Ultrathin film deposition by liquid CO2 free meniscus coating-uniformity and morphology

Ultrathin organic films of sucrose octaacetate (SOA) were deposited on 12.5 cm diameter silicon wafer substrates using high-pressure free meniscus coating (hFMC) with liquid CO2 (l-CO2) as a coating solvent. The dry film thickness across the wafer and the morphology of deposited films were characterized as a function of coating conditions-withdrawal velocity, solution concentration, and evaporation driving force (deltaP). When no evaporation driving force was applied (deltaP = 0), highly uniform films were deposited with thickness in the range of 8-105 angstroms over the entire concentration range (3-11 wt%). Uniform films were also obtained at low concentrations (3-5 wt%) with a low evaporation driving force (deltaP = 0.0138 MPa). However, films deposited at medium to high concentrations (7-11 wt%) were thicker (110-570 angstroms) and less uniform, with larger nonuniformities at higher applied evaporation driving forces. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology including drying defects and film roughness. Films deposited without evaporation had no apparent drying defects and very low root-mean-square (RMS) roughness (1.4-3.8 angstroms). Spinodal-like dewetting morphologies including holes with diameters in the range of 100-300 nm, and surface undulations were observed in films deposited at medium concentration (7 wt%) and low deltaP (0.0138-0.0276 MPa). At higher concentrations and higher evaporative driving forces, spinodal-like dewetting morphologies disappeared but concentric ring defect structures were observed with diameters in the range 20-125 microm. The film thickness and morphology of SOA films deposited from 1-CO2 hFMC were compared to those deposited from toluene and acetone under normal dip coating. Films deposited from l-CO2 hFMC were much thinner, more uniform, and exhibited much fewer drying defects and lower RMS roughness.     

Self-assembly and morphology control of new L-glutamic acid-based amphiphilic random copolymers: giant vesicles, vesicles, spheres, and honeycomb film

New amphiphilic random copolymers containing hydrophobic dodecyl (C12) chain and hydrophilic L-glutamic acid were synthesized, and their self-assembly in solution as well as on the solid surfaces was investigated. The self-assembly behavior of these polymers are largely dependent on their hydrophilic and hydrophobic balances. The copolymer with a more hydrophobic alkyl chain (～90%) self-assembled into giant vesicles with a diameter of several micrometers in a mixed solvent of ethanol and water. When the hydrophobic ratio decreased to ca. 76%, the polymer self-assembled into conventional vesicles with several hundred nanometers. The giant vesicles could be fused in certain conditions, while the conventional vesicles were stable. When the content of the hydrophilic part was further increased, no organized structures were formed. On the other hand, when the copolymer solutions were directly cast on solid substrates such as silicon plates, films with organized nanostructures could also be obtained, the morphology of which depended on solvent selection. When ethanol or methanol was used, spheres were obtained. When dichloromethane was used as the solvent, honeycomb-like morphologies were obtained. These results showed that through appropriate molecular design, random copolymer could self-assemble into various organized structures, which could be regulated through the hydrophobic/hydrophilic balance and the solvents.     

Chemical reaction-inspired crystal growth of a coordination polymer toward morphology design and control

This paper reports a novel crystal growth system of a coordination framework {[Cu3(CN)3{hat-(CN)3(OEt)3}]}n (1) (hat-(CN)3(OEt)3 = 2,6,10-tricyano-3,7,11-triethoxy-1,4,5,8,9,12-hexaazatriphenylene). The coordination polymer is crystallized through the reaction of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (hat-(CN)6), ethanol, and copper(I) complex, involving the breaking and forming of covalent bonds. The crystal morphologies obtained in the present system contain dumbbells, cogwheels, and superlattices. Moreover, in the growth perpendicular to the c-axis, periodic ramification at regular interval is observed, affording superlattice morphologies. Observation of the growth of dumbbell crystals shows that the growth rates parallel and perpendicular to the crystallographic c-axis are quite different: the former shows a drastic change with the reaction duration, while the latter is almost constant. These results are reproduced as a simple reaction-diffusion system, indicating that chemical reactions on crystal surfaces play an important role in determining the macroscopic crystal morphologies.     

Substrate-mediated interactions on solid surfaces: theory, experiment, and consequences for thin-film morphology

When two or more atoms bind to a solid surface, the substrate can mediate an interaction between them. In this review, we discuss the origins of this interaction and the theories that describe substrate-mediated interactions, including recent studies with electronic density-functional theory. We summarize the results of experimental studies, in particular those with scanning–tunneling microscopy, aimed at quantifying substrate-mediated interactions. Over the intermediate range, these interactions can be strong enough to influence the ordering of adsorbates at surfaces. We discuss the results of recent studies, employing kinetic Monte Carlo simulations that probe the ramifications of these interactions for the morphology in thin-film epitaxy.     

Sunfish cationic amphiphiles: toward an adaptative lipoplex morphology

A detailed physicochemical study is presented on a new class of cationic amphiphiles, Sunfish amphiphiles, recently designed, synthesized, and tested for gene delivery. These materials have two hydrophobic tails, connected to the cationic pyridinium headgroup at the 1- and 4-positions. Two extreme morphologies can be visualized, i.e. one by back-folding involving association of both tails at one side of the pyridinium ring and one by independent unfolding of the tails, the two molecular geometries leading to considerable differences in the aggregate morphology. The behavior of six members of the Sunfish family in mixtures with DOPE, applying different conditions relevant for transfection, has been studied by a combination of techniques (DLS, DSC, NMR, SAXS, Cryo-TEM, fluorescence, etc.). The effects of structural parameters such as the presence of unsaturation in the tails and length of the alkyl chains on the properties of the aggregates have been assessed. A correlation of these structural data with cellular transfection efficiencies reveals that the highest transfection efficiency is obtained with those amphiphiles that are easily hydrated, form fluid aggregates, and undergo a transition to the inverted hexagonal phase in the presence of plasmid DNA (p-DNA) at physiological ionic strength.     

Moving contact lines and Langmuir-Blodgett film deposition

The objective of this paper is to point out the close relationship between contact line dynamics and LB film depositions, and it is designed to serve as a blueprint for future analysis of the LB technique. Moving contact lines and contact angles play a major role in Langmuir-Blodgett ultrathin film depositions. Although the effect of contact angles has been recognized for many years, a fundamental and comprehensive explanation of the phenomena taking place at the contact line has not been formulated before. Our understanding of contact line dynamics has improved thanks to careful experiments and new theoretical developments. Flow patterns depend on dynamic contact angle and the ratio of viscosities of the gas and liquid phases. More recently dynamic contact angles-and flow patterns-have been linked to forces of molecular and double-layer origin. The dynamic relationship of flow patterns to interfacial and transport properties can be used to explain seemingly contradictory experimental results reported by researchers during more than 60 years of experience with the L-B technique. Windows of operability can be defined for X-type and Z-type depositions that are useful in the design of experimental and industrial L-B deposition equipment.     

Evolution of the interface and metal film morphology in the vapor deposition of Ti on hexadecanethiolate hydrocarbon monolayers on Au

The combination of in situ X-ray photoelectron spectroscopy, infrared reflection spectroscopy, atomic force microscopy, and time-of-flight secondary ion mass spectrometry are used to probe the nature of the evolving interface chemistry and metal morphology arising from Ti vapor deposition onto the surface of a CH(3)(CH(2))(15)S/Au{111} self-assembled monolayer (SAM) at ambient temperature. The results show that for a deposition rate of approximately 0.15 Ti atom.nm(-2).s(-1) a highly nonuniform Ti overlayer is produced via a process in which a large fraction of impinging Ti atoms do not stick to the bare SAM surface. The adsorbed atoms form isolated Ti clusters and react with CH(3) groups to form carbide products at the cluster-SAM interfaces. Further growth of Ti clusters appears to be concentrated at these scattered reaction centers. The SAM molecules in the local vicinity are subsequently degraded to inorganic products, progressing deeper into the monolayer as the deposition proceeds to give an inorganic/organic nanocomposite. A continuous overlayer does not form until metal coverage approaches approximately 50 Ti atoms per SAM molecule. These data indicate that for applications such as molecular device contacts the use of Ti may be highly problematic, suffering from both a highly nonuniform contact area and the presence of extensive inorganic products such as nonstoichiometric carbides and hydrides.     

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc.     

Optimisation of mercury film deposition on glassy carbon electrodes: evaluation of the combined effects of pH, thiocyanate ion and deposition potential

The combined effects of pH, thiocyanate ion and deposition potential in the characteristics of thin mercury film electrodes plated on glassy carbon surfaces are evaluated. Charges of deposited mercury are used as an experimental parameter for the estimation of the effectiveness of the mercury deposition procedure. The sensitivity of the anodic stripping voltammetry (ASV) method for the determination of lead at in situ and at ex situ formed thin mercury films are also examined. It was concluded that, in acidic solutions (pH 2.5-5.7) and fairly negative deposition potentials, e.g. −1.3 to −1.5 V, thiocyanate ion promotes the formation of the mercury film, in respect both to the amount of deposited mercury and to the mercury deposition rate. Also, the mercury coatings produced in thiocyanate solutions are more homogeneous, as depicted by microscopic examinations. In the presence of thiocyanate there is no obvious advantage of using high concentrations of mercury and/or high deposition times for the in situ and ex situ preparation of the mercury film electrodes. The optimised thin mercury film electrode ex situ prepared in a 5.0 mM thiocyanate solution of pH 3.4 was successfully applied to the ASV determination of lead and copper in acidified seawater (pH 2). The limit of detection (3σ) was 6×10⁻¹¹ M for lead and 2×10⁻¹⁰ M for copper for a deposition time of 5 min. Relative standard deviations (R.S.D.s) of <1.2% were obtained for determinations at the nanomolar of concentration level.     

Control of diameter,morphology, and structure of PVDF nanofiber fabricated by electrospray deposition

Poly(vinylidene fluoride) (PVDF) nanofibers were prepared by electrospray deposition (ESD). To control the diameter, morphology, and structure of PVDF nanofibers, some parameters were investigated, such as polymer concentration, nozzle‐to‐ground collector distance, feeding rate of the polymer solution, and applied voltage. The fabricated fiber was 80–700 nm in diameter. The increase in the polymer concentration caused an increase in the polymer viscosity and fiber diameter. At low polymer concentration (5 wt %), polymer nanoparticles were formed. An increase in applied voltage will increase the fiber diameter. Variation in the nozzle‐to‐ground collector distance did not result in significant changes in the fiber diameter. Increase in the feeding rate of the polymer solution decreased the fiber diameter. Differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) measurements showed that the melting point and total crystallinity were decreased. Fourier transform infrared spectroscopy (FTIR) measurement revealed that ESD process induced the formation of the oriented β‐phase PVDF structures. It was also demonstrated that the addition of hydrofluorocarbon solvent to polymer solution remarkably enhanced the formation of β‐phase crystalline structure of PVDF nanofiber. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 779–786, 2006     

Oxygen reduction on polycobaltprotoporphyrin film: I. Catalytic activity and stability of polycobaltprotoporphyrin film toward oxygen reduction

The catalytic activity of polycobaltprotoporphyrin (PCoPP) was compared with adsorbed cobaltprotoporphyrin monolayer. The results have shown that PCoPP film shows higher catalytic activity and stability than monolayer on glass carbon electrode in both alkaline and acid solution. Catalytic activity of PCoPP goes through a maximum with increase of film thickness. A model was proposed to explain such dependence. The effect of film thickness and solution pH on the stability of PCoPP film was studied.     

Electrochemical deposition of poly[ethylene-dioxythiophene] (PEDOT) films on ITO electrodes for organic photovoltaic cells: control of morphology,thickness, and electronic properties

In this article, controlled changes on morphology, thickness, and band gap of poly[ethylenedioxythiophene] (PEDOT) polymer films fabricated by electrochemical polymerization (potentiostatically) are analyzed. Electropolymerization of the monomer ethylenedioxythiophene (EDOT) was carried out on indium tin oxide (ITO) electrodes, in different dry organic electrolytic media, such as acetonitrile, acetonitrile–dichloromethane, and toluene–acetonitrile mixtures. It was found that electropolymerization kinetics can be controlled by changing the polarity of the electrolytic media, and kinetics is slower for those with low polarity. This fact combined with an accurate control of EDOT monomer concentration and electropolymerization at E_peak/2 potential, allows to control the morphology and thickness of the electropolymerized PEDOT films (E-PEDOT:ClO₄); toluene/ACN (4:1, v/v) and [EDOT]?=?0.3 mM gave the best films for application in organic photovoltaic (OPV) cells. The performance of the E-PEDOT:ClO₄ films was tested on ITO electrodes as anode buffer layer in OPV cells with the configuration ITO/E-PEDOT:ClO₄/P3HT:PC₆₁BM/Field’s metal, where Field’s metal (cathode) is a eutectic alloy that lets to fabricate OPV devices easily and in a fast and economical way at free vacuum conditions. The performance of these devices was compared with an OPV device constructed with a buffer layer anode, prepared using the classical spin coating of PEDOT:PSS on ITO. Results showed that OPV cells fabricated with E-PEDOT:ClO₄ have a slightly increased PV performance.     

4-(Trimethylsilyl)morpholine: synthesis,characterization, and prospects of use in film deposition processes

4-(Trimethylsilyl)morpholine (TMSM) was synthesized and shown to be applicable as a precursor for plasma-enhanced chemical vapor deposition of films. The temperature depen dence of the saturated vapor pressure of TMSM was determined by tensimetry and the thermodynamic characteristics of its evaporation were calculated. Thermodynamic modeling (calculation of the "equilibrium" compositions of the condensed and gas phases) was carried out for broad ranges of temperatures (300—1200 K), pressures (10^–2—10 Torr), and input gas (inert gas, H₂, NH₃) to precursor flow ratios (0—50). The calculation results were used to predict the composition of deposited condensed products occurring in equilibrium with the gas phase depending on the composition of the initial gas mixture and reaction conditions.     

Poly(ethylene oxide) thin films produced by electrospray deposition: morphology control and additive effects of alcohols on nanostructure

Nanostructured thin films were prepared by electrospray deposition (ESD) from poly(ethylene oxide) (PEO) aqueous solution. The surface morphologies of the deposited films were observed using scanning electron microscopy (SEM). The SEM images revealed the correlations between the morphologies and the ESD conditions. By changing the applied voltage and solution properties such as viscosity, surface tension, conductivity, and molecular weight, PEO thin films with diverse nanostructures--from nanospheres to nanofibers--were fabricated. It was also revealed that the addition of alcohols to polymer solution, which enables simultaneously changing the viscosity, the surface tension, and the conductivity, enhanced the formation of the fibrous structure. These results indicate that the ESD method is potentially a useful option for producing nanoengineered polymer surface.     

Influence of plasma excitation frequency fora-Si:H thin film deposition

The effect of plasma excitation frequency on the deposition rate and on the optical and electrical properties of amorphous silicon film is studied over the range 25–150 MHz. Deposition rates as high as 21 Å/sec are obtained at 70 MHz, which is a factor of 5–8 larger than typical rates obtained for the conventional 13.56-MHz silane glow-discharge system. Only minor changes occur in the defect density (as measured by the photothermal deflection spectroscopy method), the optical bandgap, and the electrical conductivity over this frequency range. In a preliminaryinterpretation given here, the large variation of the deposition rate as a function of excitation frequency is explained in terms of changes in the electron energy distribution function.     

Influence of hydrocarbon gasses on PECVD a-C:H film deposition

Hydrogenated amorphous carbon layers (a-C:H) deposited at near room temperature by CH₄ and C₂H₂-Ar rf discharges have been studied. Discharge processes were investigated using growth kinetics and optical emission spectroscopy (OES). The role of plasma chemistry and of ion bombardment is discussed. Addition of argon, necessary to stabilize the C₂H₂ discharge, is found to enhance susbstantially gas phase processes such as dissociation, formation of atomic hydrogen and of CH, C₂, C₃ species (revealed by OES). It appears that rf plasma is very efficient for dissociation and ionization processes with threshold energies in the ten eV range. The layers' properties have been characterized by means of UV-Visible absorption, Fourier transform IR and Raman spectroscopies.     

Passivity of titanium,part 1: film growth model diagnostics

Diagnostic criteria for the growth of the anodic oxide film on titanium in H₂SO₄ are reported. The criteria apply to the generalized high field model, which postulates that the electric field within the film is dependent upon the film thickness, and the point defect model, which describes the electric field as being constant during film growth. The diagnostic criteria show that the PDM more realistically models film growth than does the HFM, and we conclude that in this system the electric field strength is invariant with applied voltage and film thickness. The constancy of the electric field in the passive film on titanium, as demonstrated in this work, is attributed to band-to-band Esaki tunneling, which buffers the electric field against changes in the applied voltage and film thickness.     

Site-selective Cu deposition on Pt dendrimer-encapsulated nanoparticles: correlation of theory and experiment

The voltammetry of Cu underpotential deposition (UPD) onto Pt dendrimer-encapsulated nanoparticles (DENs) containing an average of 147 Pt atoms (Pt(147)) is correlated to density functional theory (DFT) calculations. Specifically, the voltammetric peak positions are in good agreement with the calculated energies for Cu deposition and stripping on the Pt(100) and Pt(111) facets of the DENs. Partial Cu shells on Pt(147) are more stable on the Pt(100) facets, compared to the Pt(111) facets, and therefore, Cu UPD occurs on the 4-fold hollow sites of Pt(100) first. Finally, the structures of Pt DENs having full and partial monolayers of Cu were characterized in situ by X-ray absorption spectroscopy (XAS). The results of XAS studies are also in good agreement with the DFT-optimized models.     

Improved surface chemistries, thin film deposition techniques, and stamp designs for nanotransfer printing

Nanotransfer printing represents an additive approach for patterning thin layers of solid materials with nanometer resolution. The surface chemistries, thin film deposition techniques, and stamp designs are all important for the proper operation of this method. This paper presents some details concerning processing procedures and other considerations needed for patterning two- and three-dimensional nanostructures with low density of defects and minimal distortions.