Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Surface analysis of the nanostructured W-Ti thin film deposited on silicon

The W-Ti thin films are deposited by the dc Ar⁺ sputtering of W(70%)-Ti(30%) a.t. target on silicon substrates. The surface composition and structure of the thin film, previously exposed to air, was carried out. The surface structure was undertaken using grazing incidence X-ray diffraction (GIXRD), and compared to that of the thin film interior. The surface morphology was determined by the Scanning Tunneling Microscopy (STM). The surface composition and chemical bonding of elements on the Ti-W film were analyzed by X-ray photoelectron spectroscopy (XPS) and Low Energy Ion Scattering (LEIS). The measurements show that the overlayer of metallic oxides TiO₂ and WO₃ is formed. The first atomic layer is occupied by TiO₂ only, and its thickness is estimated to about 3.2 ± 0.4 nm. The strong surface segregation of Ti is triggered by the surface oxidation, which is confirmed by the thermodynamical considerations.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Superhydrophilic stability enhancement of RF co-sputtered TixSi1−xO2 thin films in dark

Ti_xSi_1−xO₂ compound thin-film systems were deposited by reactive RF magnetron co-sputtering technique. The effect of Ti concentration on the hydrophilicity of Ti_xSi_1−xO₂ compound thin films was studied and it was shown that the films with Ti_0.6Si_0.4O₂ composition possess the best hydrophilic property among all the grown samples. Surface ratio and average roughness of the thin films were measured by atomic force microscopy (AFM). Surface chemical states and stoichiometry of the films were determined by X-ray photoelectron spectroscopy (XPS). In addition, XPS revealed that the amount of Ti-O-Si bonds in nanometer depth from the surface of the Ti_0.6Si_0.4O₂ films was the maximum, which resulted in the most stable superhydrophilic property. According to XRD data analysis for the pure TiO₂ films, the polycrystalline anatase phase was formed with an average grain size of about 15 nm. Moreover, amorphous phase was also formed for the Ti_xSi_1−xO₂ compound systems due to presence of silicon in the films. Finally, optical properties of the films such as transmission, reflection and band gap energy were investigated using UV-vis spectrophotometry. It was found that the transmittance of the films was decreased with increasing Ti concentration in the films.     

Study of asymmetric charge writing on Pb(Zr,Ti)O3 thin films by Kelvin probe force microscopy

Polycrystalline Pb(Zr_0.55Ti_0.45)O₃ thin film was deposited on Pt/Ti/SiO₂/Si(1 0 0) by radio-frequency-magnetron sputtering method, and the writing of charge bits on the surface of PZT thin film was studied by Kelvin probe force microscopy. It is found that the surface potential of the negative charge bits are higher than those of the corresponding positive ones. When ferroelectric polarization switching occurs, the potential difference becomes even more remarkable. A qualitative model was proposed to explain the origin of the asymmetric charge writing. It is demonstrated that the internal field in the interface layer, which is near the ferroelectric/electrode interface in ferroelectric film, is likely to be the cause for the occurrence of this phenomenon.     

Effect of a LaSrCoO3 buffer layer on Pb1 − xLaxTi1 − x/4O3 films studied by polarized Raman spectroscopy

A confocal Raman investigation of Pb_1 − xLa_xTi_1 − x/4O₃ (PLT) thin films grown by RF magnetron sputtering on PbO_x/Pt/Ti/SiO₂/Si substrates with an intermediate LaSrCoO₃ (LSCO) layer was performed. The influence of the LaSrCoO₃ buffer layer was analyzed taking advantage of the observed Raman spectral band variation, which varied according to different manufacturing procedures. In the presence of a LSCO layer, the A1(1TO) Raman mode, which was indicative of tetragonal distortion, was pronouncedly enhanced, and a slight deviation from the (0 0 1) plane of the film was observed from the angular dependence of the polarized Raman spectral intensity. Furthermore, the spectral band variation as well as the residual stress along the in-depth direction was measured in the film from cross-sectional spectral line scans. This latter measurement showed a relaxation of the lattice mismatch in the presence of LSCO and PbO layers.     

Combinatorial study of phase transformation characteristics of a Ti-Ni-Pd shape memory thin film composition spread in view of microactuator applications

Phase transformation characteristics of a Ti-Ni-Pd shape memory thin film composition spread have been investigated. The thin film composition spread was fabricated from elemental targets using an ultra-high vacuum combinatorial magnetron sputter-deposition system and subsequent annealing at 500 °C for 1 h in situ. Automated temperature-dependent resistance measurements (R(T)), energy dispersive X-ray analysis (EDX) and X-ray diffraction measurements (XRD) have been applied for the high-throughput characterization of the composition spread. Reversible phase transformations within the measurement range of −40 to 250 °C within the Ti-Ni-Pd system were observed for compositions with Ti content between 50 and ∼59 at.%. For Ti-richer films, Ti₂Ni and Ti₂Pd precipitates are inhibiting reversible phase transformations. The transformation temperatures and the thermal hysteresis were determined from R(T) measurements. Rising transformation temperatures with increasing Pd content and significantly lower thermal hysteresis for the B2-B19, compared to the B2-R-B19′ transformations were found in good agreement with published data. For low Pd contents (<7-12 at.%, depending on the Ti content) two-stage B2-R-B19′ transformations were observed. Compositions with higher Pd contents showed a single-stage B2-B19 transformation. Increasing Ti content within the B2-B19 transformation region results in a linear increase of the thermal hysteresis and decreasing transformation temperatures.     

Preparation and characterization of GaN films by radio frequency magnetron sputtering and carbonized-reaction technique

Radio frequency magnetron sputtering/post-carbonized-reaction technique was adopted to prepare good-quality GaN films on Al₂O₃(0 0 0 1) substrates. The sputtered Ga₂O₃ film doped with carbon was used as the precursor for GaN growth. X-ray diffraction (XRD) pattern reveals that the film consists of hexagonal wurtzite GaN. X-ray photoelectron spectroscopy (XPS) shows that no oxygen can be detected. Electrical and room-temperature photoluminescence measurements show that good-quality polycrystalline GaN films were successfully grown on Al₂O₃(0 0 0 1) substrates.     

XPS study of the deposited Ti layer in a magnetron-type sputter ion pump

X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of the anode deposits in a miniature magnetron ion pump. The pump was mounted on an UHV system with the ultimate pressure of 1 × 10⁻⁹ mbar. A stable discharge was established in the nitrogen atmosphere with some traces of CO at about 10⁻⁷ mbar. The cathode was made of pure titanium. The sputtered titanium atoms deposited on the anode, where they reacted with gases to form a film of titanium compounds. The thickness of the deposited titanium layer on the anode was about 100 nm. The results from XPS investigations indicate that active gases such as O₂ and N₂ react with Ti forming TiO₂ and TiN. While carbon containing molecules just adsorb on the surface and do not form carbide. In the bulk of the deposited layer almost pure TiN was found with some traces of oxygen and carbon. The part of carbon was bonded to TiC, which can be caused by ion sputtering during the depth profiling.     

Raman spectroscopic studies of PbxLa1−xTi1−x/4O3 thin films grown on Si substrates by RF magnetron sputtering

A systematic spectroscopic investigation of Pb_xLa_1−xTi_1−x/4O₃ (PLT) thin films grown on PbO_x/Pt/Ti/SiO₂/Si substrate by RF magnetron sputtering was performed by using confocal Raman spectroscopy. Influence of the growth condition modification including different growth temperatures, with various buffer layer thickness, and post-annealing treatments were analyzed with taking advantages of the corresponding Raman spectral band variation in the respective process. Significant change in the spectral bands occurred with the alteration of the growth condition, and the related mechanisms were discussed after spectral deconvolution, providing reliable information about the direction for film growth.     

Color-neutral switchable mirrors based on magnesium-titanium thin films

In an investigation of smart-window applications of switchable mirror thin films, Pd-capped magnesium-titanium thin films were prepared by dc magnetron sputtering. Their optical properties, switching durability and crystalline structures have been investigated. We show that Pd/Mg-Ti thin films with specific thicknesses are completely color-neutral in the transparent state and their optical switching properties are suitable for building and automobile window glass applications. The ternary hydrides of Mg_(1-x)Ti_x thin films with Pd overlayers are identified by in situ X-ray diffraction measurements during a hydrogen gas loading of 4%. Pd/Mg_(1-x)Ti_x thin film switchable mirrors show fast hydriding and dehydriding kinetics as compared to a Pd-capped pure Mg thin film due to the catalytic role of doped metallic Ti. PACS 75.20.En; 78.20.-e; 78.70.Ck; 42.70.-a     

Growth and characterization of Y2O3 thin films

Y₂O₃ thin films were grown on silicon (1 0 0) substrates by pulsed-laser deposition at different substrate temperatures and O₂ pressures. The structure and composition of films are studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Y₂O₃ thin films deposited in vacuum strongly oriented their [1 1 1] axis of the cubic structure and the film quality depended on the substrate temperature. The magnitude of O₂ pressure obviously influences the film structure and quality. Due to the silicon diffusion and interface reaction during the deposition, yttrium silicate and SiO₂ were formed. The strong relationship between composition and growth condition was discussed.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Diffusion and chemical composition of TiNxOy thin films studied by Rutherford Backscattering Spectroscopy

Thickness and chemical composition of the TiN_xO_y thin films deposited by reactive magnetron sputtering from Ti target at controllable oxygen flow rate were determined by Rutherford Backscattering Spectroscopy (RBS) using 2 MeV He⁺ ions. The films were deposited on carbon foils and amorphous silica (a-SiO₂) substrates at 25 °C and 250 °C. The estimated film thickness is of 75-100 nm. The O/Ti atomic ratio in the films increases up to 1.5 with increasing oxygen flow rate, while that of N/Ti decreases from about 1.1 for TiN to 0.4 at the highest oxygen flow rate. Substantial out-diffusion of carbon from the substrate is observed which is independent of the substrate temperature. Films grown onto a-SiO₂ substrates can be treated as homogeneous single layers without interdiffusion. It is more difficult to determine the nitrogen and oxygen content due to superposition of RBS signals arising from film and substrate. RBS analysis of the depth profile indicates that for the investigated films the carbon diffusion and oxidation not only at the topmost surface layers but over the bulk of the films were found. Comparison with XPS results indicates substantial oxygen adsorption at the surface of TiN_x thin films obtained at zero oxygen flow rate.     

Formulation for XPS spectral change of oxides by ion bombardment as a function of sputtering time

XPS measurement revealed that the original state of TiO₂ was changed to Ti₂O₃ and TiO by ion bombardment. TiO₂ decreased and Ti₂O₃ increased at the initial stage. TiO increased at a later stage than Ti₂O₃. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO₂ to Ti₂O₃ and from Ti₂O₃ to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO₂ to Ti₂O₃ is about ten times larger than that from Ti₂O₃ to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment.     

Comparative study of cathode and magnetron sputtering methods for depositing Pb(TiZr)O<Subscript>3</Subscript> ferroelectric film

The radial distribution of the composition and thickness of lead zirconate titanate films deposited in several modes of magnetron and diode sputtering was measured. It was shown that the effects of deposited film resputtering with preferential lead sputtering are pronounced during ion-plasma sputtering of Pb(Zr,Ti)O₃. During magnetron sputtering, this leads to a nonuniform distribution of the film composition over the substrate, which cannot be compensated by varying the target composition. During diode sputtering with a short target-substrate distance, resputtering has no significant effect on the film composition.     

Femtosecond laser patterning of Ta0.1W0.9Ox/ITO thin film stack

Selective laser patterning of thin films in a multilayered structure is an emerging technology for process development and fabrication of optoelectronics and microelectronics devices. In this work, femtosecond laser patterning of electrochromic Ta_0.1W_0.9O_x film coated on ITO glass has been studied to understand the selective removal mechanism and to determine the optimal parameters for patterning process. A 775 nm Ti:sapphire laser with a pulse duration of 150 fs operating at 1 kHz was used to irradiate the thin film stacks with variations in process parameters such as laser fluence, feedrate and numerical aperture of objective lens. The surface morphologies of the laser irradiated regions have been examined using a scanning electron microscopy and an optical surface profiler. Morphological analysis indicates that the mechanism responsible for the removal of Ta_0.1W_0.9O_x thin films from the ITO glass is a combination of blistering and explosive fracture induced by abrupt thermal expansion. Although the pattern quality is divided into partial removal, complete removal, and ITO film damage, the ITO film surface is slightly melted even at the complete removal condition. Optimal process window, which results in complete removal of Ta_0.1W_0.9O_x thin film without ablation damage in the ITO layer, have been established. From this study, it is found that focusing lens with longer focal length is preferable for damage-free pattern generation and shorter machining time.     

Fabrication and structural characterization of TiO nanoparticle soft-landed on substrate by the magnetron sputtering-gas aggregation method

We have succeeded to fabricate the thin film mainly or entirely consisting of nano-crystallites TiO on a substrate at room temperature by using the magnetron sputtering combined with the gas aggregation method which has the capability to deposit grown small particles and/or clusters of the desired compound material on the substrate in soft-landed mode. The important experimental parameters to control the growth of TiO particles are identified as partial pressure of additional oxygen gas, growth-reaction distance L_td, and LN₂ cooling of growth chamber. The smallest averaged diameter of TiO nano-particles is 5.62 nm and size distribution being from 2 to 8 nm under 50 mm of L_td. The compositional uniformity is confirmed by EDS and EELS. The chemical state of the film observed by Ti 2P XPS peak confirms the primarily growth of TiO and indicates the formation of minor content of amorphous Ti_1-xO_x and/or Ti_1-xC_x particularly at the surface of the film.     

Ion sputtering rates of W-, Ti- and Cr-carbides studied at different Ar ion incidence angles

To study the ion sputtering rates of W-, Ti- and Cr-carbides, trilayer structures comprising C-graphite (59 nm)/WC (50 nm)/W (38 nm), C-graphite (56 nm)/TiC (40 nm)/Ti (34 nm) and C-graphite (46 nm)/C₃C₂ (60 nm)/Cr (69 nm) with a tolerance ±2% were sputter deposited onto smooth silicon substrates. Their precise structural and compositional characterization by transmission electron microscopy (TEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) revealed that the WC and Cr₃C₂ layers were amorphous, while the TiC layer had a polycrystalline structure. The ion sputtering rates of all three carbides, amorphous carbon and polycrystalline Cr, Ti and W layers were determined by means of Auger electron spectroscopy depth profiling as a function of the angle of incidence of two symmetrically inclined 1 keV Ar⁺ ion beams in the range between 22° and 82°. The sputtering rates were calculated from the known thicknesses of the layers and the sputtering times necessary to remove the individual layers. It was found that the sputtering rates of carbides, C-graphite and metals were strongly angle dependent. For the carbides in the range between 36° and 62° the highest ion sputtering rate was found for Cr₃C₂ and the lowest for TiC, while the values of the sputtering rates for WC were intermediate. The normalized sputtering yields calculated from the experimentally obtained data for all three carbides followed the trend of theoretical results obtained by calculation of the transport of ions in solids by the SRIM code. The sputtering yields are also presented in terms of atoms/ion. Our experimental data for two ion incidence angles of 22° and 49° and reported values of other authors for C-graphite and metals are mainly inside the estimated error of about ±20%. The influence of the ion-induced surface topography on the measured sputtering yields was estimated from the atomic force microscope (AFM) measurements at the intermediate points of the corresponding layers on the crater walls formed during depth profiling.