Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Wetting-dewetting transition line in thin polymer films

Thin polymeric films are increasingly being utilized in diverse technological applications, and it is crucial to have a reliable method to characterize the stability of these films against dewetting. The parameter space that influences the dewetting of thin polymer films is wide (molecular mass, temperature, film thickness, substrate interaction) and a combinatorial method of investigation is suitable. We thus construct a combinatorial library of observations for polystyrene (PS) films cast on substrates having orthogonal temperature and surface energy gradients and perform a series of measurements for a range of molecular masses (1800 g/mol < M < 35 000 g/mol) and film thicknesses h (30 nm < h < 40 nm) to explore these primary parameter axes. We were able to obtain a near-universal scaling curve describing a wetting-dewetting transition line for polystyrene films of fixed thickness by introducing reduced temperature and surface energy variables dependent on M. Our observations also indicate that the apparent polymer surface tension gamma(p) becomes appreciably modified in thin polymer films from its bulk counterpart for films thinner than about 100-200 nm, so that bulk gamma(p) measurements cannot be used to estimate the stability of ultrathin films. Both of these observations are potentially fundamental for the control of thin film stability in applications where film dewetting can compromise film function.     

The effect of water or salt solution on thin hydrophobic films

Hydrophobic films of polystyrene synthesized in bulk (PS) and by emulsion polymerization in the presence of the cationic surfactant cetyltrimethylammonium bromide (PS-CTAB) or the anionic surfactant sodium dodecyl sulfate (PS-SDS) were characterized by means of ellipsometry, contact angle measurements, and atomic force microscopy. Thin (approximately 65 nm) and thick (approximately 300 nm) films were spin-coated on hydrophilic silicon wafers. PS films presented scarcely tiny holes, while PS-CTAB and PS-SDS films presented holes and protuberances. The former were attributed to dewetting effects and the latter to surfactant clusters. The films were exposed to water or to a 0.1 mol/L NaCl solution for 24 h. Ex situ measurements evidenced strong topographic alterations after the exposure to the fluid. A model based on the diffusion of water (or electrolyte) molecules to the polymer/silcon dioxide interface through holes or defects on the film edges was proposed to explain the appearance of wrinkles and protuberances. In situ ellipsometric measurements were performed and compared with simulations, which considered either a water layer between a polymer and a silcon dioxide layer or an air layer between a polymer and water (medium). In the case of thin PS films, the ellipsometric angles evidenced a very thin (0.5-1.0 nm) air layer between water and the PS films. Upon increasing the PS film thickness, no air layer could be observed by ellipsometry. Regardless of the thickness, the ellipsometric data obtained for PS-CTAB and PS-SDS films did not indicate the presence of an air layer between them and the aqueous media. The dramatic changes in the topography of PS, PS-CTAB, and PS-SDS after immersion in salt solution were explained with proposed models. From a practical point of view, this study is particularly relevant because many hydrophobic polymers are used as substrates for biomedical purposes, where the physiological ionic strength is 0.15 mol/L NaCl.     

Effect of substrate surface on dewetting behavior and chain orientation of semicrystalline block copolymer thin films

Three symmetrical semicrystalline oxyethylene/oxybutylene block copolymers (EmBn) were spin-coated on different substrates including silicon, hydrophobically modified silicon, and mica. The effects of surface property on the dewetting behavior of EmBn thin films and the chain orientation of the crystalline block were investigated with atomic force microscopy and grazing incidence X-ray diffraction . The EmBn thin films on silicon exhibit an autophobic dewetting behavior, while ordinary dewetting occurs for the thin films on modified silicon. It was observed that the stems of the E crystals in the first half-polymer layer contacting the mica surface were parallel to the surface, in contrast to the perpendicular chain orientation of the other polymer layers and of the first half-polymer layer on silicon. This is attributed to the strong interaction between the E block and mica, verified by infrared spectra.     

On sub-T(g) dewetting of nanoconfined liquids and autophobic dewetting of crystallites

The glass transition temperature (T(g)) of thin films is reduced by nanoconfinement, but it is also influenced by the free surface and substrate interface. To gain more insights into their contributions, dewetting behaviors of n-pentane, 3-methylpentane, and toluene films are investigated on various substrates as functions of temperature and film thickness. It is found that monolayers of these molecules exhibit sub-T(g) dewetting on a perfluoro-alkyl modified Ni substrate, which is attributable to the evolution of a 2D liquid. The onset temperature of dewetting increases with film thickness because fluidity evolves via cooperative motion of many molecules; sub-T(g) dewetting is observed for films thinner than 5 monolayers. In contrast, monolayers wet substrates of graphite, silicon, and amorphous solid water until crystallization occurs. The crystallites exhibit autophobic dewetting on the substrate covered with a wetting monolayer. The presence of premelting layers is inferred from the fact that n-pentane crystallites disappear on amorphous solid water via intermixing. Thus, the properties of quasiliquid formed on the crystallite surface differ significantly from those of the 2D liquid formed before crystallization.     

Instabilities during the formation of electroactive polymer thin films

The solvent-induced film structure of poly(n-vinyl carbazole) (PVK) thin films on indium tin oxide (ITO)-coated glass was examined. PVK thin films were prepared via spin-coating using five different solvents. We investigated the relationship between the solvent characteristics and film properties, including surface roughness and structure, film thickness, and density. The spin-coated polymer thin films are not in thermodynamic equilibrium; rather, the film properties are affected by the dynamics of the spin-coating process. We found that water present in tetrahydrofuran (THF) induces dewetting of PVK films during the spin-coating process. Solvents with a high evaporation rate lead to high surface roughness due to Marangoni convection. The results show that the surface roughness and structure of the films are dominated by the dynamics of the film formation process, rather than thermodynamic interactions between the polymer and solvents.     

Direct visualization of dewetting of molecularly thin liquid films on solid surfaces

The effect of the surface energy gamma, disjoining pressure, Pi, and roughness on the dewetting of molecularly thin liquid lubricant films on magnetic disks, which have sub-nanometer surface topography, has been investigated by visualizing the dewetting process directly using ellipsometric microscopy. The dewetting process of thin liquids on the rough surface is determined not only by the well-known instability of films, which is determined by the sign of dPi/dh, but also by the sign of Pi and the surface topography of the substrate even if its roughness is of the sub-nanometer order. The dewetting film formed small droplets, which were not along the surface topography of the substrate, when Pi < 0. On the other hand, it formed grooves along the surface topography with a sub-nanometer roughness when Pi > 0. Moreover, the sub-nanometer roughness initiated the dewetting of the metastable liquid thin films.     

Evidence of surface charge at the air/water interface from thin-film studies on polyelectrolyte-coated substrates

The stability of thin water films on silicon substrates coated with cationic and anionic polyelectrolytes was investigated by the thin film pressure balance technique. Depending on the surface charge of the substrate, the water films are either stable (on negatively charged wafers) or rupture rapidly (on positively charged wafers). It is supposed that this behavior is due to a negative surface charge of the free water surface. The underlying assumption that the films' stability is due to electrostatic interactions is supported by measurements of the disjoining pressure on silicon wafers with a native oxide layer, which indicates a decrease of the film thickness, and thus decreasing repulsive interaction between the two film interfaces, with increasing ionic strength.     

Thickness dependence of the structural,mechanical and electrical properties of Ni films deposited on polyimide by ion beam‐assisted deposition (IBAD)

Ni thin films with different thicknesses were deposited on pre‐treated polyimide substrates by ion beam‐assisted deposition. Dependence of structural, mechanical and electrical properties of the Ni films on their thickness was investigated. The results showed a clear correlation between film properties and film thickness. The inter‐diffusion at the interface regions of the films with different deposition time were demonstrated by transmission electron microscopy and X‐ray photoelectron spectroscopy. With increasing film thickness, surface roughness of the Ni films firstly decreased and then increased, while the grain size gradually increased. Residual stress of the Ni thin films decreased with increasing Ni film thickness up to 202 nm and then slightly increased as the film thickness further increased. Resistivity decreased, and temperature coefficient of resistivity (TCR) increased with increasing film thickness due to the enhancement of crystallization degree and the increase in grain size. The decrease in surface roughness and residual stress also contributed to the decrease of resistivity and the increase of TCR of the films. An optimal film thickness is suggested, which yielded a relatively high TCR value and low levels of both surface roughness and residual stress. Copyright © 2012 John Wiley & Sons, Ltd.     

Relaxing nonequilibrated polymers in thin films at temperatures slightly above the glass transition

We have studied the dewetting process of thin polystyrene films on nonwettable substrates in the viscoelastic regime slightly above the glass transition temperature. The evolution of the shape of the dewetting rim for varying film thickness, molecular weights and dewetting temperatures allowed us to determine the relaxation rates of residual stresses, which originated from nonequilibrated polymer chain conformations formed during film preparation by spin‐coating. For long chain polymers, we found rates notably faster than the longest bulk relaxation processes, highly independent of molecular weight and temperature. Our study demonstrates that dewetting is a powerful tool for sensitive characterization of nonequilibrium properties of thin polymer films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 515–523     

A criterion for dewetting initiation from surface disturbances on ultrathin polymer films

Nanoindentation-induced defects on ultrathin (h = 17 nm) polystyrene (PS) films that are spin cast on silicon (Si) substrates, with residual depths of penetration lower than the film thickness (<17 nm), can either grow to initiate dewetting or level, which results in a flat polymer surface, upon heating above the glass-transition temperature (T(g)). The excess surface energy (DeltaF(gamma)) of the system, which is added to the initially flat coating with the formation of an indent, provides a critical value, DeltaF(gamma,crit) = 6.1 x 10(-16) J, which determines indent evolution upon annealing. An indent grows when DeltaF(gamma) > DeltaF(gamma,crit) and levels when DeltaF(gamma) < DeltaF(gamma,crit). This conclusion is in agreement with previous reports, which used DeltaF(gamma) to distinguish the two (dewetting/leveling) opposing processes (1) in the case of indents deeper than the film thickness and (2) in the case of built-in ordered surface disturbances by capillary force lithography.     

活性端基聚苯乙烯表面修饰膜的制备与摩擦学性能

以巯丙基三甲氧基硅烷为链转移剂 ,利用自由基聚合反应合成了三甲氧基硅烷封端的聚苯乙烯 ,研究了其在单晶硅基底上的自组装行为 ,并用红外、X射线光电子能谱、原子力显微等对膜进行了表征 .研究发现 ,聚合物的浓度大于 1mg mL时才能形成较完整的聚合物膜 ,均方根粗糙度低于 1nm ,自组装过程在 90℃时 1h内即可完成 .与空白基底相比 ,自组装聚苯乙烯膜具有良好的减摩抗磨性能 ,稳定摩擦系数为 0 12 .     

Dewetting of thin polystyrene films absorbed on epoxy coated substrates

Various characteristics of dewetting of thin polystyrene (PS) films absorbed on highly cross-linked epoxy-coated and silicon oxide covered substrates are studied as a function of PS film thickness (20h(c1) whereas the spinodal dewetting (SD) occurs through the growth of surface undulations for hh(c2) while the SD mechanism is observed for h相似文献   

IN SITU OBSERVATION OF MELTING AND CRYSTALLIZATION BEHAVIORS OF POLY(ε-CAPROLACTONE) ULTRA-THIN FILMS BY AFM TECHNIQUE

The melting and crystallization behaviors of poly(ε-caprolactone) (PCL) ultra-thin films with thickness from 15 nm to 8 nm were studied by AFM technique equipped with a hot-stage in real-time. It was found that melting can erase the spherulitic structure for polymer film with high thickness. However, annealing above the melting point can not completely erase the tree-like structure for the thinner polymer film. Generally, the structure formation of thin polymer films of PCL is controlled not only by melting and crystallization but also by dewetting during thermal annealing procedures, and dewetting predominates in the structure formation of ultra-thin films. However, the presence of tree-like morphology at 75 °C may be due to the strong interaction between PCL and mica surface, which may stick the PCL chains onto the mica surface during thermal annealing process. Moreover, the growth of the dendrites was investigated and it was found that crystallization is followed from a dewetted sample, and the branches did not grow with the stems. The crystallization of polymer in the ultra-thin films is a diffusion-controlled process. Both melting and crystallization behaviors of PCL in thin films are influenced by film thickness.     

RUPTURING OF POLYMER FILMS WITH RUBBING-INDUCED SURFACE DEFECTS

It has been a long-standing question whether dewetting of polymer film from non-wettable substrate surfaceswherein the bicontinuous morphology never forms in the dewetting film is due to spinodal instability or heterogeneousnucleation. In this experiment, we use a simple method to make the distinction through introduction of topographical defectsof the films by rubbing the sample surface with a rayon cloth. Spinodal dewetting is identified for those films that dewet by acharateristic wavevector, q, independent of the density of rubbing-induced defects. Heterogeneous nucleation, on the otherhand, is identified for those with q increasing with increasing density of defects. Our result shows that PS films on oxidecoated silicon with thickness less than ≈ 13 nm are dominated by spinodal dewetting, but the thicker films are dominated bynucleation dewetting. We also confirm that spinodal dewetting does not necessarily lead to a bicontinuous morphology in thedewetting film, contrary to the classic theory of Cahn.     

A novel temperature‐step method to determine the glass transition temperature of ultrathin polymer films by liquid dewetting

A novel temperature‐step experimental method that extends the Bodiguel‐Fretigny liquid dewetting method of investigating polymer thin films is described and results presented from an investigation of thickness effects on the glass transition temperature (T_g) of ultrathin polystyrene (PS) films. Unlike most other methods of thin film investigation, this procedure promises a rapid screening tool to determine the overall profile of T_g versus film thickness for ultrathin polymer films using a limited number of samples. Similar to our prior observations and other literature data, with this new method obvious T_g depression was observed for PS thin films dewetting on both glycerol and an ionic liquid. The results for PS dewetting on the two different liquids are similar indicating only modest effects of the substrate on the T_g‐film thickness relationship. In both instances, the T_g depression is somewhat less than for similar PSs supported on silicon substrates reported in the literature. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1343–1349     

Dewetting dynamics in miscible polymer-polymer thin film mixtures

Thin polystyrene films supported by oxidized silicon (SiOx/Si) substrates may be unstable or metastable, depending on the film thickness, h, and can ultimately dewet the substrate when heated above their glass transition. In the metastable regime, holes nucleate throughout the film and subsequently grow due to capillary driving forces. Recent studies have shown that the addition of a second component, such as a copolymer or miscible polymer, can suppress the dewetting process and stabilize the film. We examined the hole growth dynamics and the hole morphology in thin film mixtures composed of polystyrene and tetramethyl bisphenol-A polycarbonate (TMPC) supported by SiOx/Si substrates. The hole growth velocity decreased with increasing TMPC content beyond that expected from changes in the bulk viscosity. The authors show that the suppression of the dewetting velocity is primarily due to reductions in the capillary driving force for dewetting and to increased friction at the substrate-polymer interface. The viscosity, as determined from the hole growth dynamics, decreases with decreasing film thickness, and is connected to a depression of the glass transition of the film.     

Influence of molecular architecture on the dewetting of thin polystyrene films

The control of dewetting for thin polymer films is a technical challenge and of significant academic interest. We have used polystyrene nanoparticles to inhibit dewetting of high molecular weight, linear polystyrene, demonstrating that molecular architecture has a unique effect on surface properties. Neutron reflectivity measurements were used to demonstrate that the nanoparticles were uniformly distributed in the thin (ca. 40 nm) film prior to high temperature annealing, yet after annealing, they were found to separate to the solid substrate, a silanized silicon wafer. Dewetting was eliminated when the nanoparticles separated to form a monolayer or above while below this surface coverage the dewetting dynamics was severely retarded. Blending linear polystyrene of similar molecular weight to the polystyrene nanoparticle with the high molecular weight polystyrene did not eliminate dewetting.     

聚合物熔体膜在基体表面的润湿和铺展行为

聚合物熔体膜在基体表面上的润湿和铺展行为受铺展系数和Hamaker常数影响。对于不能在基体表面上铺展的聚合物膜,当处于其玻璃化温度以上时,聚合物熔体膜将破裂,出现非连续区域。随着体系处于聚合物玻璃化温度以上时间的延长,非连续部分尺寸不断增长,增长速率与表面张力、聚合物粘度、聚合物液滴在基体表面的平衡接触角等因素有关,平衡后聚合物以液滴的形式在基体表面稳定存在。将带功能端基聚合物加入不能在基体表面上铺展的聚合物中,通过修饰聚合物与基体界面或改变聚合物熔体膜的表面张力,可以使原来不能在基体表面铺展的聚合物保持稳定。本文综述了聚合物熔体膜的铺展和润湿动力学研究进展,并归纳了使聚合物熔体膜稳定的方法。     

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.