Investigation of thermal annealing of optical properties and residual stress of ion-beam-assisted TiO2 thin films with different substrate temperatures

Titanium oxide films were prepared by ion-beam-assisted deposition on glass substrates at various substrate temperatures. The effect of the temperature of thermal annealing from 100 degrees C to 300 degrees C on the optical properties and residual stress was investigated. The influence on the stoichiometry and residual stress of titanium oxides deposited at different substrate temperature was discussed. The residual-stress was minimum and the extinction coefficient was maximum at an annealing temperature of 200 degrees C with a substrate temperature of 150 degrees C. However, when the substrate temperature was increased to 200 degrees C and 250 degrees C, the residual stress was minimum and the extinction coefficient was maximum at an annealing temperature of 250 degrees C. The spectra of x-ray photoelectron spectroscopy reveal that the films lost oxygen and slowly generated lower suboxides at the annealing temperature at which the residual stress was minimum and the extinction coefficient was maximum. As the annealing temperature increased above the temperature at minimum stress, the lower suboxides began to capture oxygen and form stable oxides. TiO2 films deposited at substrate temperatures of 200 degrees C and 250 degrees C were more stable than films deposited at 150 degrees C.     

Effect of thermal annealing on the microstructure and morphology of erbium films

The effects of thermal annealing on the microstructure and morphology of erbium films were investigated by X-ray diffraction and scanning electron microscopy. All the erbium films were fabricated by electron-beam vapor deposition. The columnar grain sizes of as-received erbium films increased with the substrate temperatures and were enlarged by the coalescence and migration of grains during the high temperature annealing. The intrinsic stresses of erbium films, fabricated at a low substrate temperature (200 °C), were relaxed accompanied with the appearance of cracks on the films surface. The films deposited at 200 °C had (002) preferred orientation, and the film deposited at 450 °C had mixed (100) and (101) texture. The peak positions and the full width at half maximum of (100), (002), and (101) diffraction lines of erbium shift towards higher angles and sharply decrease during the annealing process, indicating that the stress inside the film was relaxed.     

Effect of thermal annealing on the optical properties and residual stress of TiO2 films produced by ion-assisted deposition

The effects of thermal annealing of titanium oxide films deposited by ion-beam assistance at annealing temperatures from 100 degrees C to 300 degrees C on the residual stress and optical properties of the films was investigated. The refractive indices and extinction coefficients increased gradually as the temperature was increased from 100 degrees C to 200 degrees C and then declined gradually as the temperature was increased further from 200 degrees C to 300 degrees C. The film lost oxygen and slowly generated lower suboxides as the annealing temperature was reduced below 200 degrees C, as determined by x-ray photoelectron spectroscopy (XPS). As the annealing temperature increased above 200 degrees C, the lower suboxides began to capture oxygen and form stable oxides. XPS measurements were made to verify both the binding energy associated with the Ti 2p line and the variation of the O 1s line. A Twyman-Green interferometer was employed for phase-shift interferometry to study the residual stress. The residual stress declined as the temperature was reduced from 100 degrees C to 200 degrees C because the lower suboxides reduced the stress in the film. Above 200 degrees C, the film began to capture oxygen, so the residual stress rose. At 300 degrees C, the film was no longer amorphous as the anatase was observed by x-ray diffraction.     

Stresses in sputtered RUOx thin films

RuO_x thin films have been deposited by reactive sputtering in an O₂/Ar atmosphere. The films were characterized for their stress and resistivity as a function of deposition temperature (room temperature, 300°C) and the O₂ content (25–100%) in the sputtering gas. Additionally, the stresses in these films were determined as a function of annealing temperature (up to 600°C) using an in-situ curvature measurement technique. The as-deposited films were found to be under a state of compressive stress for all deposition conditions. The compressive stresses sharply increased with increasing deposition temperature from a value of around 200 MPa at 200°C to 1400 MPa at 300°C. This dramatic increase has been attributed to differences in microstructure at these deposition temperatures. The microstructural differences also led to the widely differing stress-temperature behavior during annealing of these films. For films deposited at temperatures lower than 200°C, the annealing process resulted in a decrease in the compressive stress and resistivity of the films. However, films deposited at a temperature of 300°C did not show any changes in the compressive stress or resistivity after annealing. The results of this study can be used to deposit RuO_x thin films with low resistivity and minimal stresses.     

Effects of substrate temperature on the microstructure and photocatalytic reactivity of TiO2 films

Transmission electronic microscopy is used to study the structure, morphology and orientation of thin TiO2 films prepared by reactive magnetron sputtering on glass slides at different substrate temperatures (100 to 400 °C). The TiO2 films are used to purify a dye in waste water. The microstructure and photocatalytic reactivity of TiO2 films have been shown to be functions of deposition temperature. In the temperature range examined, all film samples have a porous nanostructure and the dimension of particles grown with increasing deposition temperature. Films are amorphous at temperatures of 100 °C and only anatase phase forms at 200 °C and above. Films deposited between 200 to 300 °C show a preferred orientation, while films at 400 °C change into complete random orientation. Deposition at 250 °C yields high efficiency in photocatalytic degradation owing to the high degree of preferred orientation and nanocrystalline/nanoporous anatase phase. © 1998 Kluwer Academic Publishers     

Thin transparent W-doped indium-zinc oxide (WIZO) layer on glass

Annealing effect on structural and electrical properties of W-doped IZO (WIZO) films for thin film transistors (TFT) was studied under different process conditions. Thin WIZO films were deposited on glass substrates by RF magnetron co-sputtering technique using indium zinc oxide (10 wt.% ZnO-doped In2O3) and WO3 targets in room temperature. The post annealing temperature was executed from 200 degrees C to 500 degrees C under various O2/Ar ratios. We could not find any big difference from the surface observation of as grown films while it was found that the carrier density and sheet resistance of WIZO films were controlled by O2/Ar ratio and post annealing temperature. Furthermore, the crystallinity of WIZO film was changed as annealing temperature increased, resulting in amorphous structure at the annealing temperature of 200 degrees C, while clear In2O3 peak was observed for the annealed over 300 degrees C. The transmittance of as-grown films over 89% in visible range was obtained. As an active channel layer for TFT, it was found that the variation of resistivity, carrier density and mobility concentration of WIZO film decreased by annealing process.     

Effects of annealing and deposition temperature on the structural and optical properties of AZO thin films

Al-doped ZnO (AZO) thin films were deposited on p- type Si(100) substrate by r.f magnetron sputtering at 200, 300 and 400 °C substrate temperatures. The deposited films were annealed in air atmosphere for 1 h at temperatures of 700, 800 and 900 °C. The deposition temperature and post-deposition annealing effects on structural and optical properties of the AZO samples were analyzed using X-ray diffraction, atomic force microscope and photoluminescence (PL). After annealing, the value of full width half maximum of the diffraction peaks was decreased as well as, the intensity of visible and strong UV PL emission peaks were increased with temperature. However, the deep-level emission related with zinc point defects was removed by annealing of the samples. Results revealed that all of the as-deposited and annealed AZO films have hexagonal structure along (002) direction and their crystallinity were improved with the increased deposition and post-growth annealing temperatures. In addition, the surface roughness and the particle size of the films were increased with increased deposition and annealing temperatures.     

Annealing and recrystallization of amorphous ZnO thin films deposited under cryogenic conditions by pulsed laser deposition

This article deals with the annealing of amorphous ZnO thin films prepared by pulsed laser deposition (PLD) under cryogenic conditions. The substrate holder was cooled by liquid nitrogen. X-ray diffraction analysis evidenced that as-deposited films had amorphous structures: analysis by scanning electron microscopy (SEM) revealed their fine grained surface and inner structure. Annealing at temperatures in the range of 200-800 °C resulted in a transition in the thin film crystal structure from amorphous to polycrystalline. Various properties of the ZnO films were found depending on the recrystallization temperature. In depth investigations employing SEM, X-ray diffraction, atomic force microscopy and secondary ion mass spectroscopy provided comparisons of the recrystallizations of undoped ZnO thin films during the phase transition processes from amorphous to hexagonal wurtzite structures.     

Post-deposition thermal annealing studies of hydrogenated microcrystalline silicon deposited at 40 °C

Post-deposition thermal annealing studies, including gas effusion measurements, measurements of infrared absorption versus annealing state, cross-sectional transmission electron microscopy (X-TEM) and atomic force microscopy (AFM), are used for structural characterization of hydrogenated amorphous and microcrystalline silicon films, prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) at low substrate temperature (T_S). Such films are of interest for application in thin semiconductor devices deposited on cheap plastics. For T_S ∼ 40 °C, H-evolution shows rather complicated spectra for (near-) microcrystalline material, with hydrogen effusion maxima seen at ∼ 200-250 °C, 380 °C and ∼ 450-500 °C, while for the amorphous material typical spectra for good-quality dense material are found. Effusion experiments of implanted He demonstrate for the microcrystalline material the presence of a rather open (void-rich) structure. A similar tendency can be concluded from Ne effusion experiments. Fourier Transform infrared (FTIR) spectra of stepwise annealed samples show Si-H bond rupture already at annealing temperatures of 150 °C. Combined AFM/X-TEM studies reveal a columnar microstructure for all of these (near-) microcrystalline materials, of which the open structure is the most probable explanation of the shift of the H-effusion maximum in (near-) microcrystalline material to lower temperature.     

Structural and electrical properties of RuO2 thin films prepared by rf-magnetron sputtering and annealing at different temperatures

Conductive ruthenium oxide (RuO₂) thin films have been deposited at different substrate temperatures on various substrates by radio-frequency (rf) magnetron sputtering and were later annealed at different temperatures. The thickness of the films ranges from 50 to 700 nm. Films deposited at higher temperatures show larger grain size (about 140 nm) with (200) preferred orientation. Films deposited at lower substrate temperature have smaller grains (about 55 nm) with (110) preferred orientation. The electrical resistivity decreases slightly with increasing film thickness but is more influenced by the deposition and annealing temperature. Maximum resistivity is 861 μΩ cm, observed for films deposited at room temperature on glass substrates. Minimum resistivity is 40 μΩ cm observed for a thin film (50 nm) deposited at 540°C on a quartz substrate. Micro-Raman investigations indicate that strain-free well-crystallized thin films are deposited on oxidized Si substrates.     

Characterization of pulsed laser deposited zinc oxide

The pulsed laser deposition of zinc oxide films (ZnO) has been studied as a function of laser wavelength, and substrate temperature. Optical emission spectroscopy of the laser produced plume was used to characterize the deposition process. The deposited films were characterized by X-ray diffractometry, Auger electron spectroscopy, and scanning electron microscopy. Highly textured (002) ZnO films deposited at substrate temperatures of 300 °C with laser wavelengths of 532 nm and 248 nm. However, the energy fluence of 248 nm radiation controls the degree of texturing, allowing highly textured films to be deposited at room temperature.     

The effect of substrate temperature on the spray-deposited TiO2 nanostructured films for dye-sensitized solar cells

The nanostructured TiO2 films have deposited on SnO2:F (FTO) coated glass substrate by spray pyrolysis technique at different substrate temperatures of 200-500 degrees C. The structural, surface morphological and optical properties of TiO2 films significantly vary with the substrate temperature. The surface of the TiO2 films deposited at 400 degrees C shows the nanoflakes and short nanorods (approximately 130 nm) like structures while the TiO2 films prepared at 500 degrees C shows only the nanoflakes like structures. The band gap of the TiO2 films prepared at higher temperatures (300-500 degrees C) becomes narrow due to presence the rutile phases in their crystal structure. Ruthenium (II) complex as a dye, KI/I2 as an electrolyte and carbon on FTO glass as a counter electrode has used to fabricate the dye-sensitized solar cell (DSC). The TiO2 film deposited at 400 degrees C has showed the best photovoltaic performance in DSC with the efficiency of 3.81%, the photovoltage of 773 mV, the photocurrent of 8.34 mA/cm2, and the fill factor of 56.17%. The photovoltage of the DSC increases with the increase of substrate temperature during the deposition of TiO2 films. Moreover, all the DSCs exhibit reasonably high fill factor value.     

Effect of heat treatment on characteristics of nanocrystalline ZnO films by electron beam evaporation

Zinc oxide thin films have been grown on glass substrate at room temperature by electron beam evaporation and then were annealed in annealing pressure 600 mbar at different temperatures ranging from 250 to 550 °C for 30 min. Electrical, optical and structural properties of thin films such as electrical resistivity, optical transmittance, band gap and grain size have been obtained as a function of annealing temperature. X-ray diffraction has shown that the maximum intensity peak corresponds to the (002) predominant orientation for ZnO films annealed at various temperatures. The full width at half maximum, decreases after annealing treatment which proves the crystal quality improvement. Scanning electron microscopy images show that the grain size becomes larger by increasing annealing temperature and this result agrees with the X-ray diffraction analysis.     

Characterization and sensing properties of ZnO film prepared by single source chemical vapor deposition

A novel deposition technique has been used to grow ZnO films. Good quality films were obtained on glass substrates by single source chemical vapor deposition (SSCVD), for gas sensing applications. The properties of ZnO films were investigated at different deposition temperatures 300, 350 and 400 °C. X-ray diffraction results show that all deposited films were polycrystalline. The morphological, structural, optical and electrical properties of the films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), cathodoluminescence (CL) and Hall effect techniques. The morphology of the deposited films evolves from columnar grains, to parallel plates as the substrate temperature increases. A significant increase in the relative intensities of the green and red emission with increasing deposition temperature has been observed. Electrical properties, relevant for gas sensing behavior have been investigated as well. In the particular case of CO an operating temperature of 300 °C seems to yield the best sensitivity.     

溅射工艺对BST薄膜取向行为的影响

采用射频磁控溅射法在Si(100)衬底上沉积了Ba0.65Sr0.35TiO3薄膜.借助XRD、AFM和SEM研究了衬底温度、退火温度、溅射气压等不同的溅射参数对Ba0.65Sr0.35TiO3薄膜的晶化行为和显微结构的影响.在室温下沉积并未经退火处理的Ba0.65Sr0.35TiO3 薄膜是无定形态,在较高温度下沉积的薄膜晶化相对较好;随着在氧气气氛中退火温度的升高,X射线衍射峰的半峰宽变窄,衍射峰强度增强;在0.37～1.2Pa气压下沉积的Ba0.65Sr0.35TiO3薄膜有(110)和(200)主衍射峰,且其强度随溅射气压的增加而增强;当溅射气压继续升到3.9Pa,(110)和(200)衍射峰明显增强,说明Ba0.65Sr0.35TiO3 薄膜具有(110) (200)择优取向.AFM和SEM结果显示薄膜晶粒细小均匀、结构致密、表面平整,且无裂纹、无孔洞.分析结果显示优化工艺参数制备的Ba0.65Sr0.35TiO3 薄膜是用以制备非致冷红外探测器的优质材料.     

Characterization of stepwise flash-evaporated CuInSe2 films

CuInSe₂ (CIS) films were deposited by stepwise flash evaporation from polycrystalline powder source onto glass substrates held at various temperatures ranging from 100 to 560 K. The phase purity and microstructure were analyzed by transmission electron microscopy. The investigations show that films grown at 300 K and below were amorphous, whereas those grown at 370 K and above were polycrystalline in nature. The grain size in polycrystalline films were found to improve with increase in substrate temperature and during post-deposition annealing. The films had near stoichiometric composition as revealed by Rutherford backscattering spectrometry. Analysis of the optical transmittance spectra of CIS films deposited at 520 K yielded a value of ∼0.97 eV for the fundamental band gap.     

Effect of annealing on the composition, structure and mechanical properties of carbon nitride films deposited by middle-frequency magnetron sputtering

Carbon nitride films were deposited by middle-frequency reactive magnetron sputtering and annealed at different temperatures in nitrogen ambient. X-ray photoelectron spectroscopy, Raman scattering, transmission electron microscopy, and nano-indenter were used to characterize the as-deposited and annealed films. The analysis showed that annealing resulted in the dissociation of N and C in the films. The dissociation of C happened after 500 °C and lagged behind that of N. With the increase of annealing temperature, the disorder of sp² C decreased and the films were gradually graphitized. The microstructure changed from amorphous to fullerene-like CN_x with the annealing temperature increasing to 500 °C, and then to nitridized graphite nanocrystals at 600 °C. The graphitization resulted in a drastic decreasing of hardness and modulus of the films.     

Nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition

Nano-polycrystalline vanadium oxide thin films have been successfully produced by pulsed laser deposition on Si(100) substrates using a pure vanadium target in an oxygen atmosphere. The vanadium oxide thin film is amorphous when deposited at relatively low substrate temperature (500 degrees C) and enhancing substrate temperature (600-800 degrees C) appears to be efficient in crystallizing VOx thin films. Nano-polycrystalline V3O7 thin film has been achieved when deposited at oxygen pressure of 8 Pa and substrate temperature of 600 degrees C. Nano-polycrystalline VO2 thin films with a preferred (011) orientation have been obtained when deposited at oxygen pressure of 0.8 Pa and substrate temperatures of 600-800 degrees C. The vanadium oxide thin films deposited at high oxygen pressure (8 Pa) reveal a mix-valence of V5+ and V4+, while the VOx thin films deposited at low oxygen pressure (0.8 Pa) display a valence of V4+. The nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition have smooth surface with high qualities of mean crystallite size ranging from 30 to 230 nm and Ra ranging from 1.5 to 22.2 nm. Relative low substrate temperature and oxygen pressure are benifit to aquire nano-polycrystalline VOx thin films with small grain size and low surface roughness.     

Microstructural Evolution in Cold-Rolled Squeeze-Cast SiCw/Al Composites during Annealing

A 15 vol. pct SiC_w/Al composite was fabricated by a squeeze cast route followed by hot extrusion in the extrusion ratioof 18:1 and cold rolling to 50%. Microstructural evolution in the cold rolled composite during annealing was studied usingmacrohardness measurement and transmission electron microscopy (TEM). It was found that, during cold rolling the plastic flowof the matrix was restricted by the whiskers around them along the rolling direction, which resulted in different microstructurefrom near whiskers to far away. The cold rolled composite exhibited different microstructural development on 1 h annealingat different temperatures. Under annealing at about 100℃, recovery reaction occurred obviously and the introduction ofSiC whiskers resulted in enhanced recovery reaction. Under annealing above about 200℃, recrystallization (growth of nucleiby high-angle grain boundary migration) and extended recovery took place simultaneously. When annealing temperaturewas increased up to 500℃, recrystallization     

Effect of annealing atmosphere (Ar vs. air) and temperature on the electrical and optical properties of spin-coated colloidal indium tin oxide films

Colloidal indium tin oxide (ITO) ~6 nm nanoparticles synthesized in-house were deposited by spin coating on fused silica substrates, resulting in high resistivity films due to the presence of passivating organics. These films were annealed at various temperatures ranging from 150 to 750 °C in air and argon atmospheres. The films are very transparent in the as-coated form, and they retain high transparency upon annealing, except the films annealed at 300 °C in argon, which became brown due to incomplete pyrolysis of the organics. Thermogravimetric analysis and Raman characterization showed that the removal of organics increases with an increase in the annealing temperature, and that this removal is more efficient in the oxidizing atmosphere of air, especially in the 300–450 °C temperature range than in Ar. Although ITO defect chemistry suggests that argon annealing should result in higher carrier concentration than air annealing, the faster removal of insulating organics upon annealing in air resulted in significantly lower film resistivity at intermediate annealing temperatures for films annealed in air than in Ar. At higher annealing temperatures, both Ar and air annealing, resulted in comparable film resistivities (the lowest achieved was ~10⁰ Ω cm).