Freezing transition of Langmuir-Gibbs alkane films on water

We show that adding CTAB (CTAB, hexadecyltrimethylammonium bromide) in sub-millimolar bulk concentrations to water reduces its surface tension (ST) to a level where spontaneous surface spreading of a monolayer of medium-sized alkane (C_nH_2n+2, 12 ≤ n ≤ 17) occurs. ST and X-ray reflectivity (XR) measurements are used to show that the quasi two-dimensional (2D) liquid monolayer can be driven through a reversible surface freezing phase transition upon cooling. Grazing incidence diffraction (GID) shows that the frozen monolayer is crystalline, hexagonally packed, with surface-normal molecules, and a crystalline coherence length of at least a few hundred Å, very similar to the structure of surface-frozen (SF) monolayers at the surface of similar-length alkane melts.     

X-ray mirrors on flexible polymer substrates fabricated by atomic layer deposition

Atomic layer deposition (ALD) techniques were used to fabricate W/Al₂O₃ superlattices with high X-ray reflectivity on flexible Kapton® polyimide and polyethylene naphthalate (PEN) polymer substrates. Reflectivities of 78% and 74% at λ = 1.54 Å were measured for 6-bilayer W/Al₂O₃ superlattices on Kapton® polyimide and PEN, respectively. These excellent X-ray reflectivities are attributed to precise bilayer thicknesses and ultrasmooth interfaces obtained by ALD and smoothing of the initial polymer surface by an Al₂O₃ ALD layer. The conformal ALD film growth also produces correlated roughness that enhances the reflectivity. These W/Al₂O₃ superlattices on flexible polymers should be useful for ultralight and adjustable radius of curvature X-ray mirrors.     

Surface and structural disorder in MBE and sputtering deposited Cu thin films revealed by X-ray measurements

Copper thin films have been deposited on Si substrates by molecular beam epitaxy (MBE) at different deposition rates varying from 1 up to 22 Å/s. X-ray reflectivity and θ-2θ measurements have shown that the surface roughness correlation length, the structural disorder and the grain dimensions are strongly affected by the deposition rate. Comparing these results with those obtained for sputtered deposited thin films with a low deposition rate (2.5 Å/s), a clear similarity between the MBE samples deposited with the highest deposition rate and the sputtering Cu films is observed. This result has been interpreted considering the different energies of the particles that approach the substrate in the two deposition techniques.     

Characterization of thermally stable W/Ni multilayers by X-rays and cross-sectional transmission electron microscopy

W/Ni multilayer structures (MLS) composed of 5 and 10 bilayers, with composition W(15 Å)/Ni(55 Å), have been deposited on float glass substrate using ion-beam sputtering. X-ray reflectivity and wide-angle X-ray diffraction techniques have been used to study their interface characteristics, such as layer thickness, interface roughness and change in structural parameters. The fabricated MLS were found to be oriented along (111) of Ni having superlattice modulation perpendicular to the film plane. Thermal annealing studies on these multilayers showed that these were stable up to 500 °C. Cross-sectional transmission electron microscopy and selected area electron diffraction studies on as-deposited W/Ni MLS of 10 bilayers revealed well formed interfaces without any correlated roughness. The thicknesses of different layers were found to vary along the film thickness.     

Energy-dispersive X-ray reflectivity and GID for real-time growth studies of pentacene thin films

We use energy-dispersive X-ray reflectivity and grazing incidence diffraction (GID) to follow the growth of the crystalline organic semiconductor pentacene on silicon oxide in-situ and in real-time. The technique allows for monitoring Bragg reflections and measuring X-ray growth oscillations with a time resolution of 1 min in a wide q-range in reciprocal space extending over 0.25-0.80 Å^− 1, i.e. sampling a large number of Fourier components simultaneously. A quantitative analysis of growth oscillations at several q-points yields the evolution of the surface roughness, showing a marked transition from layer-by-layer growth to strong roughening after four monolayers of pentacene have been deposited.     

Control of substrate surface temperature in millisecond annealing technique using thermal plasma jet

Temporal variations of substrate surface temperature in scanning Ar thermal plasma jet has been investigated based on an analysis of transient changes in optical reflectivity. The accuracy of the temperature measurement has been evaluated to be 30 K at temperature around 1760 K. The maximum surface temperature (T_max) is controlled in the range from ∼ 960 to ∼ 1780 K with keeping the annealing duration (t_a) around ∼ 3 ms by changing the Ar gas flow rate (f) and distance between the plasma jet and the substrate (d) under a constant scanning speed (ν) of 500 mm/s.     

Temperature-dependent growth of pulsed-laser-deposited bismuth thin films on glass substrates

Bismuth thin films were grown by pulsed-laser deposition on glass substrates with the substrate temperature from − 40 °C to 200 °C. The structure of the films was characterized by X-ray diffraction. The surface morphology was studied by atomic force microscopy and X-ray reflectivity. The electrical properties of the films were probed by Hall and van der Pauw measurements. We observed changes in the orientation, grain size and roughness of the bismuth films as a function of the substrate temperature. In particular, at − 30 °C, the surface roughness was drastically reduced, leading to very smooth bismuth films with highly (111)-preferred orientation. Furthermore, the preferred orientation disappeared at around − 40 °C.     

Pulsed laser ablated off-stoichiometric thin films of the Heusler alloy Co2TiSn on Si (100) substrate

We report the growth of thin films of ferromagnetic Heusler alloy Co₂TiSn on Si (100) substrate using KrF excimer pulsed laser ablation. Films of thicknesses ranging from 8 to 220 nm were deposited on Si (100) substrate heated up to 200 ± 10 °C, with an aim to study the structural, morphological and magnetic properties. The grown films are off-stoichiometric, polycrystalline, having single-phase with high degree of (220) texturing. Angle dependent fluorescence measurements suggest no segregation of alloying elements as a function of depth. X-ray reflectivity measurements indicate that all the films are having low density layer at the top as well as at the film-substrate interface. Magneto optical Kerr effect measurements at room temperature reveal clear hysteresis loops suggesting ferromagnetic behavior of the films. Thermal annealing at temperature ≥ 220 °C suggest transformation of Co₂TiSn phase into cobalt silicide phase, which confirms the necessity of low substrate temperature (< 220 °C) to produce such single-phase Co₂TiSn films.     

Fabrication of calix[4]pyrrole nanofilms at the glassy carbon surface and their characterization by spectroscopic, optic and electrochemical methods

meso-Octamethylcalix[4]pyrrole (CP) and meso-heptaethylcalix[4]pyrrole-meso-4-aminophenyl (4APCP) modified glassy carbon (GC) electrodes were prepared by the electrochemical oxidation in acetonitrile solution. Binding of the calix[4]pyrroles with the glassy carbon surface was investigated that it is through the etheric linkage revealed from the reflection-absorption infrared spectroscopy (RAIRS). Surface films of CP and 4APCP were investigated by cyclic voltammetry (CV), ellipsometry, X-ray photoelectron spectroscopy, RAIRS and the contact angle measurements. The thicknesses of the films were determined by ellipsometry which confirmed that the film was multilayer and homogeneous over the surface. Ellipsometric measurements also provided that the CP and 4APCP film thicknesses were 2.49 nm and 4.58 nm for 6 CV cycle modification, corresponding to 66 μF/cm² and 106 μF/cm² capacitances obtained by CV. The wetting behavior was examined by contact angle measurements and found that the hydrophobicity of the GC-4APCP surface was higher than that of GC-CP, probably due to the aromatic meso substituent present in the former.     

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

A high electron density (> 10¹¹ cm^− 3) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 Å/s is achieved at a substrate temperature of 150 °C with a high Raman crystallinity and a low defect density of (1-2) × 10¹⁶ cm^− 3. Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H_α/SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity.     

Interfacial electron density profile in Nb/Si bilayer films: an X-ray reflectivity study

This article describes a systematic study of the nature of interfaces involved in a Nb layer deposited on Si (Nb-on-Si) and Si layer deposited on Nb (Si-on-Nb) bilayer films by using a UHV electron beam evaporation technique, having individual layer thickness of 35 and 100 Å each. By using Grazing angle X-ray reflectivity and adopting a proper modelling technique the electron density profile (EDP) as a function of depth has been determined in the samples. EDP determined in as-deposited 35 Å Nb and 35 Å Si bilayer films show that the width of Si-on-Nb and Nb-on-Si interfaces are 20 Å and 40 Å, respectively. The difference observed in the width of two interfaces is attributed to the different growth morphology of 35 Å Nb and 35 Å Si single-layer films as revealed by atomic force microscopy (AFM) investigations. EDP determined from measured XRR data for 100 Å Nb and 100 Å Si deposited bilayer film shows that the width of Si-on-Nb interface is 10 Å. This observed width is smaller than the similar interface in the case of samples having an individual layer thickness of 35 Å. The corresponding interface width of Nb-on-Si is found to be 45 Å and marginally more than the similar interface in the case of the 35 Å Nb/35 Å Si bilayer samples. AFM studies carried out on 100 Å Nb and Si layers deposited separately on float glass substrate indicate similar gross as well as subtle morphological features and cannot be attributed to the observed asymmetry in this case. The observed asymmetry in EDP of two interfaces in this case is due to the enhanced diffusion of Si into the formed metal layer relative to the diffusion into the already deposited metal layer.     

Immobilization of dendrimers on Si-C linked carboxylic acid-terminated monolayers on silicon(111)

Poly(amidoamine) dendrimers were attached to activated undecanoic acid monolayers, covalently linked to smooth silicon surfaces via Si-C bonds. The resulting ultra-thin dendrimer films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XR) and atomic force microscopy (AFM). XPS results suggested amide bond formation between the dendrimer and the surface carboxylic acid groups. XR yielded thicknesses of 10 Å for the alkyl region of the undecanoic acid monolayer and 12 Å for the dendrimer layer, considerably smaller than the diameter of these spherical macromolecules in solution. This was consistent with AFM images showing collapsed dendrimers on the surface. It was concluded that the deformation arose from a large number of amine groups on the surface of each dendrimer reacting efficiently with the activated surface, whereby the dendrimers can deform to fill voids while spreading over the activated surface to form a homogeneous macromolecular layer.     

Characterization of magnetron co-sputtered W-doped C-based films

In this paper, W-doped C-based coatings were deposited on steel and silicon substrates by RF magnetron sputtering, using W and C targets, varying the cathode power applied to the W target and the substrate bias. The chemical composition was varied by placing the substrates in a row facing the C and W targets. W content in the films increased from 1 to 2 at.% over the C target to ∼ 73 at.% over the W target. The coatings with W content lower than ∼ 12 at.% and ∼ 23 at.%, for biased and unbiased conditions, respectively, showed X-ray amorphous structures, although carbide nanocrystals must exist as shown by the detection of the WC_1−x phase in films with higher W content. C-rich films were very dense and developed a columnar morphology with increasing W content. An improvement in the hardness (from 10 GPa, up to 25 GPa) of the films was achieved either when negative substrate bias was used in the deposition, or when the WC_1−x phase was detected by X-ray diffraction. The adhesion of the coatings is very low with spontaneous spallation of those deposited with negative substrate bias higher than 45 V. Varieties in cathode power (90 W or 120 W) applied to the W target showed no observable influence on the characteristics of the films.     

Investigations of thin film structures of WO3 and WO3 with Pd for hydrogen detection in a surface acoustic wave sensor system

A single thin film sensor structure of WO₃ (∼ 50 nm) and bilayer sensor structure of WO₃ (∼ 50 nm) with a very thin film of palladium (Pd ∼ 18 nm) on the top, have been studied for hydrogen gas-sensing application at ∼ 30 °C and ∼ 50 °C. The structures were obtained by vacuum deposition (first the WO₃ and than the Pd film) onto a LiNbO₃ Y-cut Z-propagating substrate making use of the surface acoustic wave method and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneously monitoring of the planar resistance of the structure. In the case of a bilayer structure a very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases of the bilayer structure resistance. These frequency changes are on the level of 2.4 kHz to 4% of hydrogen concentration in dry air, whereas in the case of a single WO₃ structure almost no frequency shift is observed.     

Characteristics of highly orientated BiFeO3 thin films on a LaNiO3-coated Si substrate by RF sputtering

BiFeO₃ (BFO) films were grown on LaNiO₃-coated Si substrate by a RF magnetron sputtering system at temperatures in the range of 300-700 °C. X-ray reflectivity and high-resolution diffraction measurements were employed to characterize the microstructure of these films. For a substrate temperature below 300 °C and at 700 °C only partially crystalline films and completely randomly polycrystalline films were grown, whereas highly (001)-orientated BFO film was obtained for a substrate temperature in the range of 400-600 °C. The crystalline quality of BFO thin films increase as the deposition temperature increase except for the film deposited at 700 °C. The fitted result from X-ray reflectivity curves show that the densities of the BFO films are slightly less than their bulk values. For the BFO films deposited at 300-600 °C, the higher the deposition temperature, the larger the remnant polarization and surface roughness of the films present.     

Temperature treatment of semiconducting polymers: An X-ray reflectivity study

The influence of temperature treatment on three types of conjugated polymer thin films, named poly(3-hexylthiophene) (P3HT), polyarylamine (PAA) and octylfluorene-bithiophene copolymer (F8T2) is studied. A detailed knowledge of the film morphology and crystalline structure is important since the performance of organic thin film transistors is extremely sensitive to small changes of morphology and structure. Samples are prepared via a spin-casting process on thermal oxidized silicon wafers. The influence of heat treatment in the range from ambient temperatures to 600 K is studied with specular X-ray reflectivity, X-ray diffraction and differential scanning calorimetry. The morphological parameters like layer thicknesses, electron densities and roughnesses of the interface and of the surface are calculated from the XRR measurements. The maximum change of layer thickness due to heat treatment is 15% of the initial layer thicknesses. The maximum variation of the mean electron densities are about 20% and the rms surface roughness vary from 2 Å up to 20 Å as a result of annealing. Interface roughness show variation of about 1 Å. Strong variations of the morphological parameters next to phase transition temperatures are observed as well.     

Effects of ion-assisted growth on the layer definition in Cr/Sc multilayers

Nano-structural evolution of layer morphology and interfacial roughness in Cr/Sc metal multilayers grown with ion assistance during magnetron sputter deposition has been investigated by high resolution transmission electron microscopy and hard X-ray reflectivity. Calculations based on a binary collision model predict an ion-assisted growth window for optimized Cr/Sc multilayer interface sharpness, within the ion energy range of 21 eV to 37 eV and an ion flux of ∼ 10 ions per deposited atom. Multilayers with nominal modulation periods in the range of 1.6 nm to 10.2 nm, grown with these conditions, exhibit a well-defined layer structure with an improved flattening and abruptness of the interfaces. It is shown that multilayers with a modulation period smaller than 3.4 nm have clear benefit from the reduced intermixing obtained by utilizing a two-stage ion energy modulation for each individual layer. The amorphization of Sc and Cr layers, below certain thicknesses, is found to be independent of the low energy ion-assistance. It is also shown that the Cr/Sc multilayers, containing periods less than ∼ 2 nm are ‘self healing’ i.e. they re-gain abrupt interfaces and flat layers after morphological disturbances during ion assisted growth. In comparison, multilayers grown without ion-assistance exhibited severe roughness and layer distortions.     

Ultra-thin films based on random copolymers containing perfluoropolyether side chains

Random copolymers were synthesised by copolymerizing methylmethacrylate and perfluoropolyetherurethanemethacrylate monomers, differing for the structural unit of the fluorinated chain, its end group and its molecular weight. The copolymers obtained had similar molecular weight and polydispersity, with a fluorine content between 5 and 10% wt/wt; they showed remarkable features such as biphasicity with coexistence of soft domains made of the perfluoropolyether chains and hard domains due to the methylmethacrylate backbone: the glass transition temperature T_g of the soft and hard phases was T_g1 < 90 °C and T_g2 ≅ 110 °C respectively. All the copolymers were highly hydrophobic: water contact angle was always higher than 105°. The copolymers were used for the preparation of ultra thin films by spin coatings: by atomic force microscopy and X-ray reflectivity the thickness was found in the range of 20-400 Å depending on the spinning conditions, in particular the concentration of the spun solutions. The films were also highly smooth, with a roughness lower than 5 Å.     

Low temperature (< 100 °C) fabrication of thin film silicon solar cells by HWCVD

Amorphous silicon films have been made by HWCVD at a very low substrate temperature of ≤ 100 °C (in a dynamic substrate heating mode) without artificial substrate cooling, through a substantial increase of the filament-substrate distance (∼ 80 mm) and using one straight tantalum filament. The material is made at a reasonable deposition rate of 0.11 nm/s. Optimized films made this way have device quality, as confirmed by the photosensitivity of > 10⁵. Furthermore, they possess a low structural disorder, manifested by the small Γ/2 value (half width at half maximum) of the transverse optic (TO) Si-Si vibration peak (at 480 cm^− 1) in the Raman spectrum of ∼ 30.4 cm^− 1, which translates into a bond angle variation of only ∼ 6.4°. The evidence gathered from the studies on the structure of the HWCVD grown film by three different techniques, Raman spectroscopy, spectroscopic ellipsometry and transmission electron microscopy, indicate that we have been able to make a photosensitive material with a structural disorder that is smaller than that expected at such a low deposition temperature.Tested in a p-i-n solar cell on Asahi SnO₂:F coated glass (without ZnO at the back reflector), this i-layer gave an efficiency of 3.4%. To our knowledge, this is the first report of a HWCVD thin film silicon solar cell made at such a low temperature.     

A simple and low-temperature hydrothermal route for the synthesis of tubular α-FeOOH

Tubular α-FeOOH was synthesized via hydrothermal reaction at 120 °C. X-ray diffraction (XRD) pattern indicates that the as-prepared sample is the pure orthorhombic phase α-FeOOH. Fourier transform infrared (FT-IR) analysis further confirms the formation of orthorhombic phase α-FeOOH. The morphology and structure of the as-obtained product were characterized by transmission electron microscopy (TEM) techniques. TEM images show a high degree of contrast between the bright central part and the darker edges, demonstrating the hollow core of the product. The obtained tubular α-FeOOH was ∼ 10 nm in outer diameter and ∼ 6 nm in inner diameter, respectively. High-resolution TEM image of one single nanotube shows the clearly resolved interplanar spacing of about 4.18 Å, which corresponds to the spacing between (110) planes of the orthorhombic-type α-FeOOH crystal. The room-temperature UV-Vis absorption spectrum of the tubular α-FeOOH nanostructures is presented.