Relationship between surface free energy and development process (swelling and dissolution kinetics) of poly(4-hydroxystyrene) film in water and 2.38 wt% tetramethylammonium hydroxide aqueous solution

2021 ◽  
Author(s):  
Yuko Tsutsui Ito ◽  
Takahiro KOZAWA
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Surface Free Energy ◽  
Water Intake ◽  
Dissolution Kinetics ◽  
Exposure Dose ◽  
Tetramethylammonium Hydroxide ◽  
Polar Components ◽  
Dispersion Component ◽  
Chemically Amplified Resists

Abstract With the sharpening of optical images, the capability of resist materials has become a serious concern in lithography. The dissolution of a resist polymer is key to the realization of ultrafine patterning. However, the details of the dissolution of resist polymers remain unclarified. In this study, the relationships of surface free energy with swelling and dissolution kinetics were investigated using poly(4-hydroxystyrene) (PHS) film with triphenylsulfonium-nonaflate (TPS-nf). Developers were water and 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. PHS and TPS-nf are a typical backbone polymer (a dissolution agent) and a typical acid generator of chemically amplified resists, respectively. The water intake and dissolution of PHS film with TPS-nf became fast with increasing UV exposure dose. It was found that the increase in the polar components (particularly, the hydrogen bonding component) and the decrease in the dispersion component of surface free energy underlie the fast water intake and dissolution.

Molecular orientation of liquid aliphatic hydrocarbons on the surface and at the interface with water

1989 ◽  
Vol 54 (12) ◽  
pp. 3171-3186 ◽  
Author(s):  
Jan Kloubek
Keyword(s):  
Free Energy ◽  
Surface Free Energy ◽  
Molecular Orientation ◽  
Phase Changes ◽  
Aliphatic Hydrocarbons ◽  
Water Molecules ◽  
Free Energies ◽  
Dispersion Component ◽  
System Water ◽  
Orientation Of Molecules

The validity of the Fowkes theory for the interaction of dispersion forces at interfaces was inspected for the system water-aliphatic hydrocarbons with 5 to 16 C atoms. The obtained results lead to the conclusion that the hydrocarbon molecules cannot lie in a parallel position or be randomly arranged on the surface but that orientation of molecules increases there the ration of CH3 to CH2 groups with respect to that in the bulk. This ratio is changed at the interface with water so that the surface free energy of the hydrocarbon, γH, rises to a higher value, γ’H, which is effective in the interaction with water molecules. Not only the orientation of molecules depends on the adjoining phase and on the temperature but also the density of hydrocarbons on the surface of the liquid phase changes. It is lower than in the bulk and at the interface with water. Moreover, the volume occupied by the CH3 group increases on the surface more than that of the CH2 group. The dispersion component of the surface free energy of water, γdW = 19.09 mJ/m2, the non-dispersion component, γnW = 53.66 mJ/m2, and the surface free energies of the CH2 and CH3 groups, γ(CH2) = 32.94 mJ/m2 and γ(CH3) = 15.87 mJ/m2, were determined at 20 °C. The dependence of these values on the temperature in the range 15-40 °C was also evaluated.

scholarly journals Optical Properties and van der Waals - London Dispersion Interactions of Polystyrene Determined by Vacuum Ultraviolet Spectroscopy and Spectroscopic Ellipsometry

2007 ◽  
Vol 60 (4) ◽  
pp. 251 ◽  
Author(s):  
Roger H. French ◽  
Karen I. Winey ◽  
Min K. Yang ◽  
Weiming Qiu
Keyword(s):  
Free Energy ◽  
Optical Properties ◽  
Surface Free Energy ◽  
Vacuum Ultraviolet ◽  
Van Der Waals ◽  
Interband Transitions ◽  
Dispersion Interactions ◽  
Dispersion Component ◽  
London Dispersion ◽  
Hamaker Constants

The interband optical properties of polystyrene in the vacuum ultraviolet (VUV) region have been investigated using combined spectroscopic ellipsometry and VUV spectroscopy. Over the range 1.5–32 eV, the optical properties exhibit electronic transitions we assign to three groupings, E1, E2, and E3, corresponding to a hierarchy of interband transitions of aromatic (π → π*), non-bonding (n → π*, n → σ*), and saturated (σ → σ*) orbitals. In polystyrene there are strong features in the interband transitions arising from the side-chain π bonding of the aromatic ring consisting of a shoulder at 5.8 eV (E1′) and a peak at 6.3 eV (E1), and from the σ bonding of the C–C backbone at 12 eV (E3′) and 17.1 eV (E3). These E3 transitions have characteristic critical point line shapes associated with one-dimensionally delocalized electron states in the polymer backbone. A small shoulder at 9.9 eV (E2) is associated with excitations possibly from residual monomer or impurities. Knowledge of the valence electronic excitations of a material provides the necessary optical properties to calculate the van der Waals–London dispersion interactions using Lifshitz quantum electrodynamics theory and full spectral optical properties. Hamaker constants and the van der Waals–London dispersion component of the surface free energy for polystyrene were determined. These Lifshitz results were compared to the total surface free energy of polystyrene, polarity, and dispersive component of the surface free energy as determined from contact angle measurements with two liquids, and with literature values. The Lifshitz approach, using full spectral Hamaker constants, is a more direct determination of the van der Waals–London dispersion component of the surface free energy of polystyrene than other methods.

Effects of film thickness and alkaline concentration on dissolution kinetics of poly(4-hydroxystyrene) in alkaline aqueous solution

2022 ◽  
Author(s):  
Naoki Tanaka ◽  
Kyoko Matsuoka ◽  
Takahiro KOZAWA ◽  
Takuya Ikeda ◽  
Yoshitaka Komuro ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Film Thickness ◽  
Thick Films ◽  
Dissolution Kinetics ◽  
Dissolution Behavior ◽  
Chemically Amplified ◽  
Fundamental Understanding ◽  
Chemically Amplified Resists ◽  
Kinetics Of ◽  
Simple Combination

Abstract The dissolution behavior of a simple combination of poly(4-hydroxystyrene) (PHS) films and tetramethylammonium hydroxide (TMAH) aqueous solution was analyzed to gain a fundamental understanding of the effects of film thickness and alkaline concentration on the dissolution kinetics of chemically amplified resists (CARs). Films of four different thicknesses, from thick (approximately 900 nm) to thin (approximately 50 nm), were developed in 22 different developers of different concentrations. The dissolution behavior of each combination was observed using a quartz crystal microbalance (QCM). Differences in dissolution kinetics due to film thickness were observed even between relatively thick films such as 900- and 500-nm thick films in dilute developers. These differences were considered to be caused by the diffusion of the solution into the films. Thin films also showed characteristic behavior with dilution. This behavior was due to the interaction between the substrate and the films, unlike in the case of thick films.

scholarly journals Influence of Low-Pressure RF Plasma Treatment on Aramid Yarns Properties

Molecules ◽  
2020 ◽  
Vol 25 (15) ◽  
pp. 3476
Author(s):  
Alicja Nejman ◽  
Irena Kamińska ◽  
Izabela Jasińska ◽  
Grzegorz Celichowski ◽  
Małgorzata Cieślak
Keyword(s):  
Weight Loss ◽  
Free Energy ◽  
Radio Frequency ◽  
Plasma Treatment ◽  
Surface Free Energy ◽  
Low Pressure ◽  
Rf Plasma ◽  
Polar Component ◽  
Specific Strength ◽  
Dispersion Component

The aim of the study was to modify the surface free energy (SFE) of meta- (mAr) and para-aramid (pAr) yarns by their activation in low-pressure air radio frequency (RF) (40 kHz) plasma and assessment of its impact on the properties of the yarns. After 10 and 90 min of activation, the SFE value increased, respectively, by 14% and 37% for mAr, and by 10% and 37% for pAr. The value of the polar component increased, respectively by 22% and 57% for mAr and 20% and 62% for pAr. The value of the dispersion component for mAr and pAr increased respectively by 9% and 25%. The weight loss decreased from 49% to 46% for mAr and 62% to 50% for pAr after 90 min of activation. After 90 min, the specific strength for mAr did not change and for pAr it decreased by 40%. For both yarns, the 10 min activation in plasma is sufficient to prepare their surface for planned nanomodification.

Interactions of components and elements of the surface free energy at interfaces

1991 ◽  
Vol 56 (2) ◽  
pp. 277-295 ◽  
Author(s):  
Jan Kloubek
Keyword(s):  
Free Energy ◽  
Surface Free Energy ◽  
Polar Phase ◽  
Free Energies ◽  
Dispersion Component ◽  
Liquid Systems ◽  
Interfacial Free Energies ◽  
Total Surface Free Energy ◽  
Solid Liquid ◽  
New Hypothesis

A new hypothesis is suggested for the evaluation of the components (γd and γab) and the elements (γa and γb) of the surface free energy. The respective equations are introduced for the interactions at interfaces between a non-polar acid and non-polar base, a polar phase and non-polar acid or base, and two polar phases. The dispersion component, γd, equals the total surface free energy of non-polar phases. However, they can interact at the interface as an acid or a base through their single permanent elements γa or γb, respectively. Otherwise, induced elements γia and γib can also be effective. The surface free energy of polar phases is additively composed of the dispersion, γd, and acid-base components, γab = 2(γaγb)1/2. The proposed equation are verified using the known values of the surface and interfacial free energies for the liquid-liquid systems and they are applied to the solid-liquid interfaces. The values of the elements are determined for water, γwa = 67.7 and γwb = 10.6 mJ/m2, and for other liquids, such as glycerol, formamide, mercury, benzene, diethyl ether and trichloromethane.

Effect of Heat Treatment on Properties of Mineral Attapulgite

2008 ◽  
Vol 58 ◽  
pp. 41-46 ◽  
Author(s):  
Qing Guo Tang ◽  
Jin Sheng Liang ◽  
Jun Ping Meng ◽  
Fei Wang ◽  
Li Wei Li ◽  
...  
Keyword(s):  
Heat Treatment ◽  
Particle Size ◽  
Free Energy ◽  
Surface Free Energy ◽  
Water Vapor Adsorption ◽  
Heat Temperature ◽  
Heat Treated ◽  
Dispersion Component ◽  
Medium Particle ◽  
Medium Particle Size

Mineral attapulgite powders were heat treated at different temperature from 100°C to 800°C. The effect of heat treatment on properties of attapulgite were studied by particle size distribution, surface free energy, and water vapor adsorption performance. The results show that the medium particle size and surface free energy of attapulgite increase and hygroscopic capacity promptly reduce with the increase of heat temperature .The medium particle size of the raw palygorskite is 3.09 μm, and it becomes 14.12 μm after heat treatment at 800 °C. The surface free energy, polarity component and dispersion component of the natural attapulgite are 45.16mN•m-1, 13.92mN•m-1, 31.24mN•m-1, respectively, and they become 116.22 mN•m-1，116.22 mN•m-1，0.0 mN•m-1 after heat treatment at 800°C. Moreover, the hygroscopic capacity of attapulgite in 24h decreases from 17.1 % to 5.6% after heat treatment at 800°C.

Interaction at interfaces and induction of surface free energy components

1987 ◽  
Vol 52 (2) ◽  
pp. 271-286 ◽  
Author(s):  
Jan Kloubek
Keyword(s):  
Free Energy ◽  
Surface Free Energy ◽  
Organic Liquid ◽  
Interaction Mechanism ◽  
Work Of Adhesion ◽  
Polar Component ◽  
Published Data ◽  
Free Energies ◽  
Dispersion Component ◽  
Mechanism Of Interaction

A set of published data on surface free energy (γ1, γ2) and interfacial energy (γ12) for interfaces mercury-organic liquid, mercury-water, and water-organic liquid (125 pairs altogether) has been critically evaluated. It has been found that the Antonow rule does not hold, that the Neumann equation is suitable for determining the work of adhesion, if γ1 and γ2 are not too different, and that the Fowkes equation can be used to assess the type of interaction at the interface. A hypothesis has been suggested which states that, besides the interaction between dispersion components of the surface free energies of the adjoining phases and the interaction between the non-dispersion components of the same type in bulk, a non-dispersion component of one phase may interact by inducing a component of the same type in the other phase near the interface. Relations concerning the mechanism of interaction at the interface have been derived. Also, the relation between the Girifalco-Good, Neumann and complemented Fowkes equation has been evaluated. For the particular liquids the dispersion portion of their surface free energies and the interaction mechanism at their interface with water and mercury have been estimated. For water, e.g. the polar component of the surface free energy (14.7 mJ m-2) and the hydrogen-bond component (36.3 mJ m-2) have been determined. The introduction of the induced component of the surface free energy is shown, as an example, for water-aromatic hydrocarbons and water-alcohols systems.

The Effect of Ethyl Xanthogenate on the Electrokinetic Properties and Surface Free Energy of Galena

1993 ◽  
Vol 58 (2) ◽  
pp. 259-266
Author(s):  
M. Espinosa-Jiménez ◽  
A. Hayas-Barrú ◽  
F. González-Caballero
Keyword(s):  
Free Energy ◽  
Zeta Potential ◽  
Surface Free Energy ◽  
Potential Of Zero Charge ◽  
Liquid Drops ◽  
Angle Measurements ◽  
Dispersion Component ◽  
Contact Angle Measurements ◽  
Previously Treated ◽  
Oxidized Products

An experimental investigation is described on the zeta potential and surface free energy of the system galena/potassium ethyl xanthogenate. The behavior of the zeta potential of galena with different electrolytes and with pH is also showed. The potential of zero charge of galena was found to be at pH 4.8. The negative zeta potential, obtained from electrophoretic measurements of the galena/ethyl xanthogenate system, increased with the increasing concentration of this compound in solution. This shows that the adsorption of the ethyl xanthogenate onto galena is the responsible of the above mentioned increase of the zeta potential of the system. The uptake of -S- group of ethyl xathogenate by the oxidized products existing on the galena surface could be the cause of the increase in the negative electric charge of the interface. The surface free energy of galena and their dispersion and nondispersion components have been obtained from the contact angle measurements of both water and diiodomethane liquid drops, onto galena previously treated with different concentrations of xanthogenate in solution. While the dispersion component of the surface free energy of galena increases weakly with the concentration of the ethyl xanthogenate in solution, the nondispersion component has a significant decrease with it. therefore, the increasing hydrophobicity of the galena can be correlated with the increase in the zeta potential of this mineral, which is due to the adsorption of the collector.

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