Solvent penetration and photoresist dissolution: A fluorescence quenching and interferometry study

A novel method, based upon fluorescence quenching measurements, is described for the study of the mechanistic details of solvent penetration into thin polymer films. Here poly(methyl methacrylate) (PMMA) labelled with phenanthrene (Phe) groups was coated as a film (0.8 μm thick) onto quartz disks. Diffusion of solvent (1 : 1 2-butanone/2-propanol) into the film was followed by a decrease in Phe fluorescence, while film dissolution was monitored simultaneously by laser interferometry. In the case of PMMA (M_w = 411,000, films annealed at 160°C) both processes occur at approximately the same rate and exhibit non-Fickian (relaxation-controlled) diffusion behavior. Correlating the results of these two experiments shows that, once the steady state is reached, the dissolution rate is controlled by the advance of the solvent front into the PMMA film. The “transition layer,” an important dissolution parameter, increases its thickness from 50 to 90 nm during the plasticization stage of solvent penetration and maintains its thickness until the solvent front reaches the quartz substrate.     

General formula for bending beam determination of case II diffusion in polymer-containing bilayer structures

An exact formula has been presented to correlate the bending curvature cariation ratio, Ω, of any given bilayer structure comprising a solvent-swellable polymer layer with diffusion time, t, under case II diffusion. The formula can be used to determine the diffusion front velocity, v, for layered structures comprising a thick polymer film on a thin substrate or vice versa when subjected to solvent diffusion. According to this formula, there is little effect from plasticization or swelling in the transverse direction on the diffusion curve of Ω vs. t if the polymer layer to be investigated is relatively thin and its intrinsic hygroscopic strain ratio is less than unity. By using this model, the diffusion of N-methyl pyrollidinone (NMP) in a 18-μm rodlike pyromellitic dianhydride p-phenylene-diamine (PMDA-PDA) polymide film, coated on a 75-μm silicon substrate, is found to be case II with a diffusion front velocity of 1.84 × 10^-7 cm/s. © 1995 John Wiley & Sons, Inc.     

Dynamics of solvent diffusion in an aromatic polyimide

Diffusion behaviors of two polyimides (PIs) synthesized from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 4,4′-oxydianiline (ODA), and 4,4′-diaminodiphenylsulfone (DDS) were investigated by the gravimetric method. The weight uptake of penetrants (solvents) was nearly proportional to the exposure time in solvent. This phenomenon was considered as the Case II diffusion (non-Fickian) mechanism. Two PI films had an affinity to N-methyl-2-pyrrolidinone (NMP) rather than to dimethylsulfoxide (DMSO). The solubility parameter differences between two polyimides and NMP are less than 5, whereas that between polyimides and DMSO are greater than 5, as calculated by Hoy's group contribution method. The solvent uptake of anisotropic films contributed to an increase in the thickness. The swollen amount of anisotropic films increased with the swelling temperature but tended to decrease with the imide content and the thickness of the anisotropic films. Isotropic films of two PIs did not swell in both NMP and DMSO. © 1994 John Wiley & Sons, Inc.     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Residual stresses in polymeric passivation and encapsulation materials

The residual stresses caused by polyiinide (Pi 5878 and PI 2566), and silieone (3-6550 and 1-2577) films used as passivation/encapsulation layers in microelectronic circuit manufacturing are investigated by X-ray curvature measurements. For both PI types, the maximum stress is between 20–40 MPa. This stress is independent of film thickness for films thinner than 10 μm. For films thicker than this value, however, some dependency of the film stress on film thickness is observed. The variation of stress during the cure cycle is significantly different for PI 5878 and PI 2566. This is due to void nucleation and growth in the 5878 films during solvent volatilization. The silieone films have no residual stress at room temperature for all thicknesses. The compensating stresses in the Si wafer are insignificant for all cases studied.     

Experiments and modeling of bubbles colliding head-on in water

Experiments and modeling of head-on collision of a pair of bubbles driven by buoyancy in quiescent water are presented. The experiments showed that two bubbles after contacting for a few milliseconds may coalesce or bounce back depending on the collision velocity. As theoretical comparisons, the influence of velocity boundary conditions on the liquid film drainage and the characteristics of two film drainage models with the assumptions of “partially” and fully mobile interfaces under variable-velocity approach condition are studied. The “partially” mobile model is found to be easier to predict rebound case and longer drainage time, and could not obtain the drainage process where the film is thinned to the thickness below 10⁻⁷ m at both low and relatively high Re. As a whole, the fully mobile model with variable-velocity approach shows more reasonable prediction results for the coalescence and rebound of bubbles in the ultrapure water.     

Guidelines for dryer design based on results from non‐Fickian model

In polymer solution coatings below the glass transition temperature of the pure polymer, the coating can go undergo a glass transition and develop stresses during drying. When stresses develop, a non‐Fickian model accurately describes solvent mass transport in drying polymer coatings. The non‐Fickian model includes the solvent transport due to both stress and concentration gradients. This article presents a non‐Fickian model, which predicts a lower residual solvent than does the corresponding Fickian model. We showed in an earlier article that the non‐Fickian model predicts trapping skinning (higher residual solvent under more intense operating conditions) at higher drying gas‐flow rates. In this article, the non‐Fickian model was used to investigate how the gas‐flow rate, dry film thickness, and substrate thickness affect the residual solvent for a single‐zone dryer. This work recommends guidelines for choosing gas‐flow rates, gas temperatures, and substrate thickness to minimize the residual solvent. The model predictions show that, at any gas temperature, the residual solvent is minimum at an intermediate gas‐flow rate. The trapping skinning effect is less evident in thicker coatings and substrates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 477–486, 2003     

Hydrogel capsules for sustained drug release

Interpenetrating polymer networks (IPNs) based on polyacrylamide and polyvinyl alcohol for hydrogel capsules were synthesized. These polymer networks were evaluated as drug-delivery devices using Crystal Violet and Bromothymol Blue as model drugs. The observed drug release is higher for semi-II-IPN than full-IPN. The drug-release behaviors from these capsules were analyzed by the exponent relation Mt/Mα = Ktⁿ, where “K” and “n” are constants and Mt/Mα is the fraction of the drug released until time “t.” The constant “n” was found to be above 0.5, which suggests that the release of drug from the capsules follows the non-Fickian diffusional model. The mechanical behavior of hydrogel disks were also analyzed. © 1994 John Wiley & Sons, Inc.     

Mechanical properties of thin and thick coatings applied to various substrates. Part II. Young's modulus determination of coating materials*

To determine Young's modulus of coating materials when they are applied to substrates, theoretical and experimental analyses are performed. Significant residual stresses are generated within thin and thick coatings applied to substrates. As a result of these stresses, the bi-material strip assumes a certain curvature. The curved beam theory was used to establish the equivalent bending stiffness of bi-layer materials as functions of (a) the initial radius of curvature generated by residual stresses, (b) the mechanical radius of curvature during flexure testing, and (c) mechanical (Young's moduli) and geometrical (widths and thicknesses) characteristics of bi-layered systems. The relevant expression was transformed to a second- or third-order equation in order to calculate Young's modulus of the coating undergoing residual stresses (using models developed in Part I and by Stoney, Röll, and Inoue).     

The nanostructure and dewetting of block copolymer thin films annealed in different neutral solvents

The morphology of polystyrene‐b‐poly(2‐vinyl pyridine) thin films annealed under various neutral solvents was investigated. The morphological transition depends on the vapor pressure of the solvent, the quantity of the solvent in the film, and annealing time. We introduced the volume fraction of solvent in a film (Q) to correlate these factors to the morphology. At low Q, the amount of solvent that penetrates into the film is limited and it cannot induce enough chain mobility. Thus, thin film shows short stripes or a worm‐like structure. At high Q, the great diffusion of solvent into the film facilitates polymer mobility, leading to an ordered structure. Our results also suggested that the dewetting mechanism of thin film depends on Q. At low Q, dewetting develops via the nucleation and growth. At high Q, the condensation of solvent on the surface removes some polymer and dewetting is dominated by spinodal mechanism. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Influence of solvent and nanoparticles on the morphology and gas separation properties of copolyimide membranes

In this study, the effect of solvent type and nanoparticles of silica and zeolite 4A on the gas separation properties of polyimide (PI) membranes were investigated. Gas separation of the membranes based on pure solvents of dimethylformamide (DMF), n-methyl-2-pirrolidone (NMP), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO) were studied. The prepared PI membranes using DMAc and DMSO showed the highest selectivity and permeability, respectively. In this regard, the influence of their mixing on transport properties of the PI was evaluated. The prepared membrane using the mixture of DMSO/DMAc with the volume ratio of 1:3 showed the best gas separation performance in comparison to the Robeson's upper bound. Incorporation of 20 wt% of silica and zeolite 4A nanoparticles into the PI membrane indicated that the selectivity of CO₂/CH₄ increased from 39.4 to 57.6 and 68.5, respectively. Besides, gas transport properties of the PI-based mixed matrix membranes were satisfactory predicted by modified Maxwell model. Furthermore, characteristic parameters of the encapsulated particles by interfacial layer were determined.     

Examination of the role of CS2 in the CS2/NMP mixed solvents to coal extraction

The roles of CS₂ in the CS₂/NMP mixed solvent to coal extraction and solubilization were investigated in this study. There was little effect of removing of CS₂ from the solutions on the solubilities of UF coal extract and pyridine insoluble (PI) of the extract in the NMP/CS₂ mixed solvent, suggesting that NMP has high enough solubilities to the UF coal extract and PI. Six Argonne different rank coals were extracted with the CS₂/NMP mixed solvent and NMP, respectively. It was found that the extraction yield difference between NMP and CS₂/NMP mixed solvent for UF coal is largely deviated from the curve obtained for the other 5 coals, suggesting that the pre-swelling of CS₂ in the mixed solvent may be one of important roles for high extraction yield of UF coal in the CS₂/NMP mixed solvent. FTIR indicated that there was a strong interaction between CS₂ and NMP in the CS₂/NMP mixed solvent of 1 : 1 volume ratio, which made the strong absorbance at 2156 cm^− 1 in the FTIR spectra, and this interaction may disrupt the dipole based association of NMP thus making the CS₂/NMP mixed solvent lower viscosity, to penetrate more quickly into the network structure of coal, resulting in the larger solvent partner (NMP) to enter and break the stronger coal–coal interactions.     

Sorption and diffusion of alcohols in amorphous polymers

The effects of polymer composition and penetrant molecular size on the solubility and diffusivity of alcohol vapors in a series of well characterized isoprene-methyl methacrylate copolymers and their corresponding homopolymers has been investigated at room temperature. The rate of sorption behavior changes progressively from Fickian to non-Fickian, to Case II to “Super Case II” transport with increasing methyl methacrylate (MMA) content in the polymers. The equilibrium solubility of the alcohols increases linearly with increasing penetrant molecular size for polymers which are above their glass transition temperature and decreases for polymers which are below their T_g. The solubility also initially increases as an approximately linear function of MMA content in the copolymers. At about 55 mole percent MMA, the sorbed concentration either levels off or passes through a maximum depending on the size of the penetrant. The apparent “diffusion coefficients” (D) decrease with increasing molecular volume of the penetrants. An exponential dependence was found between these two variables for PMMA. These “diffusion coefficients” also decrease exponentially with increasing MMA content in these polymers. However, at 55 mole percent MMA the copolymer undergoes a rubber to glass transition at the temperature of the experiments. On this basis, it is suggested that the hindered chain segmental motion contributes to the sorption process in addition to strictly thermodynamic considerations. Free volume theory can be used to explain the mechanism of diffusion through the rubbery polymers while the “hole” theory can be applied to explain the transport of the penetrants through the glassy polymers.     

Control of molecular orientation

I. Amorphous polymers . The mechanical performance of a glassy amorphous polymer is strongly dependent upon molecular orientation. The pattern of molecular orientation is governed by the kinematics (and temperature) of mechanical forming operations. Three types of controllable orientation are: (a) uniaxial, (b) biaxial, and (c) “crossed.” The optimum pattern of orientation in a part is one which is appropriate for the mechanical stresses encountered in service. For a fiber subjected to tensile and bending loads, uniaxial orientation is appropriate. A shell structure, subjected to multiaxial stresses, requires either biaxial or crossed orientation for maximum performance. As a rule, the maximum achievable multidirectional strength in such a structure is less than the maximum strength of a uniaxially oriented fiber. II. Crystalline polymers . Oriented crystalline polymer structures can be created in two distinct ways. An isotropic polycrystalline polymer can be deformed below the melting point, with extensive reorganization of the crystal morphology, or an oriented amorphous melt can undergo crystallization to yield oriented crystalline polymer. Performance of an oriented semicrystalline polymer depends upon orientation of the amorphous portion as well as orientation of the crystallites. As with amorphous polymers, orientation can be uniaxial, biaxial, or crossed. “Orientation” usually denotes c-axis orientation only, but drawing followed by rolling can result in double orientation—orientation of a-axis, b-axis, and c-axis.     

Photocatalytic degradation of malic acid using a thin coated TiO2‐film: Insights on the mechanism of photocatalysis

Decontamination of opaque fluids using photocatalysts and near Ultraviolet (UV) irradiation involves major technical challenges. This study considers a thin TiO₂ layer placed in a new Chemical Reactor Engineering Centre (CREC)‐photoreactor cell. This new photoreactor cell is used for the photocatalytic degradation of malic and malonic acids, typical apple juice components. Conversion of organic species can only proceed through the “dark side” of the TiO₂ layer, which is in direct contact with the fluid. Under the selected operating conditions both external mass‐transfer limitations and photolysis are found to be negligible. Macroscopic radiation balance shows that 92% of near UV radiation is absorbed by the ‘back side” of the TiO₂‐film. Photocatalytic degradation experiments with 10, 20, 30, and 40 ppm malic acid initial concentrations, show that malonic acid is a main intermediate. Complete malic acid conversion occurs after 5–8 h of irradiation. Kinetic modeling of malic and malonic acid photodegradation with kinetic parameter estimation is performed using both an “in series” and an “in series‐parallel” reaction networks. The “in series‐parallel” reaction network displays better ability for predicting CO₂ formation, showing maximum quantum yields of 14.2%. Given that in the CREC‐photoreactor cell with a thin TiO₂‐film, photocatalysis can only proceed via the transfer of mobile “h⁺” sites from the irradiated side to the “dark side', this study demonstrates the significance of this step on the overall photocatalysis mechanism. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3286–3299, 2014     

Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

Optimal conditions for obtaining polymeric membranes in binary systems: a numerical analysis

The mathematical model, describing solvent evaporation from a cast film, is used with the aim of formulating a general approach to the optimization of RO membrane production.The results were correlated in terms of a “productivity factor.” This productivity factor approaches unity when the casting film has a thin and compact layer with high asymmetric character on the evaporating surface.The model is tested for different values of the parameters contained in the concentration dependence law of the mutual diffusion coefficient in solvent-polymer binary system. Also different solvent rates at the evaporating surface (low, medium, high) are employed. The numerical results were expressed in terms of intrinsic properties of the binary system with the aid of the free volume theory.Testing the model indicates that increased productivities should be expected for solutions of low free-volume polymers in high cross-section solvents. However, in general, for a given polymer-solvent system, it is very important to adjust solvent evaporation rates by varying solvent concentration in the casting atmosphere.On the other hand it could be necessary to control the plasticizing action of the solvent on the polymer in order to influence the diffusion process.     

Swelling of poly(methyl methacrylate) thin films in low molecular weight alcohols

The effects of solvent size, temperature, and polymer molecular weight on the swelling of poly(methyl methacrylate) (PMMA) thin films in low molecular weight alcohols were investigated using an in situ ellipsometer. Apparent activation energies were indicative of non-Fickian diffusion, although optical data showed substantial Fickian character for swelling in methanol and moderate Fickian character in ethanol. Penetration rates were strongly dependent on the solvent molar volume for methanol, ethanol, and isopropanol, but 1-butanol and 2-pentanol had rates similar to isopropanol. The effective cross sections of these longer molecules are similar to isopropanol, and this apparently explains the similar penetration rates. The effect of polymer molecular weight (MW) on methanol penetration rates (21–27°C) was investigated with monodisperse PMMA (M_n = 6.4–40.0 × 10⁴ g/mol). A minimum at intermediate MW was observed. Isopropanol swelling rates (45–52°C) were insensitive to MW. The swelling data were also used to determine parameters for transport models that describe the swelling of thin polymer films.     

Temperature field and residual stress analysis of multilayer pyroelectric thin film

The two-dimensional finite element model was built for the multilayer pyroelectric thin film. The temperature field and residual stress were simulated. The results show that porous silica film as a thermal-insulation layer and a reasonable model structure are effective for decreasing the heat loss. The silicon substrate and pyroelectric thin film that influence the temperature variation rate in pyroelectric thin film are also discussed. The annealing temperature and model structure have significant influence on residual stresses of pyroelectric thin film. The residual stresses increase rapidly with the increase of annealing temperature. The scanning electron microscopy (SEM) is employed to investigate the morphology of the pyroelectric thin film. The results show that the pyroelectric thin film annealed at 750 °C has a crack structure.