Glass transition under confinement-what can be learned from calorimetry

Calorimetry is an effective analytical tool to characterize the glass transition and phase transitions under confinement. Calorimetry offers a broad dynamic range regarding heating and cooling rates, including isothermal and temperature modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of calorimeters. The broad dynamic range, comparable to dielectric spectroscopy, is especially of interest for the study of kinetically controlled processes like crystallization or glass transition. Accuracy of calorimetric measurements is not very high. Commonly it does not reach 0.1% and often accuracy is only a few percent. Nevertheless, calorimetry can reach high sensitivity and reproducibility. Both are of particular interest for the study of confined systems. Low addenda heat capacity chip calorimeters are capable to measure the step in heat capacity at the glass transition in nanometer thin films. The good reproducibility is used for the study of glass forming materials confined by nanometer sized structures, like porous glasses, semicrystalline structures, nanocomposites, phase separated block copolymers, etc. Calorimetry allows also for the frequency dependent measurement of complex heat capacity in a frequency range covering several orders of magnitude. Here I exclusively consider calorimetry and its application to glass transition in confined materials. In most cases calorimetry reveals only a weak dependence of the glass transition temperature on confinement as long as the confining dimensions are above 10 nm. Why these findings contradict many other studies applying other techniques to similar systems is still an unsolved problem of glass transition in confinement.     

Calorimetric study of blend miscibility of polymers confined in ultra-thin films

Miscibility in blends of polystyrene and poly(phenylene oxide) (PS/PPO) confined in thin films (down to 6 nm) was investigated using a recently developed sensitive differential alternating current (AC) chip calorimeter. Comparison of composition dependence of glass transition in thin films with common models should provide information on miscibility. This study focuses on the blend system polystyrene and poly(phenylene oxide) (PS/PPO) because it is thought as a miscible model system in the whole composition range. Furthermore, its local dynamic heterogeneity is already identified by dynamic mechanic thermal analysis (DMTA) and solid state NMR techniques. For this blend, we find that even for the thinnest films (6 nm, corresponding to about half of PPO’s radius of gyration R _g) only one glass transition is observed. The composition dependence of T _g is well described by the Fox, Couchman or Gordon-Taylor mixing law that are used for the miscible bulk blends. Although there is a contradicting result on whether T _g decreases with decreasing film thickness between our calorimetric measurements and Kim’s elipsometric measurements on the same blend (Kim et al. Macromolecules 2002, 35, 311–313), the conclusion that the good miscibility between PS and PPO remains in ultrathin films holds for both studies. Finally, we show that our chip calorimeter is also sensitive enough to study the inter-layer diffusion in ultrathin films. PS chain in a thin PS/PPO double layer that is prepared by spin coating PPO and PS thin film in tandem will gradually diffuse into the PPO layer when heated above T _g of PS, forming a PS_xPPO_100−x blend. However, above the PS_xPPO_100−x blend, there exists an intractable pure PS like layer (∼30  nm in our case) that does not diffuse into the blend beneath even staying at its liquid state over 10 hours.     

Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses

The effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5–20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS.     

Fluorescence studies of confinement in polymer films and nanocomposites: Glass transition temperature, plasticizer effects, and sensitivity to stress relaxation and local polarity

Confinement effects in polystyrene and poly(methyl methacrylate) films and nanocomposites are studied by fluorescence. The ability to employ an intensive measurable, the excited-state fluorescence lifetime, in defining the glass transition temperature, T_g, of polymers is demonstrated and compared to the use of an extensive measurable, fluorescence intensity. In addition, intrinsic fluorescence from the phenyl groups in polystyrene is used to determine the T_g-confinement effect in films as thin as ~15 nm. The decrease in T_g with decreasing film thickness (below ∼60 nm) agrees well with results obtained by extrinsic pyrene fluorescence. Dye label fluorescence is used to quantify the enhancement in T_g observed with decreasing thickness (below ~90 nm) in poly(methyl methacrylate) films; addition of 2–4 wt% dioctyl phthalate plasticizer reduces or eliminates the T_g-confinement effect in films down to 20 nm thickness. Intrinsic polystyrene fluorescence, which is sensitive to local conformation, is used to quantify the time scales (some tens of minutes) associated with stress relaxation in thin and ultrathin spin-coated films at T_g + 10 K. Finally, the shape of the fluorescence spectrum of pyrene doped at trace levels in polystyrene films and polystyrene-silica nanocomposites is used to determine effects of confinement on microenvironment polarity.     

Glass transition and dynamics of single and stacked thin films of poly(2-chlorostyrene)

The glass transition temperature and the dynamics of the α-process have been investigated using dielectric relaxation spectroscopy for single and stacked thin films of poly(2-chlorostyrene) (P2CS). The stacked film consists of 10 layers of single thin films with thickness of 12 nm or 18 nm. The glass transition temperature T _g of the single thin films of P2CS is found to decrease with decreasing film thickness in a similar way as observed for polystyrene thin films. The magnitude of the depression of T _g for the stacked thin films is larger than that of the single thin films with corresponding thickness. The depression of the temperature at which the dielectric loss shows a peak due to the α-process at a given frequency, T _α, is larger than that of the single thin films, although the magnitude is smaller than that of T _g . Annealing at a high temperature could cause the T _g and T _α of the stacked thin films to approach the values of the bulk system.     

Electrical and optical properties of reactive dc magnetron sputtered silver-doped indium oxide thin films: role of oxygen

Silver-doped indium oxide thin films have been prepared on glass and quartz substrates at room temperature (300 K) by a reactive dc magnetron sputtering technique using an alloy target of pure indium and silver (80:20 at. %). During sputtering, the oxygen flow rates are varied in the range 0.00–2.86 sccm keeping the magnetron power constant at 40 W. The resistivity of these films is in the range 10⁰–10^-3 Ω cm and they show a negative temperature coefficient of resistivity. The films exhibit p-type conductivity at an oxygen flow rate of 1.71 sccm. The work function of these silver–indium oxide films has been measured by a Kelvin probe technique. The refractive index of the films (at 632.8 nm) varies in the range 1.13–1.20. Silver doping in indium oxide narrows the band gap of indium oxide (3.75 eV). PACS 73.30.+y; 81.15.Cd; 78.20.Ci; 73.61.Le     

Structure and optical properties of carbon films obtained by multipulse pulsed laser deposition

We have obtained carbon thin films on silicon and glass substrates with multipulse pulsed laser irradiation of graphite under vacuum (p ≈ 2.6 Pa) using a high-frequency series of nanosecond laser pulses (τ = 85 ns, λ = 1060 nm) with pulse repetition frequency f ≈ 10–20 kHz and laser power density q ≈ 15–40 MW/cm². We established the optimal laser power density and laser pulse repetition frequency for obtaining amorphous nanostructured diamond-like films.     

Determination of the optimal parameters for the fabrication of ZnO thin films prepared by spray pyrolysis method

In this work, ZnO thin films have been prepared by spray pyrolysis deposition method on the glass substrates. The effect of deposition parameters, such as deposition rate, substrate temperature and solution volume has been studied by X-ray diffraction (XRD) method, UV–Vis–NIR spectroscopy, scanning electron microscopy (SEM), and electrical measurements. The XRD patterns indicate polycrystalline wurtzite structure with preferred direction along (0 0 2) planes. Thin films have transparency around 90% in the visible range. The optical band gap was determined at 3.27 eV which did not change significantly. Evolution of electrical results containing the carriers’ density, sheet resistance and resistivity are in agreement with structural results. All the results suggest the best deposition parameters are: deposition rate, R = 3 ml/min, substrate temperature, T _s = 450°C and thickness of the thin films t = 110–130 nm.     

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol–gel route

Sol–gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn_1-xLi_xO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400–500 °C. Ferroelectricity in Zn_0.85Li_0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C–V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P_s) and coercive field were 0.15 μC/cm² and 20 kV/cm, respectively, confirming the presence of ferroelectricity. PACS 77.22Ch; 77.22Ej; 77.80Bh     

Glass transition in ultrathin polymer films: calorimetric study

The ultrasensitive differential scanning calorimetry is used to observe the glass transition in thin (1-400 nm) spin-cast films of polystyrene, poly (2-vinyl pyridine) and poly (methyl methacrylate) on a platinum surface. A pronounced glass transition is observed even at a thickness as small as 1-3 nm. Using the high heating (20-200 K/ms) and cooling (1-2 K/ms in glass transition region) rates which are typical for this technique, we do not observe appreciable dependence of the glass transition temperature over the thickness range from hundreds of nanometers down to 3 nm thick films. The evolution of calorimetric data with film thickness is discussed in terms of broadening of transition dynamics and loss of transition contrast.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Structural and optical characterization of DC magnetron sputtered molybdenum oxide films

Thin films of molybdenum trioxide were deposited on glass substrates employing direct current (DC) magnetron sputtering by sputtering of molybdenum at different oxygen partial pressures in the range 8 × 10⁻⁵–1 × 10⁻³ mbar and at a substrate temperature of 473 K. The glow discharge characteristics of magnetron cathode target of molybdenum were studied. The influence of oxygen partial pressure on the structural and optical properties of molybdenum trioxide films was investigated. The films formed at an optimum oxygen partial pressure of 2 × 10⁻⁴ mbar were polycrystalline in nature with orthorhombic α- phase and an optical band gap of 3.16 eV. The refractive index of the films formed at an oxygen partial pressure of 2 × 10⁻⁴ mbar decreased from 2.08 to 1.89 with increase of wavelength from 450 to 1,000 nm, respectively. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Observation of slowly decreasing molecular oscillations in ultrathin liquid films using X-ray reflectivity

We studied ~0.5 μm and 30–80 ? thick films of a normal dielectric liquid, tetrakis(2-ethylhexoxy)silane (TEHOS), at temperature range 228–286 K, deposited onto silicon (111) substrate with native oxide using X-ray reflectivity. TEHOS is spherical with size ~10 ?, non-polar, non-reactive, and non-entangling; TEHOS has been reported to show interfacial layering at room temperature and surface layering at 0.23 T_c (T_c≈ 950 K). For films m thick, the reflectivity data did not change significantly as a function of temperature; for films 30–80 ? thick, the reflectivity data did change. The data could be fitted with an electron density model composed of a minimum necessary number of Gaussians and a uniform density layer with error-function broadened interfaces. When the film thickness is 60–80 ? below 246 K, we found that the interface and the surface layering coexist but do not overlap. When the film thickness is 30–40 ? below 277 K, they overlap and the electron density profile shows slowly decreasing molecular oscillations at the air-liquid interface.     

Is the dynamics of polystyrene films consistent with their glass transition temperature?

Experiments in the past 1.5 decades have found that the glass transition temperature of polymer films can be noticeably different from the bulk when the film thickness is decreased below ∼100  nm. On the other hand, many dynamic measurements have found results inconsistent with the observed change in the glass transition temperature. One frequently cited reason is that the dynamic properties being probed may not be directly related to the glass transition. Viscosity is a property traditionally used to characterize the dynamic slowing down occurring to a material at the glass transition. In this paper, we report experimental result showing that the viscosity of polystyrene films supported by oxide-coated silicon decreases with decreasing film thickness, consistent with the observed glass transition temperature of the films.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

Thickness dependence of the dynamics in thin films of isotactic poly (methylmethacrylate)

The film thickness dependence of both the glass transition temperature (T(g)) and the 1 kHz alpha relaxation were studied for thin films of isotactic Poly (methylmethacrylate) (i-PMMA) supported on aluminium substrates. Films in the thickness range 7-200 nm were studied. The ellipsometrically determined T(g) was found to show reductions for films thinner than 60 nm, with the largest observed reduction being 12 K for a 7 nm thick film. Measurements of the T(g) were also performed on i-PMMA films supported on silicon substrates. Dielectric studies of the temperature dependent 1 kHz alpha relaxation peak, showed that the position (T(alpha)) and shape of the peak have no film thickness dependence. This was shown to hold for films with one free surface and films with a 30 nm thermally evaporated capping layer. Capping the films was shown to have no effect on the thickness dependence of either T(g) or T(alpha). The implications of these results are discussed further and the different film thickness dependencies of T(g) and T(alpha) are discussed. This is done within the framework of the Vogel-Fulcher-Tamann (VFT) theory of glass forming materials and also in the context of the existence of a dynamic correlation length xi.     

Structural and optical properties of thermally evaporated antimony telluride thin films

Antimony telluride thin films were prepared on the well-cleaned glass substrates under a pressure of 10 – 5 torr by thermal evaporation method. The thicknesses of the films were measured using Multiple Beam Interferometer (MBI) technique. The structure of the sample was analyzed by X-ray diffraction technique. The film attains crystalline structure as the temperature of the substrate is increased to 373 K. The d spacing and the lattice parameters of the sample were calculated. Optical behavior of the film samples with the various thicknesses was analyzed by obtaining their transmittance spectra in the wavelength range of 400 – 800 nm. The transmittance is found to decrease with increase in film thickness and also it falls steeply with decreasing wavelength. The optical constants were estimated and the results are discussed. The optical band gap energy decreases with increase in the film thickness. The optical transition in these films is found to be indirect and allowed. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Manifestation of a size effect in the behavior of the intrinsic absorption edge of nanostructured polycrystalline zinc oxide thin films

We have studied the behavior of the intrinsic absorption edge in zinc oxide thin films in the temperature range 80–300 K. We have observed that the intrinsic absorption edge in films with crystal sizes of ≈45 nm or larger is described by the empirical Urbach’s rule, while in films with crystallite sizes of ≈15 nm, it is described by a modified Urbach’s rule. We have calculated the effective frequency of phonons taking part in formation of the absorption edge. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 275–277, March–April, 2007.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001