Thermal stability of amorphous molybdenum trioxide films prepared at different oxygen partial pressures by reactive DC magnetron sputtering

Thin films of MoO₃ were prepared on quartz and Si (1 0 0) substrates by reactive dc magnetron sputtering of a Mo target in an oxygen and argon atmosphere. The structural and optical changes induced in the films due to post-growth annealing have been systematically studied by Rutherford backscattering (RBS), X-ray diffraction (XRD), X-ray reflectivity (XRR) and by optical methods. RBS studies reveal no change in composition of the films upon annealing at high temperatures. Grazing angle XRD studies show that the as-deposited films are amorphous and crystallize to β-MoO₃ phase with small contribution of α-MoO₃ upon annealing at 300 °C. The film prepared at 0.40 Pa transforms to α-MoO₃ upon annealing at 650 °C, while the film deposited at 0.19 Pa still has some β-MoO₃ phase contribution. XRR measurements reveal that the film thickness decreases upon annealing with simultaneous increase of film density. The surface roughness of the films strongly increases after crystallization. The contraction of the film deposited at 0.40 Pa is much greater than the contraction of the film prepared at 0.19 Pa. The mass variation of the film deposited at 0.19 Pa and that deposited at 0.40 Pa are completely different. The optical properties of MoO₃ films deposited at 0.19 and 0.40 Pa are changed strongly by annealing.     

Overview about the optical properties and mechanical stress of different dielectric thin films produced by reactive-low-voltage-ion-plating

Thin films of Ta₂O₅, Nb₂O₅, and HfO₂ were deposited by reactive-low-voltage-ion-plating (RLVIP) on unheated glass and silicon substrates. The film thickness was about 200 nm. Optical properties as well as mechanical film stress of these layers were investigated in dependence of various deposition parameters, i.e. arc current and oxygen partial pressure. For an arc current in the range between 40 and 50 A and an oxygen partial pressure of at least 11 · 10^− 4 mbar good results were obtained. The refractive index and film thickness were calculated from spectrophotometric transmission data using the Swanepoel theory. For example at 550 nm wavelength the refractive index for thin RLVIP-Nb₂O₅-films was found to be n₅₅₀ = 2.40. The optical absorption was obtained by photo-thermal deflection spectrometry. For the investigated materials absorption coefficients in the range of k = 5 · 10^− 4 at 515 nm wavelength were measured. The mechanical film stress was determined by measuring the difference in bending of silicon substrates before and after the deposition process. For dense films, i.e. no water vapour sorption on atmosphere, the mechanical film stress was always compressive with values of some hundred MPa. In case of films deposited with higher arc currents (I_arc > 60A) and lower oxygen pressure (< 15 · 10^− 4 mbar) the influence of a post deposition heat treatment at 350 °C for 4 h on air was also investigated. For these films the properties could clearly be improved by such treatment. However, by using lower arc currents and higher oxygen partial pressure during the ion plating process, immediately dense and environmental stable films with good optical as well as mechanical properties could be achieved without post deposition heat treatment. All the results obtained will be presented in graphs and diagrams.     

Conversion of a plasma enhanced chemical vapor deposited silicon-carbon-nitride thin film at ultra-low temperature by oxygen plasma

In this work we present an ultra-low temperature method for the oxidation of an amorphous silicon-carbide-nitride (SiCN) material. The SiCN is deposited on silicon substrates by plasma enhanced chemical vapor deposition using CH₄, SiH₄, and N₂ chemistry. The physical and chemical properties are characterized for the as-deposited SiCN and post-oxidized films are discussed. The SiCN film is exposed to oxygen plasma, where it undergoes a chemical transformation into a binary SiO₂ material system. A 1.7 nm/min oxidation rate is typical for this process and compares favorably to oxidation methods utilizing much higher temperatures. The substrate temperature remains extremely low throughout the oxidation process, T_s < 200 °C. Changes in film stress, optical constants, film thickness, surface roughness, and film density are measured. Chemical analysis by X-ray photoelectron spectroscopy is reported for both the as-deposited and oxidized film and confirms the resultant film to be the chemical equivalent of thermally grown SiO₂. We discuss applications specifically targeted to the conversion of SiCN to SiO₂.     

Structure and magnetic properties of high coercive [PrFeBx/Cu]n films with out-of-plane orientation

Pr-Fe-B single layer and [PrFeB_x/Cu]_n films were prepared by magnetron sputtering on Si substrate heated at 650 °C. The influence of the composition and thickness of Cu spacer layer on the structure and magnetic properties of films with out-of-plane orientation are investigated. The [PrFeB_x/Cu]_n films present an enhanced coercivity and a lower remanence, in comparison with the results of Pr-Fe-B single layer. The coercivity H_c⊥ of about 19.7 kOe and the remanence ratio M_r/M_s of about 0.90 are achieved in the Mo(50 nm) / [PrFeB(300 nm) / Cu(2 nm)]₂ / Mo(50 nm) film.     

Investigation of low resistance transparent MoO3/Ag/MoO3 multilayer and application as anode in organic solar cells

Depending on the resistivity and transmittance, transparent conductive oxides (TCO) are widely used in thin film optoelectronic devices. Thus doped In₂O₃ (ITO), ZnO, SnO₂ are commercially developed. However, the deposition process of these films need sputtering and/or heating cycle, which has negative effect on the performances of the organic devices due to the sputtering and heat damages. Therefore a thermally evaporable, low resistance, transparent electrode, deposited onto substrates room temperature, has to be developed to overcome these difficulties. For these reasons combination of dielectric materials and metal multilayer has been proposed to achieve high transparent conductive oxides. In this work the different structures probed were: MoO₃ (45 nm)/Ag (x nm)/MoO₃ (37.5 nm), with x = 5-15 nm. The measure of the electrical conductivity of the structures shows that there is a threshold value of the silver thickness: below 10 nm the films are semiconductor, from 10 nm and above the films are conductor. However, the transmittance of the structures decreases with the silver thickness, therefore the optimum Ag thickness is 10 nm. A structure MoO₃ (45 nm)/Ag (10 nm)/MoO₃ (37.5 nm) resulted with a resistivity of 8 × 10^− 5 Ω cm and a transmittance, at around 600 nm, of 80%. Such multilayer structure can be used as anode in organic solar cells according to the device anode/CuPc/C₆₀/Alq₃/Al. We have already shown that when the anode of the cells is an ITO film the introduction of a thin (3 nm) MoO₃ layer at the interface anode (ITO)/organic electron donor (CuPc) allows reducing the energy barrier due to the difference between the work function of ITO and the highest occupied molecular orbital of CuPc [1]. This property has been used in the present work to achieve a high hole transfer efficiency between the CuPc and the anode. For comparison MoO₃/Ag/MoO₃/CuPc/C₆₀/Alq₃/Al and ITO/MoO₃/CuPc/C₆₀/Alq3/Al solar cells have been deposited in the same run. These devices exhibit efficiency of the same order of magnitude.     

Filtered vacuum arc deposition of transparent conducting Al-doped ZnO films

Transparent conducting ZnO:Al and ZnO films of 380-800 nm thickness were deposited on glass substrates by filtered vacuum arc deposition (FVAD), using a cylindrical Zn cathode doped with 5-6 at.% Al or a pure Zn cathode in oxygen background gas with pressure P = 0.4-0.93 Pa. The crystalline structure, composition and electrical and optical properties of the films were studied as functions of P. The films were stored under ambient air conditions and the variation of their resistance as function of storage time was monitored over a period of several months.The Al concentration in the film was found to be 0.006-0.008 at.%, i.e., a few orders of magnitude lower than that in the cathode material. However, this low Al content influenced the film resistivity, ρ, and its stability. The resistivity of as-deposited ZnO:Al films, ρ = (6-8) × 10^− 3 Ω cm, was independent of P and lower by a factor of 2 in comparison to that of the ZnO films deposited by the same FVAD system. The ρ of ZnO films 60 days after deposition increased by a factor of ∼ 7 with respect to as-deposited films. The ZnO:Al films deposited with P = 0.47-0.6 Pa were more stable, their ρ first slowly increased during the storage time (1.1-1.4 times with respect to as-deposited films), and then stabilized after 30-45 days.     

Preparation and colossal magnetoresistance in a trilayer La0.67Sr0.33MnO3/La0.75MnO3/La0.67Sr0.33MnO3 device by dc magnetron sputtering

Epitaxial trilayer films of La_0.67Sr_0.33MnO₃ (LSMO)/La_0.75MnO₃ (L0.75MO)/La_0.67Sr_0.33MnO₃ (LSMO) have been prepared on (0 0 1) oriented LaAlO₃ substrates by dc magnetron sputtering. The structure and MR are studied. All as-deposited trilayer films exhibit a semiconductor to metal transition at temperature ranging from 116 to 185 K. The MR is also shown to be dependent on the thickness of the middle oxide layer. A maximum MR value of 32% (ΔR/R₀) has been obtained at 132 K under 0.4 T magnetic field for a LSMO (300 nm)/L0.75MO (70 nm)/LSMO (300 nm) trilayer film. The MR of trilayer film prefers to that of both LSMO and L0.75MO single layer films.     

Chemistry of post-annealing of epitaxial CoFe2O4 thin films

CoFe₂O₄ thin films of different thicknesses were grown on SrTiO₃ substrates. The X-ray diffraction analysis and atomic force microscopy indicated both epitaxy and a granular microstructure. We studied the magnetic properties of these films as a function of oxygen post-annealing and film thickness. All as-deposited films exhibited similar magnetic properties with saturated magnetization (M_s) of approximately 50% of the bulk M_s, (80 Am² kg^− 1). After the post-annealing the M_s changes as a consequence of crystallographic restructuring of the film. Cation ordering in 100 nm thick films reduces M_s, whereas re-oxidation increases M_s for thinner films. 13 nm films, annealed for 1 h, reach the bulk M_s. For even thinner films the quantum-size effect reduces M_s. For a synthesis of ≥ 30 nm films an annealing cycle after deposition of every 15 nm layer is recommended.     

Large area Ba1 − xSrxTiO3 thin films for microwave applications deposited by pulsed laser ablation

Large area Ba_1 − xSr_xTiO₃ (BST) thin films with x = 0.4 or x = 0.5 were deposited on 75 mm diameter Si wafers in a pulsed laser deposition (PLD) chamber enabling full-wafer device fabrication using standard lithography. The deposition conditions were re-optimized for large PLD chambers to obtain uniform film thickness, grain size, crystal structure, orientation, and dielectric properties of BST films. X-ray diffraction and microstructural analyses on the BST films grown on Pt/Au/Ti electrodes deposited on SiO₂/Si wafers revealed films with (110) preferred orientation with a grain size < 100 nm. An area map of the thickness and crystal orientation of a BST film deposited on SiO₂/Si wafer also showed (110) preferred orientation with a film thickness variation < 6%. Large area BST films were found to have a high dielectric tunability of 76% at an electric field of 400 kV/cm and dielectric loss tangent below 0.03 at microwave frequencies up to 20 GHz and a commutation quality factor of ~ 4200.     

Texture optimization process of ZnO:Al thin films using NH4Cl aqueous solution for applications as antireflective coating in thin film solar cells

ZnO:Al thin films varying the thickness from 80 to 110 nm were deposited on polished float zone < 100 > Si wafers by radio frequency magnetron sputtering at 100 °C. To texturize these surfaces with the aim of being used as antireflective coating, a wet etching process based on NH₄Cl was applied. Taking into account that the layer thickness was small, the control of the etch parameters such as etchant concentration and etching time was evaluated as a function of the textured film properties. An appropriate control of the etching rate to adjust the final thickness to the 80 nm required for the application was realized. Using NH₄Cl concentrations of 10 wt.% and short times of up to 25 s, an increase of the film roughness up to a factor of 5.6 of the as-deposited films was achieved. These optimized textured films showed weighted reflectance values below 15% and considerable better electrical properties than the as-deposited 80 nm-thick ZnO:Al films.     

Thin film preparation and characterization of wide band gap Cu3TaQ4 (Q = S or Se) p-type semiconductors

The structural, optical, and electronic properties of thin films of a family of wide band gap (E_g > 2.3 eV) p-type semiconductors Cu₃TaQ₄ (Q = S or Se) are presented. Thin films prepared by pulsed laser deposition of ceramic Cu₃TaQ₄ targets and ex-situ annealing of the as-deposited films in chalcogenide vapor exhibit mixed polycrystalline/[100]-directed growth on amorphous SiO₂ substrates and strong (100) preferential orientation on single-crystal yttria-stabilized zirconia substrates. Cu₃TaS₄ (E_g = 2.70 eV) thin films are transparent over the entire visible spectrum while Cu₃TaSe₄ (E_g = 2.35 eV) thin films show some absorption in the blue. Thin film solid solutions of Cu₃TaSe_4 − xS_x and Cu₃TaSe_4 − xTe_x can be prepared by annealing Cu₃TaSe₄ films in a mixed chalcogenide vapor. Powders and thin films of Cu₃TaS₄ exhibit visible photoluminescence when illuminated by UV light.     

Effect of high temperature annealing on the electrical performance of titanium/platinum thin films

In this study, the influence of post deposition annealing steps (PDA) on the electrical resistivity of evaporated titanium/platinum thin films on thermally oxidised silicon is investigated. Varying parameters are the impact of thermal loading with maximum temperatures up to T_PDA = 700 °C and the platinum top layer thickness ranging from 24 nm to 105 nm. The titanium based adhesive film thickness is fixed to 10 nm. Up to post deposition annealing temperatures of T_PDA = 450 °C, the film resistivity is linearly correlated with the reciprocal value of the platinum film thickness according to the size effect. Modifications in the intrinsic film stress strongly influence the electrical material parameter in this temperature regime. At T_PDA > 600 °C, diffusion of titanium into the platinum top layer and its plastic deformation dominate the electrical behaviour, both causing an increase in film resistivity above average.     

Annealing effects on microstructure and mechanical properties of sputtered multilayer Cr(1 − x)AlxN films

Multilayer Cr_(1 − x)Al_xN films with a total thickness of 2 μm were deposited on high-speed steel by medium frequency magnetron sputtering from Cr and Al-Cr (70 at.% Al) targets. The samples were annealed in air at 400 °C, 600 °C, 800 °C and 1000 °C for 1 hour. Films were characterized by cross-sectional scanning electron microscopy and X-ray diffraction analysis. The grain size of the as-deposited multilayer films is about 10 nm, increasing with the annealing temperature up to 100 nm. Interfacial reactions have clearly changed at elevated annealing temperatures. As-deposited films' hardness measured by nanoindentation is 22.6 GPa, which increases to 26.7 GPa when the annealing temperature goes up to 400 and 600 °C, but hardness decreases to 21.2 GPa with further annealing temperature increase from 600 to 1000 °C. The multilayer film adhesion was measured by means of the scratch test combined with acoustic emission for detecting the fracture load. The critical normal load decreased from 49.7 N for the as-deposited films to 21.2 N for the films annealed at 1000 °C.     

Effects of oxygen addition on electrochromic properties in low temperature plasma-enhanced chemical vapor deposition-synthesized MoOxCy thin films for flexible electrochromic devices

Electrochromic organomolybdenum oxide (MoO_xC_y) films are deposited onto 60 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates by low temperature plasma-enhanced chemical vapor deposition (PECVD) using a precursor of molybdenum carbonyl vapor, which is carried by argon gas, mixed with oxygen gas and synthesized by radio frequency power at room temperature (23 °C). The MoO_xC_y films with modified surface morphology and compositions of varying oxygen contents are proven to offer noteworthy electrochromic performance. Porous surface of the MoO_xC_y film (398 nm thick) provides Li⁺ ion diffusion coefficient value of 1.7 × 10^− 10 cm²/s for Li⁺ de-intercalation at a potential scan rate of 2 mV/s. High x/y value at high surface composition of oxygen to carbon in the MoO_xC_y film offers light modulation with transmittance variation of up to 63% and coloration efficiency of 36 cm²/C at a wavelength of 800 nm for 200 cycles of Li⁺ intercalation and de-intercalation. PECVD-synthesized MoO_xC_y thin films show promising electrochromic properties for applications in flexible electrochromic devices.     

Correlation between hardness and stress in Al-(Nb, Mo, Ta) thin films

The thin films of Al_xNb_1 − x (95 ≥ x ≥ 20), Al_xMo_x (90 ≥ x ≥ 20) and Al_xTa_1 − x (95 ≥ x ≥ 20) were prepared by magnetron codeposition at room temperature. The average film thickness was from 325 to 400 nm, depending on the film composition. The structure of the as-deposited films was examined by the X-ray diffraction. The stress of the films was determined from the substrate deformation by the profilometer, and the microhardness (load 2 mN) was examined by the micro- and nano-hardness device. For the purpose of the examination of the hardness, the samples were deposited onto the sapphire wafers, while the examination of the film stress, was performed by using thin glass substrates. For all the Al-(Nb, Mo, Ta) alloy compositions, the microhardness is predominantly under the influence of the harder element, and monotonically decreases with the increase of the aluminum content. However, the microhardness of the amorphous AlTa films was higher than the bulk value of a harder element (Ta) in the alloy. A simple empirical linear relationship between the Vickers hardness, the bulk value hardness of the transition metal (harder element) and the elastic energy fraction of the identation deformation, was established. The elastic energy fraction in the microhardness is also linearly correlated with the stress in films.     

Crystal structure and optical absorption investigations on β-In2S3 thin films

The crystal structure of annealed β-In₂S₃ thin films with different thickness was investigated by X-ray diffraction technique. Lattice parameters, crystallite size and microstrain were calculated. It was found that the lattice parameters are independent on film thickness, while annealing temperatures increase them. Crystallite sizes were increased with the increase of the film thickness and improved by annealing temperatures. In all cases, the microstrains were decreased gradually with the increase in both film thickness and annealing temperatures. Optical properties of β-In₂S₃ thin films were performed in the spectral range from 400 to 2500 nm to determine the optical constants (n and k), the high frequency dielectric constant, ε_∞, the lattice dielectric constant, ε_L, and the energy gap. The optical constants were found to be independent on film thickness in the range from 200 to 630 nm. The high frequency dielectric and lattice dielectric constants of the as-deposited film increased by annealing temperatures. The energy gap for the as-deposited In₂S₃ was found to be 2.60 eV and increased to 2.70 and 2.75 eV by annealing at 423 and 473 K for 1 h, respectively.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

AC conductivity and dielectric properties of Sb2Te3 thin films

Sb₂Te₃ films of different thicknesses, in the thickness range 300-620 nm, were prepared by thermal evaporation. X-ray analysis showed that the as-deposited Sb₂Te₃ films are amorphous while the source powder and annealed films showed a polycrystalline nature. The AC conductivity and dielectric properties of Sb₂Te₃ films have been investigated in the frequency range 0.4-100 kHz and temperature range 303-373 K. The AC conductivity σ_AC(ω) was found to obey the power law ω^s where s?1 independent of film thickness. The temperature dependence of both AC conductivity and the exponent s can be reasonably well interpreted by the correlated barrier hopping (CBH) model. The experimental results of the dielectric constant ε₁ and the dielectric loss ε₂ are frequency and temperature dependent and thickness independent. The maximum barrier height W_M calculated from dielectric measurements according to the Guintini equation agrees with that proposed by the theory of hopping of charge carriers over a potential barrier as suggested by Elliott for chalcogenide glasses. The effect of annealing at different temperatures on the AC conductivity and dielectric properties was also investigated. Values of σ_AC, ε₁ and ε₂ were found to increase with annealing treatment due to the increase of the degree of ordering of the investigated films. The Cole-Cole plots for the as-deposited and annealed Sb₂Te₃ films have been used to determined the molecular relaxation time τ. The temperature dependence of τ indicates a thermally activated process.     

Developments in hot-filament metal oxide deposition (HFMOD)

Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MO_x, WO_x and VO_x. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 °C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min^− 1 for MoO_x, are obtained. The film stoichiometry depends on the exact deposition conditions. MoO_x films, for example, present a mixture of MoO₂ and MoO₃ phases, as revealed by XPS. As determined by Li⁺ intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm² C^− 1 at a wavelength of 700 nm. MO_x and WO_x films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VO_x films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented.     

Structural characterization and optical properties of Cd(1−x)MnxSe thin films

Stoichiometric bulk ingot materials of the ternary mixture Cd_(1−x)Mn_xSe (0.05 ≤ x ≤ 0.9) were prepared by direct fusion of the constituent elements in vacuum sealed silica tubes. X-ray diffraction studies indicate that the investigated samples exhibited a hexagonal structure. The lattice parameters varied linearly with Mn content, following Vegard's law. Thin films were deposited by thermal evaporation from the pre-synthesized ingot material, onto glass substrates. X-ray and electron diffraction studies on the as-deposited and annealed films revealed an amorphous-to-crystalline phase transition at T_a ≈ 423 K. EDAX studies on the prepared films show that the as-deposited films are nearly stoichiometric. The transmittance and reflectance of the deposited Cd_(1−x)Mn_xSe films were measured at normal light incident in the wavelength spectral range 500-2500 nm. Analysis of the transmittance spectra in the entire wavelength range allowed the determination of the refractive index. The dispersion parameters have been calculated, from which the static refractive index as well as static dielecric constant were calculated. Analysis of the absorption coefficient of the investigated films revealed the existence of both the allowed direct and forbidden direct optical transition mechanisms. The corresponding energies were estimated.