The influence of annealing temperature on the structural, electrical and optical properties of ion beam sputtered CuInSe2 thin films

CuInSe₂ (CIS) thin films were prepared by ion beam sputtering deposition of copper layer, indium layer and selenium layer on BK7 glass substrates followed by annealing at different temperatures for 1 h in the same vacuum chamber. The influence of annealing temperature (100-400 °C) on the structural, optical and electrical properties of CIS thin films was investigated. X-ray diffraction (XRD) analysis revealed that CIS thin films exhibit chalcopyrite phase and preferential (112) orientation when the annealing temperature is over 300 °C. Both XRD and Raman show that the crystalline quality of CIS thin film and the grain size increase with increasing annealing temperature. The reduction of the stoichiometry deviation during the deposition of CIS thin films is achieved and the elemental composition of Cu, In and Se in the sample annealed at 400 °C is very near to the stoichiometric ratio of 1:1:2. This sample also has an optical energy band gap of about 1.05 eV, a high absorption coefficient of 10⁵ cm⁻¹ and a resistivity of about 0.01 Ω cm.     

Characteristics of organic-inorganic hybrid plasma polymer thin films for low-κ ILD applications

This study investigated the effects of plasma power and tetraethylorthosilane (TEOS) to cyclohexene ratios on low-κ organic-inorganic hybrid plasma polymer thin films deposited on silicon (100) substrates. These films were deposited using a plasma enhanced chemical vapor deposition (PECVD) method, in addition to the electrical and mechanical properties of the resulting composites. Cyclohexene and TEOS were used as organic and inorganic precursors, respectively, with hydrogen and argon as precursor bubbler gases. Furthermore, additional argon was used as a carrier gas. The as-grown polymerized thin films were analyzed using ellipsometry, Fourier-transform infrared (FT-IR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The ellipsometry results showed the thickness of the hybrid thin film, and the FT-IR spectra showed that the hybrid polymer thin films were completely fragmented and polymerized between cyclohexene and TEOS. AFM results showed that polymer films with a smooth surface could be grown under various deposition conditions, while TEM and XRD showed that the hybrid thin film was an amorphous plasma polymer thin film without porosity. In addition, current-voltage (C-V) curves were prepared to calculate the dielectric constants. Post-annealing was applied to investigate the thermal stability of hybrid plasma polymer thin films in the hardness, Young's modulus, thermal shrinkage, and the dielectric constant at 400 °C.     

Diffusion barrier performance of amorphous W-Ti-N films in Cu metallization

W-Ti-N films were prepared on a Si wafer by reactive sputter-deposition, followed by a deposition of a Cu thin film by DC magnetron sputtering. The Cu/W-Ti-N/Si samples prepared were annealed at different temperatures under vacuum and then characterized using X-ray diffraction, scanning electron microscopy and auger electron microscopy. The sheet resistivity was determined by four point probe analysis. The results show that the amorphous W-Ti-N film is mainly composed of TiN and W and the crystallization temperature is above 800 °C. W-Ti-N thin films prepared have good thermal stability at 700 °C, but the Cu film tends to agglomerate when the temperature is above 700 °C. A failure mechanism of the diffusion barrier is proposed based on the thermal stress and interface reaction.     

Contribution study of properties of copper indium diselenide thin films

Stoichiometric powder of CuInSe₂ (CIS) was prepared from molten stoichiometric quantities of the elements. The structure analyzed by X-ray diffraction powder (XRD), shows mainly the chalcopyrite phase. CIS polycrystalline thin films deposited from this powder have been grown on glass substrates in vacuum by thermal evaporation method. The structural and electrical properties of both as-deposited and annealed films were studied using X-ray diffraction and dark conductivity measurements respectively. As-prepared films at room temperature showed an amorphous structure. However, the chalcopyrite structure with (112) preferential orientation was observed after annealing in vacuum at 400 °C during 30 min. The influence of the annealing process on the dark conductivity of the films was also discussed.     

Synthesis of epitaxial BaZrO3 thin films by chemical solution deposition

This work reports on the low temperature preparation and characterization of BaZrO₃ (BZO) epitaxial thin films by chemical solution deposition (CSD). The X-ray θ-2θ scan and φ-scan measurements have demonstrated that the BZO films exhibit cube-on-cube epitaxy on (100) MgO substrates, with the full width at half maximum (FWHM) for the ω-scan and φ-scan of 0.35° and 0.46°, respectively. The SEM and AFM analyses revealed that the morphology of the films is strongly correlated with annealing temperature. The root mean square roughness for the film annealed at 600 °C is 3.63 nm, while for the film grown at 1000 °C is 5.25 nm.     

Effect of samarium addition and annealing on the properties of electrodeposited ceria thin films

Samarium (Sm)-doped ceria (CeO₂) (SDC) is a promising material for high temperature electrochemical devices. Our work demonstrates that thin SDC films can be prepared by a cost-effective electrodeposition method at a low-temperature (30 °C) and − 0.8 V/SCE (saturated calomel electrode) potential. Analysis of the structural properties of the obtained SDC films, as-grown and annealed at 600 °C, has been carried out by X-ray diffraction (XRD). Morphology and film composition were studied using scanning electronic microscopy and energy dispersive X-ray analysis. Vibrational properties were determined by Raman spectroscopy. The effects of samarium addition into the deposition bath on the final film composition have been studied. According to XRD results, film crystallographic properties are directly linked to the percentage of Sm incorporated in the CeO₂ lattice. We report on the electrochemical deposition of the SDC films performed over a large range of Sm additions (0-30%). The effect of temperature annealing has been studied as well.     

Studies on phase transformation and molecular orientation in nanostructured zinc phthalocyanine thin films annealed at different temperatures

Studies on the electronic and optical properties of thin films of organometallic compounds such as phthalocyanine are very important for the development of devices based on these compounds. The nucleation and grain growth mechanism play an important role for the final electronic as well as optoelectronic properties of the organic and organometallic thin films. The present article deals with the change in the film morphology, grain orientation of nanocrystallites and optical properties of zinc phthalocyanines (ZnPc) thin films as a function of the post deposition annealing temperature. The effect of annealing temperature on the optical and structural property of vacuum evaporated ZnPc thin films deposited at room temperature (30 °C) on quartz glass and Si(100) substrates has been investigated. The thin films have been characterized by the UV-vis optical absorption spectra, X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. From the studies of UV-vis absorption spectra and XRD data, a metastable α to β-phase transformation has been observed when the thin films were annealed at a temperature greater than about 250 °C. The FESEM images have shown the particlelike structure at room temperature and the structure became rodlike when the films were annealed at high temperatures. TEM image of ZnPc film dissolved in ethanol has shown spectacular rod-shaped crystallites. High resolution transmission electron microscopy image of a single nanorod has shown beautiful “honey-comb” like structure. Particle size and root mean square roughness were calculated from AFM images. The changes in band gap energy with increase in annealing temperature have been evaluated.     

Nanocone SiGe antireflective thin films fabricated by ultrahigh-vacuum chemical vapor deposition with in situ annealing

In this study, we fabricated nanocone-presenting SiGe antireflection layers using only ultrahigh-vacuum chemical vapor deposition. In situ thermal annealing was adopted to cause SiGe clustering, yielding a characteristic nanocone array on the SiGe surface. Atomic force microscopy indicated that the SiGe nanocones had uniform height and distribution. Spectrophotometric measurements revealed that annealing at 900 °C yielded SiGe thin films possessing superior antireflective properties relative to those of the as-grown SiGe sample. We attribute this decrease in reflectance to the presence of the nanostructured cones. Prior to heat treatment, the mean reflectance of ultraviolet rays (wavelength < 400 nm) of the SiGe thin film was ca. 61.7%; it reduced significantly to less than 28.5% when the SiGe thin film was annealed at 900 °C. Thus, the drop in reflectance of the SiGe thin film after thermal treatment exceeded 33%.     

Effect of vacuum annealing and hydrogenation on ZnSe/Mn multilayer diluted magnetic semiconductor thin films

Multilayer thin films of ZnSe/Mn diluted magnetic semiconductor have been physically deposited onto a glass substrate using thermal evaporation technique and vacuum annealed at 333 K for 1 h at base pressure of 10⁻⁵ Torr. These thin films have been hydrogenated at different pressures (15-45 psi) for half an hour at room temperature. Hydrogenation process has been performed for as- grown as well as annealed thin films and named as-grown hydrogenated and annealed hydrogenated DMS thin films respectively. Structural characteristics of as-grown and vacuum annealed thin films have been performed by X-ray diffractometer. Current-voltage measurement has been studied for both as- grown hydrogenated and annealed hydrogenated DMS thin films by Keithly electrometer. X-ray diffraction pattern has been revealed nanocrystalline single phase of cubic zinc blende structure of film. Due to the annealing the conductivity has been found to be increased indicating the mixing of multilayer whereas the conductivity for as-grown hydrogenated and annealed hydrogenated ZnSe/Mn DMS thin films was found to be reduced indicating the electronic passivation effect of hydrogenation. Raman spectra of as-grown and annealed hydrogenated samples have been taken to see the presence of hydrogen in these samples. Surface topography of as-grown and annealed multilayer thin films has been confirmed by optical microscopy. Surface topography of annealed hydrogenated samples clearly shows the effect of hydrogenation at the surface.     

Effect of phosphorus on the copper diffusion barrier properties of electroless CoWP films

The properties of electroless CoWP barrier films with different phosphorus contents in Cu/CoWP/Si stacked samples were explored. The Cu/CoWP/Si stacked samples with 30 nm CoWP films, contained about 5.7, 8.2 and 10.8 at.% P, were prepared by electroless deposition, and then annealed in a rapid thermal annealer at a temperature between 300 and 700 °C. The effect of phosphorus content in CoWP film on the barrier properties in preventing copper diffusion and the failure of the Cu/CoWP/Si stacked samples after thermal annealing were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES), and sheet resistance measurement. Increasing the phosphorus content in the electroless CoWP film markedly improves the barrier properties. The failure temperature of Cu/CoWP/Si increased from 500 to 600 °C with the phosphorus content in CoWP film increasing from 5.7 to 10.8 at.%, and the failure of the Cu/CoWP/Si has mainly arisen from the interdiffusion of copper and cobalt during thermal annealing.     

Growth and characterization of shape memory alloy thin films for Si microactuator technologies

NiTi thin film alloys have been grown on Si (1 0 0) substrates by sequential multilayer deposition of Ni and Ti layers followed by metal interdiffusion via annealing. Short-time (5 min) annealing of the deposited layers at 500 °C leads to alloying of Ni and Ti, provided that preferential oxidation of Ti is avoided. This has been achieved by capping the layers with AlN, which constitutes a very efficient barrier preventing oxygen contamination of the film. For uncapped films, annealing has to be performed under high vacuum conditions. The structure of the processed films strongly depends on the temperature and time of the thermal process, obtaining Ni- and Ti-rich phases when the films are annealed at higher temperatures and/or during longer times. As-grown and processed films are analyzed by X-ray diffraction, in-depth Auger electron spectroscopy and X-ray photoelectron spectroscopy techniques. Finally, resistivity measurements show the existence of a phase transition in the films annealed at 600 °C without the capping layers (vacuum furnace). This contrasts with the behavior observed for AlN capped films, where cracking of the film occurs during cooling, which has been attributed to generation of stress in the buried film during the phase transition.     

Effect of deposition temperature on the properties of sputtered YIG films grown on quartz

Yttrium Iron Garnet (YIG), Y₃Fe₅O₁₂, is an oxide material that has potential applications in the magneto-optical recording media and microwave device industries. These materials, when synthesized in thin film form, usually require post-deposition annealing in order to enhance their physical properties. Furthermore, integration of YIG based optical components requires the synthesis of high quality YIG material on quartz, a process that may be problematic due to poor adhesion and lattice mismatch. Thus, we have conducted a study on the effect of deposition temperature (from 25 to 800 °C) and post-deposition annealing (at 740 °C) on the crystalline quality and chemical composition of YIG thin films, grown by radio-frequency magnetron sputtering, on quartz substrates. X-ray diffraction (XRD) shows that as-grown layers are amorphous, and subsequent annealing is necessary to induce film crystallization. Rutherford backscattering spectrometry analyses were also conducted and the chemical composition of the films was found to depend on initial deposition temperature and is affected by post-deposition anneals. Comparison of the XRD and RBS results point out to the existence of an optimal deposition temperature at about 700 °C for the formation of high crystalline quality and stoichiometric YIG thin films. Magnetic measurements were found to correlate to the XRD and RBS analyses.     

Comparative study of sputtered and electrodeposited CI(S,Se) and CIGSe thin films

Copper indium disulphide CuInS₂ (CIS) and diselenide CuInSe₂ (CISe) and their alloys with gallium CuIn_1 − xGa_xSe₂ (CIGSe) thin films have been prepared using both high- and non-vacuum processes. The well known two-stage process consisting in a sequential sputtering of Cu and In thin layers and a subsequent sulfurisation has led to the formation of good quality CuInS₂ ternary compound. The films exhibit the well known chalcopyrite structure with a preferential orientation in the (112) plane suitable for the production of the efficient solar cells. The absorption coefficient of the films is higher than 10⁴ cm^− 1 and the band gap value is about 1.43 eV. A non-vacuum technique was also used. It consists on a one step electrodeposition of Cu, In and Se and in a second time Cu, In, Se and Ga. From the morphological and structural point of view, the films obtained are similar to those prepared by the first technique. The band gap value increases up from 1 eV for the CIS films to 1.26 eV for the CuIn_1 − xGa_xSe₂ with 0 < x < 0.23. The resistivity at room temperature of the films was adjusted to 10 Ωcm after annealing. The films exhibit an absorption coefficient more than 10⁵ cm^− 1. The most important conclusion of this study is the interesting potential of electrodeposition as a promising option in low-cost CISe and CIGSe thin film based solar cells processing.     

Structural studies of ZnS thin films grown on GaAs by RF magnetron sputtering

X-ray diffraction (XRD) studies of ZnS thin films grown on GaAs (001) substrates at different temperatures by rf magnetron sputtering have been carried out using CuKα radiation. XRD analysis reveals that deposited films below 335 °C, assumed the zinc blend structure. Samples annealed at above 335 °C showed mixed phases of the zinc blend and wurzite structures. Information about crystallite size is obtained from (001), (111) and (104) diffraction peaks. The average crystallite size of the film was determined to be ∼ 32 nm using the Scherrer formula.     

Influence of annealing on humidity response of RF sputtered nanocrystalline MgFe2O4 thin films

Humidity response of Radio Frequency sputtered MgFe₂O₄ thin films onto alumina substrate, annealed at 400 °C, 600 °C and 800 °C has been investigated. Crystalline phase formation of thin films annealed at different temperature was analyzed by X-ray Diffraction. A particle/grain like microstructure in the grown thin films was observed by Scanning Electron Microscope and Atomic Force Microscope images. Film thickness for different samples was measured in the range 820-830 nm by stylus profiler. Log R (Ω) response measurement was taken for all thin films for 10-90% relative humidity (% RH) change at 25 °C. Resistance of the film increased from 5.9 × 10¹⁰ to 3 × 10¹² at 10% RH with increase in annealing temperature from 400 °C to 800 °C. A three-order magnitude, 10¹² Ω to 10⁹ Ω drop in resistance was observed for the change of 10 to 90% RH for 800 °C annealed thin film. A good linear humidity response, negligible humidity hysteresis and minimum response/recovery time of 4 s/6 s have been measured for 800 °C annealed thin film.     

High-temperature growth and in-situ annealing of MgZnO thin films by RF sputtering

We report the effect of growth temperature and annealing on microstructural, elemental and emission properties of as-grown and in-situ annealed MgZnO thin films, containing ∼ 10 at. % Mg, grown at high temperature by RF sputtering. Microstructural analysis carried out by TEM reveals formation of thin oxide layer with increased layer thickness on growth temperature, in the interface between Si substrate and MgZnO thin film. Irrespective of growth temperature, increase in Mg mole fraction with increase in thickness of MgZnO thin film is observed from EDX and AES spectroscopy, and a maximum of 14 at. % Mg is observed at 800 °C. The photoluminescence investigation shows blue shift of 104 meV in MgZnO film grown at 800 °C, compared to the film grown at 600 °C, which is due to the enhancement of the Mg incorporation at higher temperature. In addition, annealing at the growth temperature enhanced the intensity ratio of the UV/deep level emission and increased the grain size. Thermal treatment in a vacuum improved the emission efficiency and changed the origin of the point defects.     

Growth temperature dependent dielectric properties of BiFeO3 thin films deposited on silica glass substrates

We have studied the dependence of dielectric properties on the deposition temperature of BiFeO₃ thin films grown by the pulsed laser deposition technique. Thin films have been grown onto amorphous silica glass substrates with pre-patterned Au in-plane capacitor structures. It is shown that on the amorphous glass substrate, BiFeO₃ films with a near-bulk permittivity of 26 and coercive field of 80 kV/cm may be grown at a deposition temperature of about 600 °C and 1 Pa oxygen pressure. Low permittivity and higher coercive field of the films grown at the temperatures below and above 600 °C are associated with an increased amount of secondary phases. It is also shown that the deposition of BiFeO₃ at low temperature (i.e. 500 °C) and post deposition ex-situ annealing at elevated temperature (700 °C) increases the permittivity of a film. The applied bias and time dependence of capacitance of the films deposited at 700 °C and ex-situ annealed films are explained by the de-pinning of the ferroelectric domain-walls.     

Study of annealing-induced changes in CdS thin films using X-ray diffraction and Raman spectroscopy

We have investigated as grown and annealed (300 °C, 400 °C and 500 °C) thin films of CdS grown on GaAs (001) by chemical bath deposition. X-ray diffraction (XRD) shows that the as grown CdS film is polycrystalline and predominantly cubic. A residual compressive stress of the order of 1.45% in the as grown film relaxes on annealing the film at 300 °C. Furthermore, CdS film undergoes a structural phase transition from the metastable cubic phase to the stable hexagonal phase, when, annealed at 500 °C. This is accompanied by significant improvement in crystalline quality of the film. Line shape analysis of the asymmetry of the longitudinal optical phonon shows a disorder-activated mode, which correlates well with the crystalline quality estimated from XRD and photoluminescence measurements. The additional features observed in the Raman spectra ∼ 254 cm^− 1 and 309 cm^− 1 are investigated using temperature dependent Raman spectroscopy and identified as superposition of transverse optical: E₁ (TO) and E₂ phonons at q = 0 and combination mode (two zone-edge E₂ phonons) respectively.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Growth of a-b-axis orientation ZnO films with zinc vacancies by SSCVD

Zinc oxide (ZnO) films were grown on silicon (1 0 0) substrates by single-source chemical vapor deposition (SSCVD). X-ray diffraction (XRD) showed that ZnO thin films have a polycrystalline hexagonal wurtzite structure with (1 0 0) and (1 0 1) orientation, i.e., a-b-axis orientation. Atomic force microscopy (AFM) and scanning electronic microscopy (SEM) showed the films to be of relatively high density with a smooth surface. X-ray photoelectron spectroscopy (XPS) showed that the deposited films were very close to stoichiometry but contained a small number of zinc instead of O vacancies as normally found with ZnO films produced by other methods. These results were also confirmed by photoluminescence (PL) measurements.