variation in film cooling effectiveness and heat transfer.

20 FOSSIL-FUELED POWER PLANTS↗

Layer-by-Layer Synthesis of Thick Mesoporous TiO 2 Films with Vertically Oriented Accessible Nanopores and Their Application for Lithium-Ion Battery Negative Electrodes

TiO 2 films of varying thicknesses (up to ≈1.0 µm) with vertically oriented, accessible 7–9 nm nanopores are synthesized using an evaporation-induced self-assembly layer-by-layer technique. The hypothesis behind the approach is that epitaxial alignment of hydrophobic blocks of surfactant templates induces a consistent, accessible mesophase orientation across a multilayer film, ultimately leading to continuous, vertically aligned pore channels. Characterization using grazing incidence X-ray scattering, scanning electron microscopy, and impedance spectroscopy indicates that the pores are oriented vertically even in relatively thick films (up to 1 µm). These films contain a combination of amorphous and nanocrystalline anatase titania of value for electrochemical energy storage. When applied as negative electrodes in lithium-ion batteries, a capacity of 254 mAh g -1 is obtained after 200 cycles for a single-layer TiO 2 film prepared on modified substrate, higher than on unmodified substrate or nonporous TiO 2 film, due to the high accessibility of the vertically oriented channels in the films. Thicker films on modified substrate have increased absolute capacity because of higher mass loading but a reduced specific capacity because of transport limitations. These results suggest that the multilayer epitaxial approach is a viable way to prepare high capacity TiO 2 films with vertically oriented continuous nanopores.

25 ENERGY STORAGE↗

Combinatorial Growth of Vertically Aligned Nanocomposite Thin Films for Accelerated Exploration in Composition Variation

Combinatorial growth is capable of creating a compositional gradient for thin film materials and thus has been adopted to explore composition variation mostly for metallic alloy thin films and some dopant concentrations for ceramic thin films. This study uses a combinatorial pulsed laser deposition method to successfully fabricate two‐phase oxide–oxide vertically aligned nanocomposite (VAN) thin films of La 0.7 Sr 0.3 MnO 3 (LSMO)‐NiO with variable composition across the film area. The LSMO‐NiO compositional gradient across the film alters the two‐phase morphology of the VAN through varying nanopillar size and density. Additionally, the magnetic anisotropy and magnetoresistance properties of the nanocomposite thin films increase with increasing NiO composition. This demonstration of a combinatorial method for VAN growth can increase the efficiency of nanocomposite thin film research by allowing all possible compositions of thin film materials to be explored in a single deposition.

36 MATERIALS SCIENCE↗

Surface and interface of epitaxial CdTe film on CdS buffered van der Waals mica substrate

We report single crystal CdTe films are desirable for optoelectronic device applications. An important strategy of creating films with high crystallinity is through epitaxial growth on a proper single crystal substrate. We report the metalorganic chemical vapor deposition of epitaxial CdTe films on the CdS/mica substrate. The epitaxial CdS film was grown on a mica surface by thermal evaporation. Due to the weak van der Waals forces, epitaxy is achieved despite the very large interface lattice mismatch between CdS and mica (~21–55%). The surface morphology of mica, CdS and CdTe were quantified by atomic force microscopy. The near surface structures, orientations and texture of CdTe and CdS films were characterized by the unique reflection high-energy electron diffraction surface pole figure technique. The interfaces of CdTe and CdS films and mica were characterized by X-ray pole figure technique and transmission electron microscopy. The out-of-plane and in-plane epitaxy of the heteroepitaxial films stack are determined to be CdTe(111)//CdS(0001)//mica(001) and [$\overline{1}2\overline{1}$] CdTe //[$\overline{1}100$] CdS //[010] mica , respectively. The measured photoluminescence (PL), time resolved PL, photoresponse, and Hall mobility of the CdTe/CdS/mica indicate quality films. Finally, the use of van der Waals surface to grow epitaxial CdTe/CdS films offers an alternative strategy towards infrared imaging and solar cell applications.

36 MATERIALS SCIENCE↗

Dynamics of the chemo-optical response of supported films of nematic liquid crystals

We report a study that elucidates key physicochemical phenomena that underlie the dynamics of adsorbate-induced ordering transitions in micrometer-thick films of nematic liquid crystals (LCs) supported on chemically functionalized surfaces. By flowing a gas containing dimethyl methylphosphonate (DMMP) over a film of nematic 4-cyano-4'-pentylbiphenyl (5CB) supported on a surface decorated with aluminum perchlorate, we quantify the dynamics of the optical response (intensity of transmitted light) of the LC film as a function of key experimental parameters, including linear flow rate of the gas over the surface of the film and the concentration of the DMMP within the gas. Building from prior infrared spectroscopic analysis revealing that the optical response of the LC is due to an ordering transition triggered by competitive ligand-exchange reactions at the chemically functionalized surface (i.e., between the phosphonate and nitrile groups of the DMMP and LC, respectively, with the aluminum perchlorate-decorated surface), we interpret the measurements reported herein within the framework of a simple model of mass transport. The model reveals that the rate-limiting process underlying the response of the LC is the mass transport of the DMMP across the concentration boundary layer formed on the vapor side of the LC–vapor interface, and not the mass transport of DMMP across the LC film nor the intrinsic ligand exchange kinetics. The analysis also reveals that the response of the LC is triggered once the concentration of DMMP within the LC film rises to approximately 0.25 mM. By flowing a stream of gas free of DMMP over a LC film pre-exposed to DMMP, we established that the relaxation of the LC film to the initial state is also largely controlled by mass transport of the DMMP across the vapor side of the LC–vapor interface. Analysis of the relaxation of the system leads to an estimate of the sensitivity of the supported LC film to the concentration of DMMP in the gas phase (approximately 150 ppb for the non-optimized system reported in this paper). These results and others reported in this paper identify key physical phenomena that dictate the dynamics of adsorbate-induced ordering transitions in LC systems, and provide important guidance to the design of LCs as chemo-responsive materials for use in sensors.

dimethyl methylphosphonate↗

Structured SiCu thin films in LiB as anodes

Both helical and inclined columnar Si–10 at.% Cu structured thin films were deposited on Cu substrates using glancing angle deposition (GLAD) technique. In order to deposit Cu and Si two evaporation sources were used. Ion assistance was utilized in the first 5 min of the GLAD to enhance the adhesion and the density of the films. These films were characterized by thin film XRD, GDOES, SEM, and EDS. Electrochemical characterizations were made by testing the thin films as anodes in half-cells for 100 cycles. The results showed that the columnar SiCu thin film delivered 2200 mAh g -1 , where the helical one exhibited 2600 mAh g -1 , and, their initial coulombic efficiencies were found to be 38%–50% respectively. For the columnar and the helical thin film anodes, sustainable 520 and 800 mAh g -1 with 90% and 99% coulombic efficiencies were achieved for 100 cycles. These sustainable capacities showed the importance of the thin film structure having nano-sized crystals and amorphous particles. The higher surface area of the helices increases the capacity of the electrode because the contact area of the thin film anode with Li ions is increased, and the polarization which otherwise forms on the anode surface due to SEI formation is decreased. In addition, because of larger interspaces between the helices the ability of the anode to accommodate the volumetric changes is improved, which results in a higher coulombic efficiency and capacity retention during cycling test.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Formation of Al 3 Sc in Al 0.8 Sc 0.2 thin films

We report the formation of Al 3 Sc, in 100 nm Al 0.8 Sc 0.2 films, is found to be driven by exposure to high temperature through higher deposition temperature or annealing. High film resistivity was observed in films with lower deposition temperature that exhibited a lack of crystallinity, which is anticipated to cause more electron scattering. An increase in deposition temperature allows for the nucleation and growth of crystalline Al 3 Sc regions that were verified by electron diffraction. The increase in crystallinity reduces electron scattering, which results in lower film resistivity. Annealing Al 0.8 Sc 0.2 films at 600 °C in an Ar vacuum environment also allows for the formation and recrystallization of Al 3 Sc and Al and yields saturated resistivity values between 9.58 and 10.5 μΩ-cm regardless of sputter conditions. Al 3 Sc was found to nucleate and grow in a random orientation when deposited on SiO 2 , and highly {111} textured when deposited on 100 nm Ti and AlN films that were used as template layers. The rocking curve of the Al 3 Sc 111 reflection for the as-deposited films on Ti and AlN at 450 °C was 1.79° and 1.68°, respectively. Annealing the film deposited on the AlN template reduced the rocking curve substantially to 1.01° due to recrystallization of Al 3 Sc and Al within the film.

36 MATERIALS SCIENCE↗

A General Solution Route to Nanoporous Metal Oxide Films

Metal oxide semiconductors are of interest as efficient, stable, and low-cost photoanode materials for photoelectrochemical water splitting, but their characteristically poor charge transport properties remain a fundamental challenge to practical use. Nanoporous metal oxide films that feature open bicontinuous networks of nanocrystals and nanopores can overcome such inefficient charge transport to enable high-performance photoanodes. Here, this paper describes a general method to make high-quality nanoporous films of metal oxides by spin coating and calcining molecular inks that contain a porosity-generating block copolymer. Phase-pure nanoporous films of BiFeO 3 , FeWO 4 , WO 3 , Fe 2 O 3 , and TiO 2 serve to demonstrate the versatility of the approach. It is demonstrated that the crystallite size, film porosity, and film thickness can be independently tuned by adjusting the ink composition and film processing conditions. The method is extended to fabricate core–shell nanoporous films consisting of a nanoporous film coated in a thin shell of a second metal oxide, using WO 3 –BiVO 4 and BiFeO 3 –BiVO 4 as examples. Given its simplicity and flexibility, this solution-phase route should prove useful for making nanoporous films of many different materials for a variety of applications, including energy conversion and storage, catalysis, and chemical sensing.

coating materials↗

Thickness Limit for Alignment of Block Copolymer Films Using Solvent Vapor Annealing with Shear

The swelling and deswelling of a cross-linked polydimethylsiloxane (PDMS) pad adhered to a block copolymer (BCP) film during solvent vapor annealing (SVA) provides sufficient shear force to produce highly aligned domains over macroscopic dimensions in thin films. Here in this paper, we examine how far this alignment can propagate through the thickness of a BCP film to understand the limits for efficacy of the SVA-S (SVA with shear) process. Films of cylinder-forming polystyrene-block-polyisoprene-block-polystyrene (SIS) ranging from 100 nm to more than 100 μm are examined using the same processing conditions. The SIS surface in contact with the PDMS is always well-aligned, with Herman’s orientation parameter (S) exceeding 0.9 as determined from AFM micrographs, but the bottom surface in contact with the silicon wafer is not aligned for the thickest films. The average orientation through the film thickness was determined by transmission small-angle X-ray scattering (SAXS), with S decreasing gradually with increasing thickness for SIS films thinner than 24 μm, but S remains >0.8. S precipitously decreases for thicker films. A stop-etch-image approach allows the gradient in orientation through the thickness to be elucidated. The integration of this local orientation profile agrees with the average S obtained from SAXS. These results demonstrate the effective alignment of supported thick BCP films of order 10 μm, which could be useful for BCP coatings for optical applications.

36 MATERIALS SCIENCE↗

Tuning Film Stresses for Open-Air Processing of Stable Metal Halide Perovskites

Challenges to upscaling metal halide perovskites (MHPs) include mechanical film stresses that accelerate degradation, dominate at the module scale, and can lead to delamination or fracture. In this work, we demonstrate open-air blade coating of single-step coated perovskite as a scalable method to control residual film stress after processing and introduce beneficial compression in the thin film with the use of polymer additives such as gellan gum and corn starch. The optoelectronic properties of MHP films with compression are improved with higher photoluminescence yields. MHP film stability is significantly improved under compression, under humidity, heat, and thermal cycling. By measuring the evolution of film stresses, we demonstrate for the first time that stress relaxation occurs in MHP films with tensile stress that correlates with film degradation. Finally, this discovery of a new mechanism underpinning MHP degradation shows that film stress can be used as a parameter to screen MHP devices and modules for quality control before deployment as a design for reliability criterion.

14 SOLAR ENERGY↗

Physicochemical controls on absorbed water film thickness in unsaturated geological media

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here, the problem of adsorbed water film thickness is examined through combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses, and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable, and showed that pendular rings within drained porous media retain most of the 'residual' water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (< 10 mol m{sup -3}) on surfaces with higher magnitude electrostatic potentials (more negative than - 50 mV). Adsorbed water films are predicted to usually range in thickness from 1 to 20 nm in drained pores and fractures of unsaturated environments.

54 ENVIRONMENTAL SCIENCES↗

Ultrathin amorphous carbon films synthesized by filtered cathodic vacuum arc used as protective overcoats of heat-assisted magnetic recording heads

Despite numerous investigations of amorphous carbon (a-C) films, a comprehensive study of the feasibility and optimization of sub-5-nm-thick a-C films deposited onto the write pole of heat-assisted magnetic recording (HAMR) heads is lacking. The main objective of this study was to identify the role of pulse substrate bias voltage and C+ ion incidence angle on the structure and thickness of 1–4-nm-thick a-C films deposited by a rather new thin-film deposition method, known as filtered cathodic vacuum arc (FCVA). The cross-sectional structure of a-C films synthesized under various FCVA conditions was examined by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). It was found that film growth under process conditions of low-to-intermediate substrate bias voltage (in the range of -25 to -100 V), low ion incidence angle (10°), very short deposition time (6 s), and fixed other deposition parameters (65% duty cycle of substrate pulse biasing and 1.48 × 10 19 ions/m 2 ·s ion flux) yields a-C films of thickness ≤4 nm characterized by a significant content (~50–60 at%) of tetrahedral ( sp 3 ) carbon atom hybridization. A threshold where sp 3 hybridization is greatly reduced due to limited film growth was determined from the HRTEM/STEM and EELS measurements. The results of this study demonstrate the viability of FCVA to produce extremely thin and uniform protective a-C films with relatively high sp 3 contents for HAMR heads.

Science & Technology - Other Topics↗