Measurement method for carrier concentration in TiO2 via the Mott-Schottky approach

In direct contrast to the way in which silicon is precisely doped for integrated circuit applications in order to optimize device performance, there is little nuanced understanding of the correlation between TiO₂ doping level, charge carrier concentration, and the operation of TiO₂-based photocatalysts, dye-sensitized solar cells, and sensors. The present work outlines a rigorous methodology for the determination of free carrier concentration for doped metal oxide semiconductors such as TiO₂ that are not amenable to standard metrology methods. Undoped, Cr-, Mn-, and Nb-doped polycrystalline anatase TiO₂ are synthesized via atomic layer deposition (ALD) using Ti(OCH(CH₃)₂)₄, H₂O, Cr(C₅H₇O₂)₃, Mn(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3, 5-heptanedionato), and Nb(OCH₂CH₃)₅ as the source materials for Ti, O, Cr, Mn, and Nb, respectively. Chemical composition and crystallinity are investigated and a thorough “device-like” characterization of TiO₂ Schottky diodes is carried out to justify the subsequent extraction of carrier concentration values from capacitance-voltage (C-V) measurements using the Mott-Schottky approach. The influence of factors such as substrate type, contact metal type, and surface and interface preparation are examined. Measurements of donor carrier concentration are obtained for undoped, Cr-, Mn-, and Nb-doped TiO₂ synthesized by ALD. Possible causes for the obtained carrier concentrations are discussed.     

Surface preparation influence on the initial stages of MOCVD growth of TiO2 thin films

In situ chemical surface analyses using X-ray photoelectron spectroscopy (XPS), completed by ex situ atomic force microscopy (AFM) analyses, were performed in order to compare the initial stages of MOCVD growth of TiO₂ thin films on two different surface types. The first type was a silicon native oxide free hydrogen terminated surface and the second one was a silicon dioxide surface corresponding to a thin layer of 3.5 nm thick in situ thermally grown on silicon substrate. Si(100) was used as substrate, and the growths of TiO₂ thin films were achieved with titanium tetraisopropoxide (TTIP) as precursor under a temperature of 675 °C, a pressure of 0.3 Pa and a deposition time of 1 h. Whatever the surface is, the deposited titanium amount was globally the same in the two cases. On the contrary, the deposit morphology was different: a covering layer composed of a SiO₂ and TiO₂ phases mixture on the hydrogen terminated surface, and small TiO₂ clusters homogeneously spread on the SiO₂ surface.     

Angle resolved X-ray photoemission spectroscopy double layer model for in situ characterization of metal organic chemical vapour deposition nanometric films

In situ Angle Resolved X-ray Photoemission Spectroscopy (ARXPS) characterizations of TiO₂ thin films grown on silicon by Metal Organic Chemical Vapour Deposition were performed in order to get information on interfacial reactions at the first stages of the growth, one of the aims being to understand the influence of deposition conditions. Thickness measurements were also carried out from ARXPS analyses. As the real structure of the films was shown to be a double layer system such as TiO₂/SiO₂/Si, an ARXPS model of thickness and surface coverage determination was applied to each layer independently. However, the application of this model to very thin films underestimates the surface coverage of the interfacial layer. A “Double Layer” model taking into account the attenuation of the silicon oxide and substrate signals by the external layer was also developed.     

Hydrothermal growth of rutile TiO2 nanorod films on titanium substrates

Rutile TiO₂ nanorod films have been successfully prepared on titanium substrate via a hydrothermal method using Tetra-n-butyl titanate as Ti source in the presence of concentrated hydrochloric acid. The effect of Ti substrate annealing treatment and adding of additional alkali metal chlorides in hydrothermal solution on the growth of TiO₂ nanorod films has been studied using scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and water contact angle measurement. The growth mechanism of the TiO₂ nanorods on Ti substrate has also been discussed. It has shown that the initial rutile film transformed from anatase promotes the nucleation and epitaxial growth of rutile TiO₂ nanorods. The superior wettabilities of the TiO₂ nanorods resulted from treatments of vacuum and ultraviolet show great potential for applications in orthopaedic, dental implants, and possible photocatalysis.     

On the initial growth of atomic layer deposited TiO2 films on silicon and copper surfaces

Atomic layer deposition (ALD) of TiO₂ using tetrakis(diethylamino)titanium precursor and H₂O was studied on silicon and copper surfaces in order to examine differences in nucleation. Both surfaces were patterned on the same substrate to assure identical deposition conditions. Spectral ellipsometry, X-ray photoelectron spectroscopy and surface profilometry were used to probe nucleation phenomena, growth rates, and surface morphology on both surfaces. The TiO₂ deposition on copper was found to exhibit a significant induction period of about 20-25 ALD cycles with no observable TiO₂ during the first 10-15 cycles on the copper side; in contrast, no such inhibited growth was observed in the TiO₂ deposition on silicon. This result opens up potential for selective ALD of TiO₂ films on silicon-based substrates patterned with a metal without the use of a mask, a self-assembled monolayer or soft lithography which is impractical for some nanoscale semiconductor fabrication processes. After film nucleation, the TiO₂ growth rate on both surfaces was found to be 0.10 nm/cycle.     

Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> ferroelectric nanofilms on silicon buffered with a TiO<Subscript>2</Subscript> layer

Polycrystalline, 50- to 70-nm-thick barium strontium titanate films of composition Ba_0.8Sr_0.2TiO₃ have been grown on single-crystal silicon substrates by rf ion-beam sputtering. We have determined their structure and composition and detected impurities at the film/substrate interface in the form of titanium silicide islands. The deposition of a 4- to 6-nm-thick TiO₂ buffer layer onto Si by ion-beam sputtering before ferroelectric film growth is shown to prevent uncontrolled formation of impurities near the interface. The buffered heterostructures possess high thermal stability.     

Auger and X-ray photoelectron spectroscopic depth profiling techniques applied to ultra-thin titanium films

Auger electron spectroscopy and X-ray photoelectron spectroscopy in combination with sputter profiling techniques were employed to study ultra-thin (100–500 Å) titanium films. The composition of the films was studied as a function of substrate, deposition temperature and heating. Particular attention was given to the interfacial region.The data indicated that the films were a mixture of titanium and TiO₂. At no point was a pure titanium phase present. At a deposition temperature of 450°C the interface was composed of titanium, TiO₂, silicon and SiO₂ when quartz was the substrate and titanium, TiO₂, aluminum and Al₂O₃ when sapphire was the substrate. The silicon and aluminum resulted from reduction of the substrate. When the deposition temperature was approximately 25°C the reductive interaction was minimized.     

An extended spectrum bactericidal titanium dioxide (TiO<Subscript>2</Subscript>) coating for metallic implants: in vitro effectiveness against MRSA and mechanical properties

Implant infections remain feared and severe complications after total joint arthroplasty. The incidence of multi-resistant pathogens, causing such infections, is rising continuously, and orthopaedic surgeons are confronted with an ever-changing resistance pattern. Anti-infectious surface coatings aim for a high local effective concentration and a low systemic toxicity at the same time. Antibacterial efficacy and biomechanical stability of a novel broad-spectrum anti-infectious coating is assessed in the present study. Antibacterial efficacy of a sol–gel derived titanium dioxide (TiO₂) coating for metal implants with and without integrated copper ions as antibiotic agent was assessed against methicillin resistant Staphylococcus aureus (MRSA 27065). Both bacterial surface adhesion and growth of planktonic bacteria were assessed with bare and various TiO₂-coated Ti6Al4V metal discs. Furthermore, bonding strength of the TiO₂ surface coating, using standard testing procedures, as well as surface roughness were determined. We found a significant reduction of the bacterial growth rate for the coatings with integrated copper ions, with highest reduction rates observed for a fourfold copper TiO₂-coating. Pure TiO₂ without integrated copper ions did not reduce bacterial growth compared to uncoated Ti6Al4V. The coating was not detached from the substrate by standard adhesive failure testing, which indicated an excellent durability of the implant coating. The TiO₂ coating with integrated copper ions could offer a new strategy for preventing implant-associated infections, with antibacterial properties not only against the most common bacteria causing implant infections but also against multiresistant strains such as MRSA.     

Effect of Nb coating on the sulphidation/oxidation behaviour of Ti and Ti-6Al-4V alloy

The environmental response of Nb-coated Ti and Ti-6Al-4V alloy was studied at 750 °C in an atmosphere of pS₂ ∼ 10⁻¹ Pa and pO₂ ∼ 10 ⁻¹⁸ Pa. By acting as a diffusion barrier and through the formation of a Nb_1−xS scale the Nb coating deposited enhanced the corrosion resistance of both Ti and Ti-6Al-4V alloy. The corrosion products generated on uncoated titanium in the same environment and temperature were characterized by a double layered oxide scale of TiO₂ beneath which a TiS₂ layer was formed. For the Ti-6Al-4V alloy, α-Al₂O₃ was precipitated in the external portion of the outer-layer of TiO₂ whilst a layer containing Al₂S₃, TiS₂ and vanadium sulphide (possibly V₂S₃) was idenitified underlying the inner TiO₂ layer. After prolonged exposure (168 h), the Nb coating deposited on Ti and Ti-6Al-4V alloy was consumed. A scale following the sequence of TiO₂/TiO₂+NbO₂+Nb₂O₅/Nb_1−xS/TiO₂/ TiS₂/(substrate) was observed on the surface of the Nb-coated Ti, whilst a scale with sequence of TiO₂/V₂S₃/TiO₂+NbO₂+Nb₂O₅/Nb_1−xS/TiO₂/Al₂S₃+TiS₂/(substrate) characterized the corrosion products formed on the Nb-coated Ti-6Al-4V alloy.     

RF sputtered piezoelectric zinc oxide thin film for transducer applications

This paper demonstrates the substrate dependency of the c-axis zinc oxide growth in radio-frequency sputtering system. Different deposition conditions were designed to study the influences of Si, SiO₂/Si, Au/Ti/Si, and Au/Ti/SiO₂/Si substrates on the piezoelectric and crystalline qualities of the ZnO thin films. Experimental results showed that the multilayer of Au/Ti/SiO₂/Si-coated silicon substrate provided a surface that facilitated the growth of ZnO thin film with the most preferred crystalline orientation. The 1.5 μm-thick thermally grown amorphous silicon dioxide layer effectively masked the crystalline surface of the silicon substrate, thus allowing the depositions of high-quality 20 nm-thick titanium adhesion layer followed by 150 nm-thick of gold thin film. The gold-coated surface allowed deposition of highly columnar ZnO polycrystalline structures. It was also demonstrated that by lowering the deposition rate at the start of sputtering by lowering RF power to less than one-third of the targeted RF power, a fine ZnO seed layer could be created for subsequent higher-rate deposition. This two-step deposition method resulted in substantially enhanced ZnO film quality compared to single-step approach. The influence of stress relaxation by annealing was also investigated and was found to be effective in releasing most of the residual stress in this layered structure.     

Phase maps for sputter deposited refractory metal oxide ceramic coatings: review of niobium oxide,yttrium oxide,and zirconium oxide growth

Abstract

Reactive sputter deposition is a widely used glow discharge process for growing high melting point coatings near room temperature, and metastable and multiphase structures not attainable in bulk material grown under conditions of thermodynamic equilibrium. It is therefore ideally suited for growing refractory metal oxide coatings. In this study, ‘phase maps’ are constructed for the sputter deposition of the refractory metal oxides of Nb, Y, and Zr. These diagrams interrelate process parameters, the growth environment, and metallurgical phase in the growth regime of near room substrate temperature, low surface diffusion, and sticking coefficient of unity. Phase boundaries are discussed in terms of: (i) the fractional flux of metal atoms and metal oxide molecules to the substrate; (ii) a complete oxide layer at the metal target surface; (iii) oxygen species in the plasma available for reaction at the substrate.

MST/1693     

Synthesis of vanadium dioxide films by a modified sol-gel process

Vanadium dioxide films have been grown on silicon substrates and on SiO₂ layers on silicon by a modified sol-gel process using methyl cellosolve as a solvent. We have failed to obtain vanadium dioxide layers on Pt/TiO _x /SiO₂/Si substrates. For all of the substrates studied, we have examined the effect of synthesis conditions (initial solution concentration, deposition procedure, and oxidation and reduction anneals) on the phase composition, thickness, and surface morphology of the films.     

Comparisons of immersion and electrochemical properties of highly biocompatible Ti–15Zr–4Nb–4Ta alloy and other implantable metals for orthopedic implants

Abstract

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti–15Zr–4Nb–4Ta alloy. The thickness and electrical resistance (R_p) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy. The potential (E₁₀) indicating a current density of 10 μA cm^?2 estimated from the anodic polarization curve was significantly higher for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy and other metals. Moreover, the oxide film (4–7 nm thickness) formed on the Ti–15Zr–4Nb–4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO₂ with small amounts of ZrO₂, Nb₂O₅ and Ta₂O₅ that made the film electrochemically stable. The R_p of Ti–15Zr–4Nb–4Ta was higher than that of Ti–6Al–4V, i.e. 0.9 Ω cm² in 0.9% NaCl and 1.3 Ω cm² in Eagle's medium. This R_p was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti–15Zr–4Nb–4Ta is a potential implant material for long-term clinical use. Moreover, E₁₀ and R_p were found to be useful parameters for assessing biological safety.     

Raman spectroscopy study of the phase transformation on nanocrystalline titania films prepared via metal organic vapour deposition

Raman spectroscopy (RS) was used to study the phase transformations of nanocrytalline TiO₂ thin films. The films were grown by a vertical-flow cold-wall metal organic chemical vapour deposition system, using Ti(C₁₀H₁₄O₅) as the source reagent, at different substrate temperatures. The results indicate that the anatase phase is present at around 550 °C and the rutile phase starts to form at 620 °C. The anatase phase completely transforms into the rutile phase at 680 °C. We have demonstrated that RS can be used as a powerful nondestructive technique for a quick and efficient determination of the phase of TiO₂ thin films.     

High-throughput characterization of Pt supported on thin film oxide material libraries applied in the oxygen reduction reaction

Thin film metal oxide material libraries were prepared by sputter deposition of nanoscale Ti/Nb precursor multilayers followed by ex situ oxidation. The metal composition was varied from 6 at.% Nb to 27 at.% Nb. Additionally, thin wedge-type layers of Pt with a nominal thickness gradient from 0 to 5 nm were sputter-deposited on top of the oxides. The materials libraries were characterized with respect to metallic film composition, oxide thickness, phases, electrical conductivity, Pt thickness, and electrochemical activity for the oxygen reduction reaction (ORR). Electrochemical investigations were carried out by cyclic voltammetry using an automated scanning droplet cell. For a nominal Pt thickness >1 nm, no significant dependence of the ORR activity on the Pt thickness or the substrate composition was observed. However, below that critical thickness, a strong decrease of the surface-normalized activity in terms of reduction currents and potentials was observed. For such thin Pt layers, the conductivity of the substrate seems to have a substantial impact on the catalytic activity. Results from X-ray photoelectron spectroscopy (XPS) measurements suggest that the critical Pt thickness coincides with the transition from a continuous Pt film into isolated particles at decreasing nominal Pt thickness. In the case of isolated Pt particles, the activity of Pt decisively depends on its ability to exchange electrons with the oxide layer, and hence, a dependence on the substrate conductivity is rationalized.     

Titanium oxide nanotubes with controlled morphology for enhanced bone growth

An array of vertically aligned titanium oxide nanotubes was grown on the surface of titanium substrate by anodization. A chemical treatment with NaOH solution to make them more bioactive with a formation of nanoscale sodium titanate structure. The presence of such treated TiO₂ nanotubes significantly accelerated the kinetics of hydroxyapatite growth by a factor of as much as 7. The adhesion/growth of osteoblast cells is also significantly accelerated by the topography of the TiO₂ nanotubes with the filopodia of the growing cells actually going into the nanotube pores, producing a locked-in cell structure. The number of the adhered cells on the TiO₂ nanotubes increases by as much ∼400% as compared to the Ti metal, most likely caused by the pronounced topological feature, significantly increased surface area, as well as the in-between-nanotube pathways for fluid. Such an array of TiO₂ nanotubes well adherent on Ti implant surface can be useful for accelerated bone growth in orthopaedic/dental applications.     

Preferential growth of thin rutile TiO2 films upon thermal oxidation of sputtered Ti films

Thin rutile TiO₂ films with (200) preferred orientation were fabricated by thermal oxidation of sputtered Ti metal films on a fused silica substrate. Experimental results indicate that the preferential crystal growth of (200)-oriented TiO₂ is determined by the competition between surface free energy and strain energy. The highly crystalline Ti film with (002) orientation has a greater tendency to promote the growth of (200)-oriented TiO₂. However, for the amorphous and low crystalline Ti films, orientation of the crystallites evolved in the resulting TiO₂ film tends to be randomly distributed. The extent of preferential crystal growth of TiO₂ (200) plane can be enhanced by decreasing the annealing temperature or the thickness of Ti film.     

Growth of stoichiometric TiO2 thin films on Au(100) substrates by molecular beam epitaxy

The present study reports on the growth of thin TiO₂ films onto Au(100) single crystals by Ti evaporation in a reactive O₂ atmosphere at two different substrate temperatures: room temperature (RT) and 300 °C. The growth of the oxide films was monitored by means of X-ray photoemission spectroscopy, while the valence and conduction band electronic structure was investigated by UV and inverse photoemission spectroscopy, respectively.The TiO₂ film grows epitaxially on the Au(100) substrate at 300 °C exhibiting the rutile (100) surface. The evolution of the Ti 2p lineshape with the oxide coverage shows the presence of reduced oxide species (characterized by Ti^3 + ions) at the Au(100) interface. A crystalline and stoichiometric TiO₂ oxide is produced at high substrate temperature, while growth at RT gives a measurable concentration of defects. Post growth annealing in ultra-high vacuum of the RT grown film increases this concentration, while subsequent annealing in O₂ atmosphere restores the sample to the as-grown conditions.     

Epitaxial growth of lithium niobate film using metalorganic chemical vapor deposition

Lithium niobate films grown epitaxially on sapphire substrate were prepared using a thermal chemical vapor deposition method from the metalorganic compounds Li(C₁₁H₁₉O₂) and Nb(OC₂H₅)₅. The range of operating conditions for obtaining pure epitaxially grown LiNbO₃ without other oxides is within that for obtaining pure polycrystalline LiNbO₃ grown on silicon substrate. On analyzing the composition of the epitaxially grown LiNbO₃ film, the composition of the film was similar to that of the LiNbO₃ solid solution in the phase diagram of the Li-Nb composite oxide obtained for crystal growth from a molten solution.     

The microstructure and wettability of the TiOx films synthesized by reactive DC magnetron sputtering

Different chemical state of titanium oxide films were deposited on commercially pure Ti (CP Ti) by reactive DC magnetron sputtering under different oxygen flow rates to examine a possibility of their applications to endovascular stents. The chemical composition and crystal structure of the obtained films were analyzed by XPS and XRD, respectively. In dependence on the deposition parameters employed, the obtained films demonstrated different mixture of anatase TiO₂, Ti₂O₃, TiO and Ti. The wettability of the films was measured by the water contact angle variation. By formation of titanium oxide film on CP Ti, contact angle was decreased. In order to modify and control the surface wettability, the resultant TiO_x films were etched subsequently by different plasma. The wettability was influenced by etched process according to the decreased contact angle values of etched TiO_x film. Furthermore, TiO_x films became highly hydrophilic by ultraviolet (UV) irradiation, and returned to the initial relatively hydrophobic state by visible-light (VIS) irradiation. The wettability of the TiO_x film was enabled to convert between hydrophilic and hydrophobic reversibly by alternative UV and VIS irradiation. By adjusting deposition parameter and further modification process, the wettability of the TiO_x films can be changed freely in the range of 0–90°.