Thermophysical properties of free-standing micrometer-thick Poly(3-hexylthiophene) films

The solution of Poly(3-hexylthiophene) (P3HT) in chloroform is generally adopted for fabricating P3HT thin films or nanofibers. In this work, 4 regular P3HT solution weight percentages, 2, 3, 5 and 7 wt.%, are compounded to fabricate P3HT thin films by using spin-coating technique. Raman spectrum study suggests that the density of the P3HT thin films varies with different P3HT solution weight percentages while X-ray diffraction analysis reveals that the crystal structures are identical for all P3HT thin films. The transient electrothermal technique is employed to measure the thermal diffusivity of the P3HT thin films and an efficient temperature-resistance calibration is performed to cooperatively study the thermal conductivity. When the P3HT weight percentage changes from 2% to 7%, the thermal conductivity varies from 1.29 W/m·K to 1.67 W/m·K and the thermal diffusivity goes down from around 10^− 6 m²/s to 5 × 10^− 7 m²/s. The density of P3HT thin films is also determined from the experimental data. The relationship between the density and thermophysical properties clearly demonstrates that the thermal conductivity increases with density while the thermal diffusivity decreases.     

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films is described. The thin films are deposited by a flash evaporation method, followed by annealing in hydrogen. By optimizing the annealing conditions, the resulting thin films exhibit almost perfect orientation with the c-axis normal to the substrate, and are composed of nano-sized grains with an average grain size of 150 nm. The in-plane electrical conductivity and Seebeck coefficient were measured at room temperature. The cross-plane thermal conductivity of the thin films was measured by a 3ω method, and the in-plane thermal conductivity was evaluated by using an anisotropic factor of thermal conductivity based on a single crystal bulk alloy with almost the same composition and carrier concentration. The measured cross-plane thermal conductivity is 0.56 W/(m K), and the in-plane thermal conductivity is evaluated to be 1.05 W/(m K). Finally, the in-plane power factor and figure-of-merit, ZT, of the thin films are 35.6 μW/(cm K²) and 1.0 at 300 K, respectively.     

Measurement technique for thermal conductivity of thin polymer films

We present a modified steady-state heat flow technique, which allows measuring the thermal conductivity of films applied on a substrate. The measurement technique with the here presented setup provides an accuracy (overestimation) of 5-10% for film thickness up to 100 μm. For thicker films a correction factor based on finite-element simulations has to be used or the geometry has to be adapted. The technique is validated with thin glass plates of known thermal conductivity. To demonstrate the application of the technique the thermal conductivity of a thin polymer film of fluorinated acrylate is determined as 0.19 ± 0.02 W/mK.     

Room temperature deposited vanadium oxide thin films for uncooled infrared detectors

We demonstrate the room temperature deposition of vanadium oxide thin films by pulsed laser deposition (PLD) technique for application as the thermal sensing layer in uncooled infrared (IR) detectors. The films exhibit temperature coefficient of resistance (TCR) of 2.8%/K implies promising application in uncooled IR detectors. A 2-D array of 10-element test microbolometer is fabricated without thermal isolation structure. The IR response of the microbolometer is measured in the spectral range 8-13 μm. The detectivity and the responsivity are determined as ∼6×10⁵ cm Hz^1/2/W and 36 V/W, respectively, at 10 Hz of the chopper frequency with 50 μA bias current for a thermal conductance G∼10-3 W/K between the thermal sensing layer and the substrate. By extrapolating with the data of a typical thermally isolated microbolometer (G∼10⁻⁷ W/K), the projected responsivity is found to be around 10⁴ V/W, which well compares with the reported values.     

Silicon nitride deposited by inductively coupled plasma using dichlorosilane and ammonia

Silicon nitride films were deposited at low temperature (350°C and pressure of 60 mTorr), on silicon substrates, using an inductively coupled plasma chemical vapour deposition system. Different ammonia to dichlorosilane flow ratios (1.4-9.5) and RF powers (25 and 50 W) were adopted for comparison. Deposition rates of the order of 2.6-12.3 nm min⁻¹ and refractive indexes ranging from 1.710 to 1.818 were determined by ellipsometry. Fourier transformed infrared spectra revealed the presence of SiN breathing and stretching modes, Si-NH-Si bending mode and NH stretching mode. The dielectric constant (4.5-5.8), dielectric breakdown electric field (0.36 MV/mm) and conductivity (3×10⁻¹² (Ω cm)⁻¹) were determined by capacitance-voltage and current-voltage measurements. The films present low compressive total stress but when increasing the concentration of the nitrogen in the film the total stress tends to become tensile.     

The effect of composition on the bond structure and refractive index of silicon nitride deposited by HWCVD and PECVD

Silicon nitride (SiN_x) is a material with many applications and can be deposited with various deposition techniques. Series of SiN_x films were deposited with HWCVD, RF PECVD, MW PECVD and LF PECVD. The atomic densities are quantified using RBS and ERD. The influence of the atomic densities on the Si-N and Si-Si bond structure is studied. The density of N-N bonds is found to be negligible. New Si-N FTIR proportionality factors are determined which increase with increasing N/Si ratio from 1.2 · 10¹⁹ cm^− 1 for Si rich films (N/Si = 0.2) to 2.4 · 10¹⁹ cm^− 1 for N rich films (N/Si = 1.5). The peak position of the Si-H stretching mode in the FTIR spectrum is discussed using the chemical induction model. It is shown that especially for Si-rich films the hydrogen content affects the Si-H peak position. The influence of the composition on the refractive index of the films is discussed on the basis of the Lorentz-Lorenz equation and the Kramers-Kronig relation. The decreasing refractive index with increasing N/Si ratio is primarily caused by an increase of the band gap.     

A method for accurate thermal conductivity measurements of small samples at ultra-low temperatures

A specific experimental arrangement has been developed for low temperature measurements of thermal conductivity of small samples such as single crystals of magnetic insulators with a typical length of a few millimeters. A frame of low conductance, serving as a mechanical support for ruthenium thermometers recording the temperature gradient on a sample, has been tested in the temperature range from 150 mK to 5 K by using commercial 99.95% purity polycrystalline non-annealed molybdenum. The applicability of the setup is discussed for the samples with the thermal conductance in the range 10⁻⁵-10⁻³ W/K.     

Lipon thin films grown by plasma-enhanced metalorganic chemical vapor deposition in a N2-H2-Ar gas mixture

Lithium phosphorus oxynitride (Lipon) thin films have been deposited by a plasma-enhanced metalorganic chemical vapor deposition method. Lipon thin films were deposited on approximately 0.2 μm thick Au-coated alumina substrates in a N₂-H₂-Ar plasma at 13.56 MHz, a power of 150 W, and at 180 °C using triethyl phosphate [(CH₂CH₃)₃PO₄] and lithium tert-butoxide [(LiOC(CH₃)₃] precursors. Lipon growth rates ranged from 10 to 42 nm/min and thicknesses varied from 1 to 2.5 μm. X-ray powder diffraction showed that the films were amorphous, and X-ray photoelectron spectroscopy (XPS) revealed approximately 4 at.% N in the films. The ionic conductivity of Lipon was measured by electrochemical impedance spectroscopy to be approximately 1.02 μS/cm, which is consistent with the ionic conductivity of Lipon deposited by radio frequency magnetron sputtering of Li₃PO₄ targets in either mixed Ar-N₂ or pure N₂ atmosphere. Attempts to deposit Lipon in a N₂-O₂-Ar plasma resulted in the growth of Li₃PO₄ thin films. The XPS analysis shows no C and N atom peaks. Due to the high impedance of these films, reliable conductivity measurements could not be obtained for films grown in N₂-O₂-Ar plasma.     

Study of Cu diffusion behavior in low dielectric constant SiOC(-H) films deposited by plasma-enhanced chemical vapor deposition

Carbon doped silicon oxide (SiOCH) thin films deposited using plasma-enhanced chemical vapor deposition (PECVD) are commonly used in multilevel interconnect applications. To enhance the electrical performance, the deposited SiOC(-H) films were annealed in a vacuum at various temperatures ranging from 250 to 450 °C. A Cu electrode was then deposited using thermal evaporation. The drift rate of Cu⁺ ions in the SiOC(-H) films with the Cu/SiOC(-H)/p-Si(100)/Al metal-insulator-semiconductor (MIS) structures after annealing was evaluated by C-V measurements with a flatband shift caused by bias-temperature stress (BTS). The samples were stressed at different temperatures of 150 to 275 °C and electric fields up to 1.5 MV/cm to examine the penetration of Cu⁺ ions into the SiOC(-H) films. The Cu⁺ ion drift diffusion behavior was observed by high-resolution transmission electron microscopy and depth profile analysis of the Auger electron spectra. The drift diffusion experiments suggested that the Cu⁺ ion drift rate in the of SiOC(-H) films increased with increasing annealing temperature. A thermal stress and BTS were used to evaluate the impact of Cu penetration on the dielectric properties of the SiOC(-H) films.     

Effect of tungsten on the electrochromic behaviour of sol-gel dip coated molybdenum oxide thin films

The paper describes the results obtained on the performance of Mo oxide and mixed W/Mo oxide thin films for possible electrochromic applications. Mo and W/Mo oxide films were deposited on conductive (FTO) glass substrates using sol-gel dip coating method. The films were annealed at 250 °C for 30 min. The structure and morphology of Mo and W/Mo oxide films were examined using XRD, SEM and EDS. XRD results indicate the amorphous nature of the Mo and W/Mo oxide films annealed for 30 min. The CV measurements revealed that the films prepared with 10 wt.% of tungsten exhibit maximum anodic/cathodic diffusion coefficient of 24.99/12.71 × 10⁻¹¹ cm²/s. The same film exhibits a maximum transmittance variation (ΔT%) of 83.4% at 630 nm and 81.06% at 550 nm with the optical density of 1.00 and 1.13 respectively.     

Effect of hydrogen plasma treatment on the surface morphology, microstructure and electronic transport properties of nc-Si:H

Hydrogenated nanocrystalline silicon (nc-Si:H) films, deposited by reactive radio-frequency sputtering with 33% hydrogen dilution in argon at 200 °C, were treated with low-power hydrogen plasma at room temperature at various power densities (0.1-0.5 W/cm²) and durations (10 s-10 min). Plasma treatment reduced the surface root mean square roughness and increased the average grain size. This was attributed to the mass transport of Si atoms on the surface by surface and grain boundary diffusion. Plasma treatment under low power density (0.1 W/cm²) for short duration (10 s) caused a significant enhancement of crystalline volume fraction and electrical conductivity, compared to as-deposited film. While higher power (0.5 W/cm²) hydrogen plasma treatment for longer durations (up to 10 min) caused moderate improvement in crystalline fraction and electrical properties; however, the magnitude of improvement is not significant compared to low-power (0.1 W/cm²)/short-duration (10 s) plasma exposure. The results indicate that low-power hydrogen plasma treatment at room temperature can be an effective tool to improve the structural and electrical properties of nc-Si:H.     

Dependence of field-emission threshold in diamond-like carbon films grown by various techniques

In this paper, we report field-emission measurements from ∼0.5-μm-thick hydrogenated amorphous carbon (diamond-like carbon (DLC)) films. These films were grown by a variety of easily implementable plasma-enhanced chemical vapor deposition (PECVD) based techniques and also by a method that uses a saddle-field fast atom beam source. Field-emission behavior in these materials has been discussed in light of residual stress, hardness, optical band gap, and characteristic energy of band tails (Urbach energy). Onset emission-fields as low as ∼6 V/μm, together with low residual stress of 0.25 GPa, hardness of 17.5 GPa, optical band gap of 1.5 eV, and Urbach energy of 165 meV, have been obtained in DLC films grown by pulsed-PECVD at 13.56 MHz. DLC films of comparable quality could also be grown using a saddle-field fast atom beam source, which operates on modest dc power supply and with no heated filaments or magnets.     

Thermal conductivity of InAs quantum dot stacks using AlAs strain compensating layers on InP substrate

The growth and thermal conductivity of InAs quantum dot (QD) stacks embedded in GaInAs matrix with AlAs compensating layers deposited on (1 1 3)B InP substrate are presented. The effect of the strain compensating AlAs layer is demonstrated through Atomic Force Microscopy (AFM) and X-ray diffraction structural analysis. The thermal conductivity (2.7 W/m K at 300 K) measured by the 3ω method reveals to be clearly reduced in comparison with a bulk InGaAs layer (5 W/m K). In addition, the thermal conductivity measurements of S doped InP substrates and the SiN insulating layer used in the 3ω method in the 20–200 °C range are also presented. An empirical law is proposed for the S doped InP substrate, which slightly differs from previously presented results.     

Characterization of electrolyte films deposited by using RF magnetron sputtering a 20 mol% gadolinia-doped ceria target

20 mol% Gd-doped ceria (20GDC) electrolyte films on poly-crystalline Al₂O₃ substrates were prepared by radio frequency (RF) magnetron sputtering from a 20GDC oxide target, which was made by the processes of colloidal dispersion-pressure casting-sintering. Material characteristics of the 20GDC oxide target and the deposited films before and after annealed at 900 °C for 2 h were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and conductivity measurements. Crack-free and dense 20GDC electrolyte films were observed by the deposition conditions of 200 W (RF power). Homogeneity tests revealed the chemical compositions (Ce and Gd) were uniformly distributed through the bulk of the target and the deposited films. 20GDC film with a comparable conductivity of 1.00 × 10^− 3 S/cm at 650 °C is higher than that of bulk yttria-stabilized zirconia (YSZ), but smaller than that of bulk GDCs (10GDC and 20 GDC). Sputtered-GDC films in this study can be also suggested to be used as the electrolyte films for solid oxide fuel cells (SOFCs) systems as compared to the well-known YSZ.     

Localized high-rate deposition of zinc oxide films at atmospheric pressure using inductively coupled microplasma

Linear transparent zinc oxide films were fabricated using an inductively coupled microplasma jet generated in argon under atmospheric conditions. The films were formed by the sputtering and melting of a zinc filament placed inside the plasma. Film growth rates varied between 10 to 30 nm/s for input powers between 20 and 30 W. Film roughness below 20 nm and optical transmittances up to 90% in the visible were obtained while the sheet resistances ranged between 2 × 10⁴ and 1 × 10⁵Ω/□. The presented technique may allow high-rate, localized, fabrication of functional ZnO films for optoelectronic applications.     

Determination of the thermal conductivity of polypyrrole over the temperature range 280–335 K

Samples of polypyrrole were synthesised under galvanostatic conditions to produce films possessing a range of electrical conductivity from 10^–3 to 10 S cm^–1. The electrical and thermal conductivity of these films has been determined between 280 and 335 K. The electrical conductivity was measured using a four probe technique calibrated against ASTM D4496-87. Thermal conductivity was determined from measurements of thermal diffusivity, specific heat and density. Thermal diffusivity was determined using a modified a.c. calorimetry technique, while differential scanning calorimetry (DSC) was used to determine specific heat. The polymer's density was measured using Archimedes' principle. The results were used to calculate the Lorenz number of polypyrrole. A comparison of the predicted behaviour and experimental results was made. Thermal conductivity is found to be large compared to that predicted from the electrical conductivity measurements on low conductivity films. Molecular vibration effects are found to be non-trivial and experimental means for measuring their contribution are mentioned. While polypyrrole has been regarded as a synthetic metal the thermal conductivity results show this classification is wrong.     

Enhanced conductivity in iodine doped polyaniline thin film formed by thermal evaporation

Thermal evaporation technique was employed to deposit pristine and iodine doped polyaniline (PANI) thin films on glass substrates. PANI was synthesized by the chemical oxidation method. Iodine doping was carried out by evaporation. The polymer synthesized was characterized by Thermo Gravimetric Analysis (TGA), Fourier Transform Infra Red (FTIR) and Ultraviolet-Visible (UV-VIS) spectroscopy. The evaporation temperature was optimized from TGA measurements. The thin film was deposited in vacuum at 1.33 × 10^− 4 Pa by thermal evaporation of PANI. The polymer film was characterized by FTIR and UV-VIS spectroscopy. The surface morphology of the films was studied by field emission scanning electron microscopy. The resistivity was measured by van der Pauw technique. The conductivity of the doped films was seen to increase with the iodine concentration and many fold increase in conductivity was observed in comparison to the pristine films. The increase in conductivity is due to the generation of polaron band in the band gap upon iodine doping.     

Formation of β-FeSi2 thin films on non-silicon substrates

β-FeSi₂ films were prepared on non-silicon substrates by sputtering. The crystalline growth, stress induced cracks and adhesive ability to the substrate were investigated on substrate temperature and thermal expansion coefficient of substrate materials. It was found that crack formation in β-FeSi₂ films was dependent on the thermal expansion coefficients of CaF₂, MgO and quartz glass insulating materials. High-density cracks were observed from β-FeSi₂ films on CaF₂ and quartz glass substrates with large difference of the thermal expansion coefficient between β-FeSi₂ film and substrate materials, and it was crack-free on MgO substrate with a thermal expansion coefficient close to that of β-FeSi₂ films. Polycrystalline β-FeSi₂ films grew on Mo, Ta, W, Fe and stainless steel (SS) substrates at low substrate temperature around 400 °C. There was no α-FeSi₂ phase confirmed in the films. All the films had continuous structures without noticeable cracks even though they have different thermal expansion coefficients. Capacity-voltage measurements showed that β-FeSi₂ films formed on SS substrates has n-type conductivity, with residual carrier concentrations of about 1.3∼6.4 × 10¹⁸ cm^− 3. Auger electron spectroscopy depth profile measurements identified homogeneous distribution of Fe and Si atoms in the film region, but with a large interface region between the film and the substrate.     

Conduction and dielectric polarization in Se thin films

Se films were prepared by thermal evaporation technique in thickness range 150-8500 Å. X-ray diffraction measurements showed that Se films are in the amorphous state. The ac conductivity and dielectric properties of the amorphous Se films have been investigated in the frequency range 100-100 KHz and 100-400 K temperature range. The ac conductivity σ_ac(ω) is found to be proportional to ω^s where s<1. The temperature dependence of both ac conductivity and the parameter s is reasonably well interpreted by the correlated barrier (CBH) model. The dc conductivity at the room temperature was also studied in the same thickness range. It was concluded that the same mechanism of carrier motion might be dominant in both ac polarization and dc conduction. This carrier transport mechanism might be electronic.     

In-situ monitoring of the time evolution of the effective thermal conductivity of snow

We report on a 3-month long time series of in-situ measurements of the effective thermal conductivity (k_eff) of snow at 6 heights in an Alpine snowpack in the Mont-Blanc mountain range, France, at an altitude of 2400 m. Measurements were carried out automatically every 2 days using heated-needle probes embedded in the snowpack. The experimental procedure used is presented in detail and demonstrates the applicability of single heated-needle probes for the evaluation of k_eff in snow, both for long-term measurements within the snowpack and occasional use in the field. Results based on 139 automatically collected data show k_eff values ranging between 0.04 and 0.35 W m^− 1 K^− 1, and a consistent pattern of effective thermal conductivity increase throughout the measurements campaign. The temporal rate of change of k_eff varies up to 0.01 W m⁻¹ K^− 1day^− 1, with maximum values just after snowfall.