Structural properties of the titanium dioxide thin films grown by atomic layer deposition at various numbers of reaction cycles

A dependence of structural properties of TiO₂ films grown on both Si- and Ti-substrates by atomic layer deposition (ALD) at the temperature range of 250-300 °C from titanium ethoxide and water on the number of reaction cycles N was investigated using Fourier-transform infrared (FTIR) spectroscopy and X-Ray diffraction (XRD). TiO₂ films grown on both Si- and Ti-substrates revealed amorphous structure at low values of N < 400. However, an increase of N up to values 400-3600 resulted in the growth of polycrystalline TiO₂ with structure of anatase on both types of substrates and according to XRD-measurements the sizes of crystallites rose with the increase of N. The maximum anatase crystallite size for TiO₂ grown on Ti-substrate was found to be on ∼35% lower in comparing with that for TiO₂ grown on Si-substrate. A use of titanium methoxide as a Ti precursor with the ligand size smaller than in case of titanium ethoxide allowed to observe an influence of the ligand size on both the growth per cycle and structural properties of TiO₂. The average growth per cycle of TiO₂ deposited from titanium methoxide and water (0.052 ± 0.01 nm/cycle) was essentially higher than that for TiO₂ grown from titanium ethoxide and water (0.043 ± 0.01 nm/cycle). Ligands of smaller sizes were found to promote the higher crystallinity of TiO₂ in comparison with the case of using the titanium precursor with ligands of bigger sizes.     

Photocatalytic properties of TiO2 thin films obtained by glancing angle deposition

Titanium dioxide (TiO₂) thin films with different nanostructures such as nano-particles and separated vertical columns were grown by glancing angle deposition (GLAD) in an electron beam evaporation system. The photocatalytic properties of grown TiO₂ films with different deposition angles and different annealing temperatures were evaluated by following decomposition of methyl orange under ultraviolet (UV) light irradiation. The results suggest that increased surface area due to the GLAD process could improve the photocatalytic properties of TiO₂ films.     

Influence of glucose on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method on glass substrates followed by calcinations at 500 °C for an hour. The effect of glucose on the structure and optical properties of the films was studied. The structural characteristics of the samples were analyzed by X-ray diffractometer (XRD) and atomic force microscope (AFM). The optical properties were studied by a UV-visible spectrophotometer. The results show that some of the prepared ZnO thin films have a high preferential oriented c-axis orientation with compact hexagonal wurtzite structure due to a proper amount of glucose introducing. After introducing the glucose additive in ZnO colloids, the intensity of (002) peak, the transmittance, and the optical band gap of the ZnO thin films increases because of the enhanced ZnO crystallization. On the contrary, the absorbance, the film thickness, and the surface root-mean-square (RMS) roughness of the ZnO thin films decreases. The glucose additive could not only improve the surface RMS roughness and microstructure of ZnO thin films, but also enhance the transmittance and the energy band gap more easily.     

Nanocrystalline formation and optical properties of germanium thin films prepared by physical vapor deposition

Amorphous and nanocrystalline germanium thin films were prepared on glass substrates by physical vapor deposition (PVD). The influence of thermal annealing on the characteristics of the Ge thin films has been investigated. X-ray diffraction (XRD) and SEM show amorphous structure of films deposited at room temperature. After thermal annealing, the crystallinity was improved when the annealing temperature increases. The Ge thin films annealed at different temperatures in air were nanocrystalline, having the face-centered cubic structure with preferred orientation along the 〈1 1 1〉 direction. The nanostructural parameters have been evaluated by using a single-order Voigt profile analysis. Moreover, the analysis of the optical transmission and reflection behavior was carried out. The values of direct and indirect band gap energies for amorphous and nanocrystalline phases are 0.86±0.02, 0.65±0.02 and 0.79±0.02, 0.61±0.02 eV, respectively. In addition, the complex optical functions for the wavelength range 600-2200 nm are reported. The refractive index of the nanocrystalline phase drops from 4.80±0.03 to 2.04±0.02, and amorphous phase changes from 5.18±0.03 to 2.42±0.02 for the whole wavelength range. The dielectric functions ε₁ and ε₂ of the deposited films were recorded as a function of wavelength within the range from 600 to 2200 nm.     

Investigation of BiFeO3 Multiferroic thin films prepared by metalloorganic chemical vapor deposition

BiFeO₃ thin oriented films are grown on SrTiO₃(001) and ZrO₂(Y₂O₃)(001) substrates by metalloorganic chemical vapor deposition (MOCVD) in the temperature range T= 500–800°C. Iron dipivaloylmethanate Fe(thd)₃ and triphenylbismuth Bi(C₆H₅)₃ are used as volatile precursors. It is shown that the high thermal stability of Bi(C₆H₅)₃ leads to significant deviations of the Bi: Fe ratio in the film from their ratio in the precursor flow. An increase in the residence time of the precursor flow in the reactor makes this ratio close to unity. The film-substrate epitaxial relations are determined. It is found that the film orientation on the ZrO₂(Y₂O₃)(001) substrate changes with increasing temperature. Optical second harmonic generation (SHG) measurements show the presence of ferroelectric ordering in the films. A significant decrease in the Curie temperature due to epitaxial stress is found. At the same time, the magnetization noticeably increases as compared to a BiFeO₃ single crystal.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

Physical properties of ZnS thin films prepared by chemical bath deposition

Zinc sulphide thin films are deposited on SnO₂/glass using the chemical bath deposition technique. X-ray diffraction and atomic force microscopy are used to characterize the structure of the films; the surface composition of the films is studied by Auger electrons spectroscopy, the work function and the photovoltage are investigated by the Kelvin method. Using these techniques, we specify the effect of pH solution and heat treatment in vacuum at 500 °C. The cubic structure corresponding to the (1 1 1) planes of β-ZnS is obtained for pH equal to 10. The work function (Φ_material − Φ_probe) for ZnS deposited at pH 10 is equal to −152 meV. Annealing at 500 °C increases Φ_m (by about 43 meV) and induces the formation of a negative surface barrier. In all cases, Auger spectra indicate that the surface composition of zinc sulphide thin films exhibits the presence of the constituent elements Zn and S as well as C and O as impurity elements.     

Photocatalytic hydroxyapatite/titanium dioxide multilayer thin film deposited onto glass using an rf magnetron sputtering technique

Hydroxyapatite (HA)/titanium dioxide (TiO₂) thin film was deposited on glass using a radio frequency magnetron sputtering. X-ray diffraction (XRD), Fourier-transform infrared spectrometry, ultraviolet-visible spectroscopy and measurement of its photocatalytic activity by the decomposition of formaldehyde gas and the bacterial survival test of Escherichia coli (E. coli) cells were applied to characterize the film. After heat treatment (at 500 °C), XRD analysis of the HA/TiO₂ film showed a crystalline TiO₂ crystal structure with anatase phase. The transmittance of the HA/TiO₂ film decreased after the heat treatment, however, the average transmittance remained at 87% in the visible light range.In the decomposition of formaldehyde gas, the HA/TiO₂ film showed a higher decomposition rate than either the TiO₂ or the HA film alone. However, in the bacterial survival test, survival of cells on the HA/TiO₂ film was higher than that on the TiO₂ film, which indicates the HA/TiO₂ film has a lower bactericidal effect than the TiO₂ film alone.     

Structure, electrical and optical properties of TiNx films by atmospheric pressure chemical vapor deposition

Titanium nitride (TiN_x) films with various nitride compositions (x) were prepared on glass substrates by atmospheric pressure chemical vapor deposition using TiCl₄ and NH₃ as precursors. The structural, compositional, electrical and optical properties of the films were studied and the results were discussed with respect to nitride composition. The results showed a linear relationship between the lattice constant and the nitride composition. Resistivity of the films was minimized near x = 1. All the TiN_x films exhibited a transmission band with a peak value of about 15% in the visible region (400-700 nm). As the wavelength increased to transition point (λ_T-R), the reflectance of the obtained films presented a sharp increase and then reached a high value of about 50% near 2000 nm. Moreover, the red-shift of transmission band and the transition wavelength (λ_T-R) with increasing the nitride composition were also discussed.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

Effect of Er doping on optical band gap energy of TiO2 thin films prepared by spin coating

In order to evaluate the effect of Er doping in the range of 0–1.0 mol% on optical indirect band gap energy (E_g) of the film, the Er-doped TiO₂ (Er-TiO₂) thin films were spin-coated onto fluorine-doped SnO₂ coated (FTO) glasses. Glancing angle X-ray diffraction (GAXRD) results indicated that the films whose thickness was 550 nm consisted of pure anatase and FTO substrate. The anatase (101) TiO₂ peaks became broader and weaker with the rise in Er content. The apparent crystallite size decreased from 12 nm to 10 nm with increasing the amount of Er from 0 mol% to 1.0 mol%. UV–vis spectrophotometry showed that the values of E_g decreased from 3.25 eV to 2.81 eV with the increase of Er doping from 0 to 0.7 mol%, but changed to 2.89 eV when Er content was 1.0 mol%. The reduction in E_g might be attributed to electron and/or hole trapping at the donor and acceptor levels in the TiO₂ band structure.     

Microstructure,optical and structural characterization of Cd0.98Fe0.02S thin films co-doped with Zn by chemical bath deposition method

Fe-doped CdS (Cd_0.98Fe_0.02S) and Fe, Zn co-doped CdS (Cd_0.98−xZn_xFe_0.02S (x=0.02, 0.04, and 0.06)) thin films have been successfully deposited on glass substrate by chemical bath deposition technique using aqueous ammonia solution at pH = 9.5. Phase purity of the samples having cubic structure with (111) as the preferential orientation was confirmed by X-ray diffraction technique. Shift of X-ray diffraction peak position towards higher angle side and decrease of lattice parameters, volume and crystallite size confirmed the proper incorporation of Zn into Cd–Fe–S except Zn=6%. The compositional analysis (EDX) showed that Cd, Fe, Zn and S are present in the films. The enhanced band gap and higher transmittance observed in Cd_0.94Zn_0.04Fe_0.02S films are the effective way to use solar energy and enhance its photocatalytic activity under visible light. The enhanced green band emission than blue band by Zn-doping evidenced the existence of higher defect states.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO₂ nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.     

Effect of ambient gas on structural and optical properties of titanium oxynitride films

Titanium oxynitride films have been deposited on glass substrates by reactive RF magnetron sputtering of titanium target. The influence of oxygen partial pressure in N₂ + Ar and N₂ + He mixtures was examined on structural and optical properties of titanium oxynitride films. The prepared samples were characterized by X-ray diffraction, EDS, surface profilometer, AFM and contact angle measurement system. With increase in oxygen partial pressure, the grain size decreases from ∼70 nm to ∼50 nm in N₂ + Ar mixture, while from ∼60 nm to ∼37 nm in N₂ + He mixture. The thickness calculated from optical transmission data and surface profilometer is in good agreement with each other. The deposited samples are hydrophobic by nature and the contact angle was found to decrease with increase in oxygen partial pressure. Samples prepared in oxygen partial pressure ≥5.5% show transmittance of about 97% in the visible region of the spectrum in both N₂ + Ar and N₂ + He mixtures. The atomic mass of the sputtering gas (Ar and He) significantly affects the primary crystallite size, orientation as well as band gap. We were able to relate the better crystallisation of titanium atoms with low partial pressure of oxygen when films are deposited in helium instead of argon due to Penning ionization.     

Deposition of thin rhodium films by plasma-enhanced chemical vapor deposition

Thin films of rhodium have been prepared starting from dicarbonyl-2.4-pentadionato-rhodium(I), Rh(CO)₂C₅H₇O₂, by plasma enhanced CVD. The dependence of the deposition rate and film properties on substrate temperature, partial pressure of the organometallic and on hydrogen has been studied. Metal contents of 100% and thin-film resistivities as low as 5 times the bulk resistivity of rhodium have been achieved.     

Effect of cobalt doping and annealing on properties of titania thin films prepared by sol-gel process

Undoped and cobalt doped titania (TiO₂) thin films have been prepared on Si(1 0 0) monocrystal and quartz substrate using the sol-gel deposition method and annealed in air at 450, 550, 650, 750, 850, 950 and 1050 °C. Several experimental techniques (AFM, XRD, Raman spectroscopy, XRR, EDX, XPS, XAS, UV-VIS spectroscopy) have been used to characterize these films. Further more the degree of light induced hydrophilicity was estimated by measuring the contact angle of a water droplet on the film. Increase of the annealing temperature and in smaller degree also cobalt doping predispose titania crystallite growth. The rutile phase was detected at lower temperatures in the cobalt doped films than in the undoped titania films. Cobalt in the cobalt doped TiO₂ was seen to be in Co²⁺ oxidation state, mainly in CoTiO₃ phase when films were annealed at temperatures higher than 650 °C. Cobalt compounds segregated into the sub-surface region and to the surface of the titania, where they formed islands. Cobalt doping red-shifted the fundamental absorption edge further into the visible range, however it did not enhance the light induced hydrophilicity of the thin film surface as compared to the undoped titania thin films.     

Interfacial structure and electrical properties of LaAlO3 gate dielectric films on Si by metalorganic chemical vapor deposition

LaAlO₃ (LAO) gate dielectric films were deposited on Si substrates by low-pressure metalorganic chemical vapor deposition. The interfacial structure and composition distribution were investigated by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectroscopy (SIMS), and Auger-electron spectroscopy (AES). HRTEM confirms that there exists an interfacial layer between LAO and Si in most samples. AES, SIMS, and XPS analyses indicate that the interfacial layer is compositionally graded La–Al silicate and the Al element is severely deficient close to the Si surface. Electrical properties of LAO films were evaluated. No evident difference in electrical properties between samples with and without native SiO₂ layers was observed. The electrical properties are discussed in terms of LAO growth mechanisms, in relation to the interfacial structure. PACS 73.40.Qv; 81.15.Gh; 77.55.+f; 68.35.-p     

Effect of high-temperature annealing on AIN thin film grown by metalorganic chemical vapor deposition

The effect of high-temperature annealing on A1N thin film grown by metalorganic chemical vapor deposition was investigated using atomic force microscopy, Raman spectroscopy, and deep ultra-violet photoluminescence （PL） with the excitation wavelength as short as ~ 177 nm. Annealing experiments were carded out in either N2 or vacuum atmosphere with the annealing temperature ranging from 1200 ℃ to 1600 ℃. It is found that surface roughness reduced and compres- sive strain increased with the annealing temperature increasing in both annealing atmospheres. As to optical properties, a band-edge emission peak at 6.036 eV and a very broad emission band peaking at about 4.7 eV were observed in the photoluminescence spectrum of the as-grown sample. After annealing, the intensity of the band-edge emission peak varied with the annealing temperature and atmosphere. It is also found that a much stronger emission band ranging from 2.5 eV to 4.2 eV is superimposed on the original spectra by annealing in either N2 or vacuum atmosphere. We attribute these deep-level emission peaks to the VAL--ON complex in the A1N material.     

Structural and dielectric properties of Bi4Ti3O12 thin films prepared by metalorganic solution deposition

Ferroelectric Bi₄Ti₃O₁₂ thin films with single phase and nanosized microstructure were prepared on Pt/Ti/SiO₂/Si(111) substrate by metalorganic solution deposition using titanium butoxide and bismuth nitrate at relatively low annealing temperatures. The internal strain in Bi₄Ti₃O₁₂ thin films was calculated from the peak shifts and broadening of XRD patterns. With increase in annealing temperature, the uniform strain decreased from positive to zero and then to negative, and the non-uniform strain decreased and was negative. The total strain was negative and in the range of -0.2%–-1.0%, from which the stress of the films was calculated to be about -1.4×10⁹ N/m². The mode values of strain decreased with increase in annealing temperature and increased with increase in film thickness. The dielectric constant increased with increase in annealing temperature and film thickness. The dielectric properties were interpreted by considering the influence of strain, grain size, and grain boundaries. The strain lowered the polarization and increased the dielectric constant. The larger the grain size and the thinner the grain boundary, the greater the dielectric constant. The influence of grain size and grain boundary was stronger than that of the strain. Received: 23 September 1998 / Accepted: 6 January 1999 / Published online: 24 March 1999