Co-emission of UV, violet and green photoluminescence of ZnO/TiO2 thin film

ZnO/TiO₂ thin films were fabricated on quartz glass substrates by E-beam evaporation. The structural and optical properties were investigated by X-ray diffraction (XRD), Raman spectra, optical transmittance and photoluminescence. XRD analysis indicates that the TiO₂ buffer layer can increase the preferential orientation along the (002) plane of the ZnO film. PL measurements suggest that co-emission of strong UV peak at 378 nm, violet peak at 423 nm and weak green luminescence at 544 nm is observed in the ZnO/TiO₂ thin film. The violet luminescence emission at 423 nm is attributed to the interface trap in the ZnO film grain boundaries.     

Sonochemical preparation of TiO2 nanoparticles in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethylsulfonyl)amide

Spherical shaped anatase nanoparticles (ø 5 nm) have been synthesized in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethanesulfonyl)amide from titanium tetraisopropoxide by ultrasound assisted synthesis under ambient conditions. XRD, EDX, TEM, XPS, Raman, UV–vis, PL and BET measurements have been employed for characterization of the nanostructure of as-prepared TiO₂. XRD and Raman measurements both show that the obtained material is crystalline with anatase structure. The morphology of TiO₂ nanoparticles was characterized by transmission electron microscopy (TEM). The bandgap of the TiO₂ nanocrystals estimated from XRD and UV–vis measurements is about 3.3 eV. The surface area of a typical sample is 177 m² g⁻¹. The synthesized anatase nanocrystals show good photocatalytic activity in the degradation of methylorange.     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

The effects of the thickness of TiO2 films on the performance of dye-sensitized solar cells

Nanocrystalline anatase TiO₂ thin films with different thicknesses (0.5-2.0 μm) have been deposited on ITO-coated glass substrates by a sol-gel method and rapid thermal annealing for application as the work electrode for dye-sensitized solar cells (DSSC). From the results, the increases in thickness of TiO₂ films can increase adsorption of the N3 dye through TiO₂ layers to improve the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. However, the J_sc and V_oc of DSSC with a TiO₂ film thickness of 2.0 μm (8.5 mA/cm² and 0.61 V) are smaller than those of DSSC with a TiO₂ film thickness of 1.5 μm (9.2 mA/cm² and 0.62 V). It could be due to the fact that the increased thickness of TiO₂ thin films also resulted in a decrease in the transmittance of TiO₂ thin films thus reducing the incident light intensity on the N3 dye. An optimum power conversion efficiency (η) of 2.9% was obtained in a DSSC with the TiO₂ film thickness of 1.5 μm.     

Effects of oxygen flow ratios and annealing temperatures on Raman and photoluminescence of titanium oxide thin films deposited by reactive magnetron sputtering

Titanium oxide (TiO_x) thin films were deposited on the Si(100) substrates by direct-current reactive magnetron sputtering at 3-15 % oxygen flow ratios (FO₂% = FO₂/(FO₂ + FAr) × 100%), and then annealed by rapid thermal annealing (RTA) at 350-750 °C for 2 min in air. The phase, bonding and luminescence behaviors of the as-deposited and annealed TiO_x thin films were analyzed by X-ray diffraction (XRD), Raman spectroscopy and photoluminescence (PL) spectroscopy, respectively. The as-deposited TiO_x films were amorphous from XRD and showed weak Raman intensity. In contrast, the distinct crystalline peaks of anatase and rutile phases were detected after RTA at 550-750 °C from both XRD and Raman spectra. A mixture of anatase and rutile phases was obtained by RTA at 3 FO₂% and its amount increased with annealing temperature. Only the anatase phase was detected in the 6-15 FO₂% specimens after RTA. The PL spectra of all post-annealed TiO_x films showed a broad peak in visible light region. The PL peak of TiO_x film at 3 FO₂% at 750 °C annealing can be fitted into two Gaussian peaks at ~ 486 nm (2.55 eV) and ~ 588 nm (2.11 eV) which were attributed to deep-level emissions of oxygen vacancies in the rutile and anatase phases, respectively. The peak around 550 nm was observed at 6-15 FO₂% which is attributed to electron-hole pair recombination from oxygen vacancy state in anatase phase to valence band. The variation of intensity of PL peaks is concerned with the formation of the rutile and anatase phases at different FO₂% and annealing temperatures.     

Fabrication of porous TiO2 film via hydrothermal method and its photocatalytic performances

Porous anatase (TiO₂) films were fabricated onto stainless steel substrates with Ti(OC₄H₉)₄ as a precursor via hydrothermal process. The crystallization and porous structure of TiO₂ film were dependent on the time and temperature of the hydrothermal reaction. A TiO₂ film with orderly porous structure and high crystallization was obtained upon treatment at 150 °C for 2 h. The grain size of TiO₂ is ca. 6 nm, and pore diameter is ca. 10 nm. Diffusion of Fe into the porous TiO₂ film occurred; Fe also diffused onto the surface of the film with the extension of hydrothermal reaction time or increase of the reaction temperature. The diffusion reaction has a large effect on the formation of porous TiO₂ film as well as its interface texture. However, it does not change the crystal phase of the TiO₂. The resultant TiO₂ film showed high photocatalytic activity towards degradation of gaseous formaldehyde.     

Third-order optical nonlinearities in anatase and rutile TiO2 thin films

Titanium dioxide (TiO₂) films have been fabricated on fused quartz and Si(001) substrates by pulsed laser deposition technique and the single-phase anatase and rutile films were obtained under the optimal conditions. The surface images and optical transmission spectra were investigated by scanning electron microscopy and double beam spectrophotometer, respectively. The values of optical band-gap and linear refractive index of the anatase and rutile films were determined. The optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. Through the open-aperture and closed-aperture Z-scan measurements, the real and imaginary parts of the third-order nonlinear optical susceptibility were calculated and the results show that the anatase phase TiO₂ films exhibit larger nonlinear refractive effects compared with rutile phase. The figure of merit, T, defined by T = βλ/n₂, was calculated to be 0.8 for anatase films, meeting the requirement of T < 1 and showing potential applications in all-optical switching devices.     

Effect of a pulsed Nd:YAG laser irradiation on multi-walled carbon nanotubes film

Multi-walled carbon nanotubes (MWCNTs) film have been analyzed by Raman spectroscopy to clarify the effect of a pulsed Nd:YAG laser heating. The MWCNTs film surface was flashed with the fundamental harmonic (λ = 1064 nm) or the second harmonic (λ = 532 nm) of a single pulse of Nd:YAG laser in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. At the laser fluence of 500 mJ/cm² with Nd:YAG laser (λ = 1064 nm), the surface reached the maximum temperature 1395 °C at 12 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Reactively sputtered N-doped titanium oxide films as visible-light photocatalyst

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared by reactive magnetron sputtering of a titanium metal target in gas mixtures of argon, oxygen and nitrogen. Two types of nitrogen species are formed in the films following the fraction of N₂ (F_N2) in the reactive atmosphere. One is substitutional nitrogen in anatase titania phase and the other is nitrogen in TiN phase. In a large range of F_N2 from 0 to 0.57, TiO_xN_y films in anatase structure with about 1.0–1.4 at.% substitutional nitrogen are produced and the films exhibit red shifts to ∼ 500 nm from the absorption edge of ∼ 380 nm of undoped TiO₂. The nitrogen is readily doped in the films by energetic nitrogen ions in the plasma and the films exhibited photocatalytic properties under visible light. When excess nitrogen is supplied as the F_N2 above 0.75, the resulting film contains 20.8 at.% of nitrogen with formation of TiN that makes the film opaque and destroys the photocatalytic activity largely.     

Optical investigations of multi-dimensional ZnO hybrid structures

The authors report on the optical properties of multi-dimensional ZnO hybrid structures, consisting of film (2D)/nanorods (1D)/sapphire substrate (2D), grown by metalorganic chemical vapor deposition (MOCVD). Photoluminescence investigations reveal that the sample with top layer grown at a decreased growth temperature of 240 °C and increased reactor pressure of 5 Torr exhibits superior emission properties. The presence of strong E₂^high optical phonon mode at 438.5 cm^− 1 in the visible micro-Raman spectra demonstrates the wurtzite nature of ZnO. Although the ultraviolet Raman scattering measurements of the hybrid structures reveal the presence of in-plane tensile stress in the top ZnO layer, the sample with the improved emission performance shows the release of tensile stress.     

Synthesis and tuning of ordering and crystallinity of mesoporous titanium dioxide film

Synthesis of well-organized and highly crystalline mesoporous titania (TiO₂) film is demonstrated using triblock copolymer (Pluronic P123) as a structure directing template, through the evaporation induced self-assembly (EISA) process. The issue of thermal and structural stability of a mesoporous TiO₂ film was addressed via optimization of annealing temperature and time. An anatase phase, high crystallinity TiO₂ film with ordered pores was obtained at 430 °C after annealing for 15 min. The synthesized film was crack free with TiO₂ nanoparticle size of 10–15 nm, quasi-hexagonal pore diameter in the range of 8–10 nm and film thickness of ~ 150 nm.     

Phase determination of filtered vacuum arc deposited TiO2 thin films by optical modeling

Thin films of TiO₂ were produced using filtered vacuum arc deposition. Arc currents were 275, 300, 325 A, and the oxygen pressure during deposition was 0.93 Pa. The substrates were glass microscope slides, at temperatures of 25 °C (RT), 200 °C, and 400 °C. Film thickness was in the range 100 to 250 nm, depending on the deposition conditions. Film structure and chemical composition were determined using XRD and XPS analyses, respectively. As-deposited films were amorphous, except to two samples that were found to be crystalline (deposited with 300 A, 325 A at 400 °C), and the crystalline phase was close to that of anatase. All of the films were partially crystallized by annealing in air at 450 °C for 1 h. The O:Ti atomic concentration ratio was in the range 1.6:1-2:1, independent of deposition conditions. The optical parameters, refractive index and the extinction coefficient of the films were determined using variable angle spectroscopic ellipsometry. In addition, the optical transmission of the films were determined in the UV-VIS and IR regions. The average optical transmission in the VIS spectrum was 70-85%, affected by the interference in the film with 90% maxima and 60% minima. The refractive index at λ = 550 nm was in the range 2.4 to 2.7, depending on the deposition conditions and annealing. Using the semi-empirical model of Wemple and DiDomenico for the dielectric function below the interband absorption edge of ionic and covalent solids, the dispersion energy parameters of TiO₂ (E_o, E_d) were calculated. The underlying structural order of the amorphous films was inferred by comparing the dispersion energy parameters of the amorphous films with those of crystalline TiO₂. As expected, the refractive index of the amorphous films depended on the underlying phase of the film. The optical analyses indicated that the underlying phase of the amorphous films deposited on RT substrates was close to anatase, whereas the underlying phase of the amorphous films deposited on 400 °C substrates and annealed at 450 °C for 1 h consisted of both anatase and rutile. Thus, although the XRD analyses could not indicate the underlying phase of the amorphous films, it could be determined by the optical analyses.     

Material characteristics of sputter-deposited Zr-doped In2O3/ZnO heterostructures on sapphire (0001) substrates

5 wt.% Zr-doped In₂O₃ (Zr-In₂O₃) films with thicknesses from 95 to 220 nm were grown on 90 nm-thick ZnO-buffered sapphire (0001) substrates by radio-frequency magnetron sputtering in an oxygen-deficient atmosphere. The dependence on thickness of the structural information and electrical properties of the Zr-In₂O₃ films on the ZnO-fuffered sapphire substrates was studied. The X-ray diffraction patterns show that the (002)-textured ZnO buffer-layer is a good template for the growth of the highly (222)-textured In₂O₃ films on the sapphire substrate. The surface of the Zr-In₂O₃ film becomes rougher as the film thickness increases, perhaps because of the formation of larger mounds on the film surface as the thickness of Zr-In₂O₃ increases. The carrier concentration increased markedly from 5.8 × 10²⁰ to 1.83 × 10²¹ cm^− 3 with film thickness from 95 to 220 nm, because more growth-induced defects are formed in the thick Zr-In₂O₃ film. The large increase in the number of charge carriers and the improvement in the crystalline quality in the film reduce the resistivity of the thicker Zr-In₂O₃ film.     

Stress reduction in GaN films on (111) silicon-on-insulator substrate grown by metal-organic chemical vapor deposition

The GaN film was grown on the (111) silicon-on-insulator (SOI) substrate by metal-organic chemical vapor deposition and then annealed in the deposition chamber. A multiple beam optical stress sensor was used for the in-situ stress measurement, and X-ray diffraction (XRD) and Raman spectroscopy were used for the characterization of GaN film. Comparing the characterization results of the GaN films on the bulk silicon and SOI substrates, we can see that the Raman spectra show the 3.0 cm^− 1 frequency shift of E₂(TO), and the full width at half maximum of XRD rocking curves for GaN (0002) decrease from 954 arc sec to 472 arc sec. The results show that the SOI substrates can reduce the tensile stress in the GaN film and improve the crystalline quality. The annealing process is helpful for the stress reduction of the GaN film. The SOI substrate with the thin top silicon film is more effective than the thick top silicon film SOI substrate for the stress reduction.     

Synthesis of CuS nanorods grown at room temperature by electrodeposition method

CuS thin films were deposited on stainless steel substrates from an aqueous solution of CuSO₄, Na₂S₂O₃ and Triethanolamine. Deposited films were characterized by XRD, SEM, EDAX, Raman and Optical measurements. The electrodeposition bath concentration can be used to control the diameter of the electrodeposited nanorods within the range of 35–40 nm. The formation of complexes of copper ions and TEA was found to be a key factor in the nanorods growth process. Films are polycrystalline with hexagonal crystal structure. SEM images indicate that the film surfaces are smooth, homogeneous and well-covered. A new structure of CuS nanorods having length of 5–10 μm and diameter from 35 to 40 nm has been demonstrated. By changing bath concentration and keeping deposition time fixed the agglomeration of rods is enhanced due to the formation of large number of particles during growth process. Raman shifts of samples are detected at wave numbers 473 cm⁻¹. Typical film deposited with optimized bath concentration shows optical band gap of about 2.73 eV.     

Nanocrystalline TiO2 thin films for NH3 monitoring: microstructural and physical characterization

Nanocrystalline titanium oxide thin films have been deposited by spin coating technique and then have been analyzed to test their application in NH₃ gas-sensing technology. In particular, spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of titanium oxide thin films. The structure and the morphology of such material have been investigated by X ray diffraction, Scanning microscopy, high resolution electron microscopy and selected area electron diffraction. The X-ray diffraction measurements confirmed that the films grown by this technique have good crystalline tetragonal mixed anatase and rutile phase structure. The HRTEM image of TiO₂ thin film showed grains of about 50–60 nm in size with aggregation of 10–15 nm crystallites. Selected area electron diffraction pattern shows that the TiO₂ films exhibited tetragonal structure. The surface morphology (SEM) of the TiO₂ film showed that the nanoparticles are fine with an average grain size of about 50–60 nm. The optical band gap of TiO₂ film is 3.26 eV. Gas sensing properties showed that TiO₂ films were sensitive as well as fast in responding to NH₃. A high sensitivity for ammonia indicates that the TiO₂ films are selective for this gas.     

Semiconductor characterization of Cr-doped titania electrodes with p-n homojunction devices

A nano-TiO₂ electrode with a p-n homojunction device was designed and fabricated by coating of the nano-TiO₂ (n-type) film together with the Cr³⁺-doped TiO₂ (p-type) film. The sample films were prepared with synthesized sol-gel TiO₂ which were verified as nano-size particles with anatase structure. The semiconductor characteristic of the p-type and n-type films was analyzed by current-voltage (I-V) measurements. Results show that the rectifying characteristic of the TiO₂ films was observed from the I-V data illustration for both the n-type and p-type films. In addition, the characteristic of the rectifying curves was influenced by the fabrication conditions of the sample films, such as the doping concentration of Cr³⁺, heating temperature of the films, and film thickness. From the I-V analysis, the rectifying current of this diode showed a 10² mA order higher than the one of the n-type film. The p-n homojunction TiO₂ electrode showed greater performance of electronic properties than the n-type TiO₂ electrode.     

Influence of double buffer layers on properties of Ga-polarity GaN films grown by rf-plasma assisted molecular-beam epitaxy

Ga-polarity GaN thin films were grown on sapphire (0001) substrates by rf-plasma assisted molecular beam epitaxy (MBE) using a double buffer layer, which consisted of an intermediate-temperature GaN buffer layer (ITBL) grown at 690 °C and a conventional AlN buffer layer deposited at 740 °C. Raman scattering spectra showed that the E₂ (high) mode of GaN film grown on conventional AlN buffer layer is at about 570 cm⁻¹, and shifts to 568 cm⁻¹ when an ITBL was used. This indicates that the ITBL leads to the relaxation of residual strain in GaN film caused by mismatches in the lattice constants and coefficients of thermal expansion between the GaN epilayer and the sapphire substrate. Compared to the GaN film grown on the conventional AlN buffer layer, the GaN film grown on an ITBL shows higher Hall mobility and substantial reduction in the flicker noise levels with a Hooge parameter of 3.87×10⁻⁴, which is believed to be, to date, the lowest reported for GaN material. These results imply that the quality of Ga-polarity GaN films grown by MBE can be significantly improved by using an ITBL in addition to the conventional low-temperature AlN buffer layer.     

Electrochromic properties of TiO2 anatase thin films prepared by a dipping sol-gel method

Electrochromic TiO₂ anatase thin films on ITO were prepared by the sol-gel dipping method using a solution of titanium tetraisopropoxide, diethanolamine and ethanol. The films were transparent in the visible range and can be colored in a solution of LiClO₄ in propylene carbonate. The transmittances of the colored films were found to be strongly dependent on the Li⁺ inserted charge. Combining the experimental data obtained from in situ Raman and in situ transmittance spectra with the data from chronoamperometic measurements, it was demonstrated that the fully colorated state of the TiO₂ anatase films is Li_0.5TiO₂ with a crystalline structure of Imma space group symmetry. In the Raman spectra this coloration state exhibits five characteristic bands at 176, 224, 316, 531 and 629 cm⁻¹.     

Investigation on the structure of TiO2 films sputtered on alloy substrates

Titanium dioxide (TiO₂) films have been successfully deposited on metal alloy substrates by radio-frequency magnetron reactive sputtering in an Ar+O₂ gas mixture. The effects of gas total pressure on the structure and phase transition of TiO₂ films were studied by X-ray diffraction and Raman spectra. It is suggested that the film structure changes from rutile to anatase while work gas total pressure changes from 0.2 to 2 Pa. The structure of TiO₂ films is not affected by the film thickness.