Transmission electron microscopy studies of HfO2 thin films grown by chloride-based atomic layer deposition

Detailed transmission electron microscopy characterization of HfO₂ films deposited on Si(1 0 0) using atomic layer deposition has been carried out. The influence of deposition temperature has been investigated. At 226 °C, a predominantly quasi-amorphous film containing large grains of cubic HfO₂ (a₀ = 5.08 Å) was formed. Grain morphology enabled the nucleation sites to be determined. Hot stage microscopy showed that both the cubic phase and the quasi-amorphous phase were very resistant to thermal modification up to 500 °C. These observations suggest that nucleation sites for the growth of the crystalline cubic phase form at the growing surface of the film, rather homogeneously within the film. The films grown at higher temperatures (300-750 °C) are crystalline and monoclinic. The principal effects of deposition temperature were on: grain size, which coarsens at the highest temperature; roughness with increases at the higher temperatures due to the prismatic faceting, and texture, with texturing being strongest at intermediate temperatures. Detailed interfacial characterization shows that interfacial layers of SiO₂ form at low and high temperatures. However, at intermediate temperatures, interfaces devoid of SiO₂ were formed.     

Effects of carbonization and substrate temperature on the growth of 3C-SiC on Si(1 1 1) by SSMBE

The growth of 3C-SiC on Si(1 1 1) substrate was performed at different carbonization temperatures and substrate temperatures by solid-source molecular beam epitaxy (SSMBE). The properties of SiC film were analyzed with in situ reflection high energy electron diffraction (RHEED), X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The best carbonization temperature of 810 °C was found to be optimal for the surface carbonization. The quality of SiC film grown on Si at substrate temperature of 1000 °C is best. The worse crystalline quality for the sample grown at higher temperature was attributed to the large mismatch of thermal expansion coefficient between SiC and Si which caused more dislocation when sample was cooled down to room temperature from higher substrate temperature. Furthermore, the larger size of single pit and the total area of the pits make the quality of SiC films grown at higher temperature worse. More Si atoms for the sample grown at lower temperature were responsible for the degradation of crystalline quality for the sample grown at lower temperature.     

The influence of substrate temperature variation on tungsten oxide thin film growth in an HFCVD system

Tungsten oxide (WO₃) thin films were deposited by a modified hot filament chemical vapor deposition (HFCVD) technique using Si (1 0 0) substrates. The substrate temperature was varied from room temperature to 430 °C at an interval of 100 °C. The influence of the substrate temperature on the structural and optical properties of the WO₃ films was studied. X-ray diffraction and Raman spectra show that as substrate temperature increases the film tends to crystallize from the amorphous state and the surface roughness decreases sharply after 230 °C as confirmed from AFM image analysis. Also from the X-ray analysis it is evident that the substrate orientation plays a key role in growth. There is a sharp peak for samples on Si substrate due to texturing. The film thickness also decreases as substrate temperature increases. UV-vis spectra show that as substrate temperature increases the film property changes from metallic to insulating behavior due to changing stoichiometry, which was confirmed by XPS analysis.     

Enhanced ferroelectric properties of vanadium doped bismuth titanate (BTV) thin films grown by pulsed laser ablation technique

Bi_3.99Ti_2.97V_0.03O₁₂ (BTV) thin films were grown by pulsed laser deposition at substrate temperatures ranging between 650 and 750 °C. The structural phase, and orientation of the deposited films were investigated in order to understand the effect of the deposition parameters on the properties of the BTV films. As the substrate temperature was increased to 700 °C, the films started showing a tendency of assuming a c-axis preferred orientation, while at lower temperatures polycrystalline films were formed. The Au/BTV/Pt capacitor showed an interesting dependence of the remnant polarization (P_r) as well as dc leakage current values on the growth temperature. The film deposited at 675 °C showed a very large 2P_r of 42 μC cm⁻², which is the largest for BTV thin films among the values reported so far.     

Effects of substrate temperature on properties of NbNx films grown on Nb by pulsed laser deposition

NbN_x films were deposited on Nb substrate using pulsed laser deposition. The effects of substrate deposition temperature, from room temperature to 950 °C, on the preferred orientation, phase, and surface properties of NbN_x films were studied by X-ray diffraction, atomic force microscopy, and electron probe micro analyzer. We find that the substrate temperature is a critical factor in determining the phase of the NbN_x films. For a substrate temperature up to 450 °C the film showed poor crystalline quality. With temperature increase the film became textured and for a substrate temperature of 650−850 °C, mix of cubic δ-NbN and hexagonal phases (β-Nb₂N + δ′-NbN) were formed. Films with a mainly β-Nb₂N hexagonal phase were obtained at deposition temperature above 850 °C. The c/a ratio of β-Nb₂N hexagonal shows an increase with increased nitrogen content. The surface roughness of the NbN_x films increased as the temperature was raised from 450 to 850 °C.     

Structure and optical properties of nanostructured zinc oxide films with different growth temperatures

ZnO films were prepared by pulsed laser deposition (PLD) on glass substrate with temperature ranging from room temperature (RT) to 500 °C. All the films formed the hexagonal wurtzite structure and showed the c-axis (0 0 2) preferred orientation. The films deposited at 200 °C showed the narrowest full width at half maximum of both X-ray diffraction (XRD) and rocking curve, largest height grain size, smallest macrostress and least point defects. Meanwhile, it was found that the films deposited at 350 °C displayed the most intense diffraction peak in XRD and a strong UV emission while it showed the most intense defect-related green emission, fastest growth rate and larger macrostress. In addition, the cross section images showed all films grew with a columnar form along (0 0 2) orientation.     

Highly conducting and transparent Ti-doped CdO films by pulsed laser deposition

Titanium-doped cadmium oxide thin films were deposited on quartz substrate by pulsed laser deposition technique. The effect of substrate temperature on structural, optical and electrical properties was studied. The films grown at high temperature show (2 0 0) preferred orientation, while films grown at low temperature have both (1 1 1) and (2 0 0) orientation. These films are highly transparent (63-79%) in visible region, and transmittance of the films depends on growth temperature. The band gap of the films varies from 2.70 eV to 2.84 eV for various temperatures. It is observed that resistivity increases with growth temperature after attaining minimum at 150 °C, while carrier concentration continuously decreases with temperature. The low resistivity, high transmittance and wide band gap titanium-doped CdO films could be an excellent candidate for future optoelectronic and photovoltaic applications.     

Surfactant effect of Sb on the growth of MnSi1.7 layers on Si(0 0 1)

Deposition of one monolayer of Sb prior to the deposition of Mn at 600 °C is observed to increase the MnSi_1.7 island density by about two orders of magnitude as well as to change the crystalline orientation of the silicide grains. The preferential epitaxial orientation of MnSi_1.7 grains grown by this process is determined to be MnSi_1.7(1 0 0)[0 1 0]||Si(0 0 1)[1 0 0]. This growth procedure results in the silicide growth into the Si matrix. For comparison, the same deposition process carried out without Sb leads to silicide formation on top of the substrate surface. The observed morphological changes of the MnSi_1.7 layers can be explained by a reduced surface diffusion of the Mn atoms on Si(0 0 1) in presence of the Sb monolayer. Additionally, lateral Si diffusion is considered to be nearly suppressed, which is responsible for the observed silicide growth into the substrate.     

Epitaxial growth of Sc-doped ZnO films on Si by sol-gel route

The epitaxial growth of doped ZnO films is of great technological importance. Present paper reports a detailed investigation of Sc-doped ZnO films grown on (1 0 0) silicon p-type substrates. The films were deposited by sol-gel technique using zinc acetate dihydrate as precursor, 2-methoxyethanol as solvent and monoethanolamine (MEA) as a stabilizer. Scandium was introduced as dopant in the solution by taking 0.5 wt%¹ of scandium nitrate hexahydrate. The effect of annealing on structural and photoluminescence properties of nano-textured Sc-doped films was investigated in the temperature range of 300-550 °C. Structural investigations were carried out using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.21° are obtained at an annealing temperature of 400 °C. The SEM images of ZnO:Sc films have revealed that coalescence of ZnO grains occurs due to annealing. Ostwald ripening was found to be the dominant mass transport mechanism in the coalescence process. A surface roughness of 4.7 nm and packing density of 0.93 were observed for the films annealed at 400 °C. Room temperature photoluminescence (PL) measurements of ZnO:Sc films annealed at 400 °C showed ultraviolet peak at about (382 nm) with FWHM of 141 meV, which are comparable to those found in high-quality ZnO films. The films annealed below or above 400 °C exhibited green emission as well. The presence of green emission has been correlated with the structural changes due to annealing. Reflection high energy electron diffraction pattern confirmed the nearly epitaxial growth of the films.     

Characteristics of Ni films deposited on SiO2/Si(1 0 0) and MgO(0 0 1) by direct current magnetron sputtering system with the oblique target

280 nm-thick Ni films were deposited on SiO₂/Si(1 0 0) and MgO(0 0 1) substrates at 300 K, 513 K and 663 K by a direct current magnetron sputtering system with the oblique target. The films deposited at 300 K mainly have a [1 1 0] crystalline orientation in the film growth direction. The [1 1 0]-orientation weakens and the [1 1 1]- and [1 0 0]-orientations enhance with increasing deposition temperature. The lattice constant of the Ni films is smaller than that of the Ni bulk, except for the film grown on MgO(0 0 1) at 663 K. Furthermore, as the deposition temperature increases, the lattice constant of the films grown on the SiO₂/Si(1 0 0) decreases whereas that of the films grown on the MgO(0 0 1) increases. The films deposited at 300 K and 513 K grow with columnar grains perpendicular to the substrate. For the films deposited at 663 K, however, the columnar grain structure is destroyed, i.e., an about 50 nm-thick layer consisting of granular grains is formed at the interface between the film and the substrate and then large grains grow on the layer. The Ni films deposited at 300 K consist of thin columnar grains and have many voids at the grain boundaries. The grains become thick and the voids decrease with increasing deposition temperature. The resistivity of the film decreases and the saturation magnetization increases with increasing deposition temperature.     

Influence of substrate temperature on the texture of barium ferrite film by magnetron sputtering

Barium ferrite thin films have been prepared by radio frequency magnetron sputtering on a sapphire (0 0 1) substrate at substrate temperature of 500 °C and 650 °C, respectively. The films were further annealed in air at 1000 °C for 5 h. X-ray diffraction shows that the films at the lower substrate temperatures have a good epitaxial relation with respect to the substrate, while the samples under the higher substrate temperatures have (1 0 9) planes parallel to the substrate. The remanence ratio decreases from 0.82 to 0.47 when the substrate temperature is increased. We attribute the variation of the growth direction to the enhanced vertical mobility of the deposited atoms when the substrate temperature is increased.     

Structural, electrical and optical properties of ZnS films deposited by close-spaced evaporation

ZnS films have been deposited on glass substrates by close-spaced evaporation (CSE) technique. The films were grown at different temperatures in the range, 200-350 °C. The layers have been characterized with X-ray diffractometer (XRD), atomic force microscope (AFM), energy dispersive analysis of X-rays (EDAX) and optical spectrophotometer to evaluate the quality of the layers for photovoltaic applications. The studies showed that the optimum substrate temperature for the growth of ZnS layers was 300 °C. The films grown at these temperatures exhibited cubic structure with nearly stoichiometric composition. The AFM data revealed that the films had nano-sized grains with a grain size of ∼40 nm. The optical studies exhibited direct allowed transition with an energy band gap of 3.61 eV. The other structural and optical parameters such as lattice stress, dislocation density, refractive index and extinction coefficient were also evaluated. The temperature-dependent conductivity measured in the range, 303-523 K showed a change in the conduction mechanism at 120 °C. The activation energy values evaluated using the temperature dependence of electrical conductivity are 7 and 29 meV at low and high temperature regions, respectively.     

The optoelectronic properties of silicon films deposited by inductively coupled plasma CVD

Hydrogenated amorphous and microcrystalline silicon films were deposited by inductively coupled plasma chemical vapor deposition (ICP-CVD) at low substrate temperatures using H₂-diluted SiH₄ as a source gas. High-density plasma generated by inductively coupled excitation facilitates the crystallization of silicon films at low temperatures, and microcrystalline silicon films were obtained at the substrate temperature as low as 180 °C. The columnar structure of the films becomes more and more compact with an increase of their crystallinity. The reduction of hydrogen content in the films causes a narrowing of the optical bandgap and an enhancement of the absorption with increasing the substrate temperature. The microcrystalline silicon films show two electronic transport mechanisms: one is related to the density of state distribution in the temperature region near room temperature and the other is the variable range hopping between localized electronic states close to the Fermi level below 170 K. A reasonable explanation is presented for the dependence of the optoelectronic properties on the microstructure of the silicon films. The films prepared at a substrate temperature of 300 °C have highly crystalline and compact columnar structure, high optical absorption coefficient and electrical conductivity, and a low hydrogen content of 3.8%.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Characterization of CdTe films with in situ CdCl2 treatment grown by a simple vapor phase deposition technique

A unique vapor phase deposition (VPD) technique was designed and built to achieve in situ CdCl₂ treatment of CdTe film. The substrate temperature was 400 °C, and the temperature of CdTe mixture with CdCl₂ source was 500 °C. The structural and morphological properties of CdTe have been studied as a function of wt.% CdCl₂ concentration by using X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). XRD measurements show that the presence of CdCl₂ vapor induces (1 1 1)-oriented growth in the CdTe film. SEM measurements have shown enhance growth of grains, in the presence of CdCl₂. From AFM the roughness of the films showed a heavy dependence on CdCl₂ concentration. In the presence of 4% CdCl₂ concentration, the CdTe films roughness has a root mean square (rms) value of about 275 Å. This value is about 831 Å for the non-treated CdTe films.     

Deposition of quasi-crystal Al-doped ZnO thin films for photovoltaic device applications

Quasi-crystal aluminum-doped zinc oxide (AZO) films were prepared by in situ radio frequency (RF) magnetron sputtering (sputtering without annealing) on glass substrates. The influence of deposition parameters on the optoelectronic and structural properties of the in situ deposited quasi-crystal AZO films was investigated in order to compare resulting samples. X-ray diffraction (XRD) patterns show that the quasi-crystal AZO thin films have excellent crystallization improved with increase of the RF power and substrate temperature, with an extremely preferential c-axis orientation exhibit sharp and narrow XRD pattern similar to that of single-crystal. Field emission scanning electron microscopy (FESEM) images show that quasi-crystal AZO thin films have uniform grains and the grain size increase with the increase of RF power and substrate temperature. Craters of irregular size with the columnar structure are observed in the quasi-crystal AZO thin films at a lower substrate temperature while many spherical shaped grains appeared at a higher substrate temperature. The average optical transmittance of all the quasi-crystal AZO films was over 85% in the 400-800 nm wavelength range. The resistivity of 4.176 × 10⁻⁴ Ω cm with the grain size of 76.4891 nm was obtained in the quasi-crystal AZO thin film deposited at 300 °C, under sputtering power of 140 W.     

Influence of substrate temperature on properties of MgF2 coatings

Thermal boat evaporation was employed to prepare MgF₂ single-layer coatings upon both JGS1 and UBK7 substrates at different substrate temperatures. Microstructure, transmittance and residual stress of these coatings were measured by X-ray diffraction, spectrophotometer, and optical interferometer, respectively. Measurement of laser induced damage threshold (LIDT) of the samples was performed at 355 nm, 8 ns pulses. The results showed that high substrate temperature was beneficial to crystallization of the film. Above 244 °C, the refractive index increased gradually with the substrate temperature rising. Whereas, it was exceptional at 210 °C that the refractive index was higher than those deposited at 244 and 277 °C. The tensile residual stresses were exhibited in all MgF₂ films, but not well correlated with the substrate temperature. In addition, the stresses were comparatively smaller upon JGS1 substrates. A tendency could be seen that the LIDTs reached the highest values at about 244 °C, and the films upon JGS1 had higher LIDTs than those upon UBK7 substrates at the same temperature. Meanwhile, the damage morphologies showed that the laser damage of the coating resulted from an absorbing center at the film-substrate interface. The features of the damages were displayed by an absorbing center dominated model. Furthermore, the reason of the difference in LIDT values was discussed in detail.     

Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

Temperature-dependent growth mode of W-doped ZnO nanostructures

We report on the effects of glass substrate temperature on the crystal structure and morphology of tungsten (W)-doped ZnO nanostructures synthesized by pulsed-laser deposition. X-ray diffraction analysis data shows that the W-doped ZnO thin films exhibit a strongly preferred orientation along a c-axis (0 0 0 L) plane, while scanning electron and atomic force microscopes reveal that well-aligned W-doped ZnO nanorods with unique shape were directly and successfully synthesized at substrate temperature of 550 °C and 600 °C without any underlying catalyst or template. Possible growth mechanism of these nanorods is suggested and discussed.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.