Amorphous Titanium Research Articles

Multi-Color Spaceplates in the Visible.

The ultimate miniaturization of any optical system relies on the reduction or removal of free-space gaps between optical elements. Recently, nonlocal flat optic components named "spaceplates" were introduced to effectively compress space for light propagation. However, space compression over the visible spectrum remains beyond the reach of current spaceplate designs due to their inherently limited operating bandwidth and functional inefficiencies in the visible range. Here, we introduce "multi-color" spaceplates performing achromatic space compression at three distinct color channels across the visible spectrum to markedly miniaturize color imaging systems. In this approach, we first design monochromatic spaceplates with high compression factors and high transmission amplitudes at visible wavelengths based on a scalable structure and dielectric materials widely used in the fabrication of meta-optical components. We then show that the dispersion-engineered combination of monochromatic spaceplates with suitably designed transmission responses forms multicolor spaceplates that function achromatically. The proposed multicolor spaceplates, composed of amorphous titanium dioxide and silicon dioxide layers, efficiently replace free-space volumes with compression ratios as high as 4.6, beyond what would be achievable by a continuously broadband spaceplate made of the same materials. Our strategy for designing monochromatic and multicolor spaceplates, along with the presented theoretical and computational results, show that strong space-compression effects can be achieved in the visible range. Our findings may ultimately enable a new generation of ultrathin optical devices for various applications.

Probing the Nanonewton Mitotic Cell Deformation Force by Ion-Resonance-Enhanced Photonics Force Microscopy.

Mechanical forces are essential for regulating dynamic changes in cellular activities. A comprehensive understanding of these forces is imperative for unraveling fundamental mechanisms. Here, we develop a microprobe capable of facilitating the measurement of biological forces up to nanonewton levels in living cells. This probe is designed by coating the core of anatase titania particles with amorphous titania and silica shells and an upconversion nanoparticles (UCNPs) layer. Leveraging both antireflection and ion resonance effects from the shells, the optically trapped probe attains a maximum lateral optical trap stiffness of 14.24 pN μm-1 mW-1, surpassing the best reported value by a factor of 3. Employing this advanced probe in a photonic force microscope, we determine the elasticity modulus of mitotic HeLa cells as 1.27 ± 0.3 kPa. Nanonewton probes offer the potential to explore 3D cellular mechanics with unparalleled precision and spatial resolution, fostering a deeper understanding of the underlying biomechanical mechanisms.

Amorphous-Crystalline Interface Induced Internal Electric Fields for Electrochromic Smart Window.

Balancing optical modulation and response time is crucial for achieving high coloration efficiency in electrochromic materials. Here, internal electric fields are introduced to titanium dioxide nanosheets by constructing abundant amorphous-crystalline interfaces, ensuring large optical modulation while reducing response time and therefore improving coloration efficiency. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) reveals the presence of numerous amorphous-crystalline phase boundaries in titanium dioxide nanosheets. Kelvin probe force microscopy (KPFM) exhibits an intense surface potential distribution, demonstrating the presence of internal electric fields. Density functional theory (DFT) calculations confirm that the amorphous-crystalline heterointerfaces can generate internal electric fields and reduce diffusion barriers of lithium ions. As a result, the amorphous-crystalline titanium dioxide nanosheets exhibit better coloration efficiency (35.1cm2C-1) than pure amorphous and crystalline titanium dioxide nanosheets.

Crystallization mechanism of barium titanate in amorphous titania gel pellets by acid–base chemical densification near room temperature

Crystallization mechanism of barium titanate in amorphous titania gel pellets by acid–base chemical densification near room temperature

Phase selectivity upon flash-lamp annealing of sputter deposited amorphous titanium oxide films

We report the impact of flash-lamp-annealing (FLA) on the structural evolution of amorphous titania (TiO2) films produced by DC reactive magnetron sputtering. TiO2 films were grown at room-temperature at different oxygen partial pressure (PO2) and subsequently annealed as a function of the FLA energy density. X-ray diffraction confirms that FLA induces phase formation from the initial amorphous state with a general transition from anatase to rutile by increasing the FLA energy density (temperature). Interestingly, the transformation onset of anatase to rutile is achieved at lower energy densities for higher PO2. On the contrary, films with a highly resilient anatase phase can be produced at relatively low PO2. A detailed analysis of the pristine amorphous structure carried out by X-ray absorption near-edge structure indicates the role of oxygen sites in the observed phase transformation. In particular, oxygen vacancies seem to stabilize the anatase phase at high temperatures. The results show the relevance of subtle changes in the initial amorphous structure for phase selectivity in TiO2 films upon FLA.

Amorphous TiO2 nano-coating on stainless steel to improve its biological response

This study delves into the potential of amorphous titanium oxide (aTiO2) nano-coating to enhance various critical aspects of non-Ti-based metallic orthopedic implants. These implants, such as medical-grade stainless steel (SS), are widely used for orthopedic devices that demand high strength and durability. The aTiO2 nano-coating, deposited via magnetron sputtering, is a unique attempt to improve the osteogenesis, the inflammatory response, and to reduce bacterial colonization on SS substrates. 
The study characterized the nanocoated surfaces (SS-a TiO2) in topography, roughness, wettability, and chemical composition. Comparative samples included uncoated SS and sandblasted/acid-etched Ti substrates (Ti). The biological effects were assessed using human mesenchymal stem cells (MSCs) and primary murine macrophages. Bacterial tests were carried out with two aerobic pathogens (S. aureus and S. epidermidis) and an anaerobic bacterial consortium representing an oral dental biofilm.
Results from this study provide strong evidence of the positive effects of the aTiO2 nano-coating on SS surfaces. The coating enhanced MSC osteoblastic differentiation and exhibited a response similar to that observed on Ti surfaces. Macrophages cultured on aTiO2 nano-coating and Ti surfaces showed comparable anti-inflammatory phenotypes. Most significantly, a reduction in bacterial colonization across tested species was observed compared to uncoated SS substrates, further supporting the potential of aTiO2 nano-coating in biomedical applications.
The findings underscore the potential of magnetron-sputtering deposition of aTiO2 nano-coating on non-Ti metallic surfaces such as medical-grade SS as a viable strategy to enhance osteoinductive factors and decrease pathogenic bacterial adhesion. This could significantly improve the performance of metallic-based biomedical devices beyond titanium.

Minimizing surface adhesion of Sylgard 184 for medical applications

Silicones such Sylgard 184 are widely employed in biological applications due to their versatile properties. However, their inherently adhesive surfaces can restrict their application, especially in direct contact with damaged biological tissues, potentially compromising patient comfort. To enhance the surface properties of Sylgard 184 while maintaining its transparency in the visible spectrum, a novel low-temperature method (70 °C) has been developed. This method involves immersing PDMS in a solution of titanium (IV) ethoxide in THF, thus inducing swelling of the silicone's polymer network, followed by the diffusion and condensation of titanium (IV) ethoxide within the polymer matrix. The resulting hybrid material, incorporating amorphous titanium oxide within the silicone network, exhibits significantly increased surface hardness compared to unmodified Sylgard 184, while retaining transparency and improving biological behaviour. The elaborated method holds promising potential for enhancing the performance of silicone-based materials in diverse biomedical applications.

Amorphous titanium dioxide and polyaniline dual modifying silicon for highly enhanced lithium-ion storage

Silicon (Si) anode material is promising in the next generation of lithium-ion batteries (LIBs) with high energy densities for its much higher capacity (4200 mAh/g) than that of commercial graphite (372 mAh/g). However, silicon anode material with low electronic conductivity suffers a huge volume variation and accompanies side reactions during alloyed and de-alloyed process. Here, we design an inner amorphous titanium dioxide (TiO2) and an outer flexible conductive polyaniline (PANI) network dual modified Si@TiO2@PANI material for LIBs, where the TiO2 avoids the side reactions and the PANI network layer buffers the volume expansion and increases the electronic conductivity. The as-prepared Si@TiO2@PANI exhibits a high initial discharge capacity of 3050 mAh/g and maintains 1583 mAh/g after 200 cycles at 0.5 A/g. It even delivers the discharge capacity of 1002 mAh/g after 600 cycles at 1 A/g, as well as an excellent rate ability with discharge capacity of 1890, 1260 and 432 mAh/g at the high current density of 1, 2 and 5 A/g, respectively. Our strategy shows that the innovative design of double buffer layers on Si can synergistically promote stability and accelerate kinetics of Li+ transport, offering novel resolution strategy to enhance the performance of Si-based anodes for LIBs.

Demonstration of the Optical Isotropy of TiO2 Thin Films Prepared by the Sol-Gel Method.

Titanium dioxide (TiO2) thin films prepared by the sol-gel technique have been shown to be optically isotropic and, unlike the films obtained by competitive methods, do not exhibit measurable birefringence. A series of submicrometer-thin titanium dioxide films were prepared using the sol-gel technique and then thermally annealed at different temperatures. The samples were analyzed by spectroscopic ellipsometry using the Mueller matrix formalism, X-ray diffractometry and scanning electron microscopy. The conversion of amorphous titanium dioxide to polycrystalline anatase occurred at 400 °C or higher. Crystallites of a few percent of the film thickness were observed. Nevertheless, the crystallization process did not trigger the appearance of birefringence. These observations demonstrate that high-quality planar optical waveguides can be successfully fabricated on flexible substrates, in particular those composed of efficient polymers that can withstand the aforementioned temperatures.

Amorphous titanium oxide (aTiO2) thin films biofunctionalized with CAP-p15 induce mineralized-like differentiation of human oral mucosal stem cells (hOMSCs)

Insufficient osseointegration of titanium-based implants is a factor conditioning their long-term success. Therefore, different surface modifications, such as multifunctional oxide coatings, calcium phosphates, and the addition of molecules such as peptides, have been developed to improve the bioactivity of titanium-based biomaterials. In this work, we investigate the behavior of human oral mucosal stem cells (hOMSCs) cultured on amorphous titanium oxide (aTiO2), surfaces designed to simulate titanium (Ti) surfaces, biofunctionalized with a novel sequence derived from cementum attachment protein (CAP-p15), exploring its impact on guiding hOMSCs towards an osteogenic phenotype. We carried out cell attachment and viability assays. Next, hOMSCs differentiation was assessed by red alizarin stain, ALP activity, and western blot analysis by evaluating the expression of RUNX2, BSP, BMP2, and OCN at the protein level. Our results showed that functionalized surfaces with CAP-p15 (1 µg ml−1) displayed a synergistic effect increasing cell proliferation and cell attachment, ALP activity, and expression of osteogenic-related markers. These data demonstrate that CAP-p15 and its interaction with aTiO2 surfaces promote osteoblastic differentiation and enhanced mineralization of hOMSCs when compared to pristine samples. Therefore, CAP-p15 shows the potential to be used as a therapeutical molecule capable of inducing mineralized tissue regeneration onto titanium-based implants.

Synthesis of amorphous titanium isophthalic acid catalyst with hierarchical porosity for efficient oxidative desulfurization of model feed with minimum oxidant

Deep desulfurization is an indispensable technique for obtaining clean fuel and the preparation of novel materials for upgrading desulfurization efficiency is highly pursued. Herein, we develop a novel amorphous titanium isophthalic acid (Ti-IPA) catalyst with hierarchical porosity and highly dispersion of Ti-OH defect sites via solvothermal method. Ti-IPA is suitable for a variety of oxidant desulfurization (ODS) reaction systems due to its amphiphilic nature. The optimal Ti-IPA reveal extraordinary ODS performance for oxidizing 1000 ppm sulfur of dibenzothiophene-to-dibenzothiophene sulfone in model feed within 12 min at 40 ℃ with minimum oxidant/sulfur molar ratio of 2 (the sulfur oxidation efficiency reached 99.5 %), and the reaction time can be altered to 5 min at 50 ℃. The activity per unit mass of Ti-IPA reaches 52.2 mmol h−1g−1 at 50 ℃, outperforming all the reported Ti-based organic materials. Quenching and EPR tests indicate that Ti-IPA adopts non-free-radical ODS mechanism. Experimental and characterization results verify that the terminal OH capped on the Ti defect sites can easily react with oxidant to form peroxo-titanium intermediates, which manipulate the sulfur oxidation efficiency.

Ultrathin Titanium Dioxide Coating Enables High-Rate and Long-Life Lithium Cobalt Oxide.

Lithium cobalt oxide (LCO) has been widely used as a leading cathode material for lithium-ion batteries in consumer electronics. However, unstable cathode electrolyte interphase (CEI) and undesired phase transitions during fast Li+ diffusivity always incur an inferior stability of the high-voltage LCO (HV-LCO). Here, an ultra-thin amorphous titanium dioxide (TiO2) coating layer engineered on LCO by an atomic layer deposition (ALD) strategy is demonstrated to improve the high-rate and long-cycling properties of the HV-LCO cathode. Benefitting from the uniform TiO2 protective layer, the Li+ storage properties of the modified LCO obtained after 50 ALD cycles (LCO-ALD50) are significantly improved. The results show that the average Li+ diffusion coefficient is nearly tripled with a high-rate capability of 125 mAh g-1 at 5C. An improved cycling stability with a high-capacity retention (86.7%) after 300 cycles at 1C is also achieved, far outperforming the bare LCO (37.9%). The in situ XRD and ex situ XPS results demonstrate that the dense and stable CEI induced by the surface TiO2 coating layer buffers heterogenous lithium flux insertion during cycling and prevents electrolyte, which contributes to the excellent cycling stability of LCO-ALD50. This work reveals the mechanism of surface protection by transition metal oxides coating and facilitates the development of long-life HV-LCO electrodes.

Nanostructured TiO2 synthesized by different methods: Relationship between TiO2 porosity and crystalline-amorphous structure

The present manuscript focuses on important aspects regarding TiO2, which is typically used in many applications. On one hand, a thorough review of methods for synthesizing nanostructured TiO2 is presented. Using these methods, and different post-synthesis heat-treatment conditions, close to thirty TiO2 materials have been prepared, and their porous texture and crystalline and amorphous structure have been characterized. In this large number of samples, the porous texture characterization has revealed a high contribution of mesoporosity in a large number of the synthesized materials, being in many materials around 60–70 %. Moreover, different percentages of crystalline phases, anatase, brookite, rutile, and amorphous titania are developed depending on the TiO2 preparation conditions. These fractions have been determined from X-ray diffraction data using the “simple” characterization method reported by Cano-Casanova et al., inspired by Jensen et al., and Bellardita et al., also exploring its limitations. This analysis has allowed assessing a linear relationship between porosity, particularly between the surface area, and the amorphous phase content in titanium dioxide. A relationship had been previously suggested in the literature, but never correlated in such a way. In summary, the present study constitutes a tool to help other researchers select the most suitable method for synthesizing nanostructured TiO2 materials with target properties and, also, to characterize them, and have a very easy and straightforward estimation of TiO2 amorphous phase content after the determination of their surface areas.

LED-driven photodeposition of Pt nanoparticles on TiO2: Combined effects of titania crystallinity and adopted wavelength on photoactivity

Amidst the ongoing LED technology-driven energy revolution, it’s crucial to re-examine how certain processes work. For this purpose, the present study dives into a new way of depositing platinum nanoparticles onto titania via photodeposition using LED light, carefully controlling the process by irradiating with different wavelengths. This novel approach has helped us to understand how the chosen wavelength may affect the properties of the synthesized materials, especially in relation to the shape of photodeposited nanoparticles. Moreover, the photodeposition method herein presented was proven to allow the nucleation and growth of Pt over amorphous titania, effectively expanding the application range of photodeposition. Importantly, the prepared samples were found to be highly effective at photocatalytically breaking down recalcitrant pharmaceutical drugs such as naproxen. This work significantly contributes to our understanding on how these materials can be used for technological applications such as photocatalysis, making it a noteworthy addition to the research field.

C54-TiSi2 formation using nanosecond laser annealing of A-Si/Ti/A-Si stacks

Low resistive Ti-based contacts are required to reach the targeted performances of 3D imaging devices. To fulfill this request, the C54-TiSi2 phase appears to be the most efficient. However, in view of monolithic integration, the temperature needed to form C54-TiSi2 must be drastically reduced by at least 100 °C in order to avoid damage in other parts of the device. Indeed, as these 3D imaging devices require the co-integration of Ti and Ni based silicides, it is crucial to develop a thermal treatment which allows to form the C54-TiSi2 phase without agglomerating the NiSi layer (i.e. at temperatures lower than 600 °C). In this work, a three-layer stack made of a Ti layer in between two amorphous Si thin films deposited on (100) Si substrate has been studied. Nanosecond laser annealing (NLA) followed by rapid thermal annealing (RTA) from 500 to 800 °C were performed on those stacks. Sheet resistance and X-Ray Diffraction measurements showed that the C54-TiSi2 phase could be formed with a RTA treatment at a temperature as low as 600 °C in this case. In line with some previous work, this was due to another phase sequence involving the C40-TiSi2 during the laser annealing. The most favorable microstructure to form C54-TiSi2 by a subsequent RTA treatment seemed to be a matrix made of amorphous titanium silicide containing grains of the C40-TiSi2 template phase. This hypothetical microstructure was formed by laser annealing at a lower energy density when layers of amorphous Si were used.

Enhancement of electrochromic efficiency of TiO2 nanorods

In this study, the rutile TiO2 nanorods thin films were deposited via hydrothermal method on fluorine-doped tin oxide (FTO) substrate. To form a porous morphology layer, a thin film of amorphous titanium oxide (TiOx) was deposited on the TiO2 nanorods through sputtering at high pressure. The samples were annelid at 450ᵒC to transform the amorphous surface to anatase phase. Structural, optical, morphology and electrochemical properties of the samples were examined via X-ray diffraction (XRD), Raman scattering, UV–Vis NIR and photoluminescence (PL) spectroscopies, field-emission scanning electron microscopy (FE-SEM) and Potentiostat device respectively. The samples exhibited a large optical bandgap of 3.35–3.40 eV and high transparency of over 77 % at a wavelength of 555 nm. Raman analysis confirmed the formation of anatase phase on the rutile nanorods under thermal treatment. PL analysis indicated that the oxygen vacancies reached their maximum after sputtering, while the intensity of PL emission significantly increased after annealing. Investigation of the electrochromic properties revealed an increase in coloration efficiency from 2.6 C−1cm2 for bare nanorods to 10.0 C−1cm2 for nanorods after sputtering deposition, which decreased to 5.4 C−1cm2 after thermal treatment.

Highly conductive titanium nitride core sterically reinforced nickel-vanadium layered double hydroxides for supercapacitors

Nickel vanadium layered double hydroxide (NiV-LDH) is a highly promising electrode material for supercapacitors, but its poor electrochemical durability and conductivity limit its capacitance performance as a high-performance supercapacitor electrode. In contrast, titanium nitride (TiN) stands out for its outstanding electrochemical durability and superior conductivity. In this work, a composite material (TiN@NiV-LDH) with outstanding electrochemical performance was prepared by a simple hydrothermal method, where nickel vanadium layered double hydroxide nanosheets were vertically grown in a staggered manner on the surface of amorphous titanium nitride nanoparticles. The results demonstrate that at a current density of 2 A g−1, the capacitance of TiN@NiV-LDH reaches 712.4 F g−1. In addition, the assembled TiN@NiV-LDH//AC asymmetric supercapacitor exhibits a high energy density of 136.5 Wh kg−1 at a high power density of 1549.9 W kg−1, and after 10,000 cycles at a high current density of 20 A g−1, it retains 80.2 % excellent cyclic stability. This work, based on nickel vanadium layered double hydroxide and utilizing titanium nitride modification, aims to enhance the long-term stability of nickel vanadium layered double hydroxide while preserving its advantageous properties, providing a promising strategy for designing efficient supercapacitor electrodes.

Nanomolecularly-induced Effects at Titania/Organo-Diphosphonate Interfaces for Stable Hybrid Multilayers with Emergent Properties.

Nanoscale hybrid inorganic-organic multilayers are attractive for accessing emergent phenomena and properties through superposition of nanomolecularly-induced interface effects for diverse applications. Here, we demonstrate the effects of interfacial molecular nanolayers (MNLs) of organo-diphosphonates on the growth and stability of titania nanolayers during the synthesis of titania/MNL multilayers by sequential atomic layer deposition and single-cycle molecular layer deposition. Interfacial organo-diphosphonate MNLs result in ∼20-40% slower growth of amorphous titania nanolayers and inhibit anatase nanocrystal formation from them when compared to amorphous titania grown without MNLs. Both these effects are more pronounced in multilayers with aliphatic backbone-MNLs and likely related to impurity incorporation and incomplete reduction of the titania precursor indicated by our spectroscopic analyses. In contrast, both MNLs result in two-fold higher titania nanolayer roughness, suggesting that roughening is primarily due to MNL bonding chemistry. Such MNL-induced effects on inorganic nanolayer growth rate, roughening, and stability are germane to realizing high-interface-fraction hybrid nanolaminate multilayers.

Copper-Decorated Titanium Electrodes: Impact of Surface Modifications of Substrate on the Morphology and Electrochemical Performance.

This study investigates the effect of surface modifications of the titanium substrate on the growth of electrochemically deposited copper. These materials are intended to serve as cathodes in the electroreduction of nitrates in aqueous solutions. Surface modifications included the use of hydrogen fluoride for titanium etching and anodization to promote the growth of a structured titania nanotube array. The effect of an intermediate calcination step for the nanotubes before deposition was assessed along with a comparison to an untreated substrate electrode. The materials were comprehensively characterized by SEM, XRD, contact angle, potentiodynamic tests, EIS, and cyclic voltammetry. Their electrocatalytic ability was tested in the reduction of aqueous solutions containing nitrates. The results reveal that surface finishing impacted the shape and size of the Cu microparticles, as well as the nucleation mechanism enabling a crystal-facet-controllable synthesis. All the materials exhibited microsized copper particles with a spherical shape with some clusters. On the etched titanium surface, a high number of heterogeneous submicroscopic particles were also present. The thermally treated anodized substrate promoted the development of a combination of sparse microparticles corresponding to defect sites in amorphous titanium and the presence of a diffuse coating of octahedral nanosized particles whose growth was promoted by the tetragonal structure of anatase crystals. Electrochemical tests display reduced charge transfer resistance upon copper deposition on the modified substrates, which is indicative of the enhanced conductivity of the coated materials. Additionally, cyclic voltammetry and electrolysis experiments reveal the electrodes' potential for nitrate reduction, showing a better response for the etched titanium substrate (30% nitrate removal, after 2 h at 25 mA cm-2).

Separation effect of Li+, Na+, and Mg2+ with alumina–lithium LDH doped with amorphous titanium dioxide

Alumina–lithium layered double hydroxide doped with amorphous titanium dioxide (TiO2@AlLi–LDH) was synthesized through the coprecipitation of Li+ and Al3+. The structural characteristics of TiO2@AlLi–LDH were analyzed via XRD, XPS, BET and DSC–TG. Titanium oxide anions could be inserted between layers in TiO2@AlLi–LDH, and TiO2@AlLi–LDH consists of nanoflake-sized particles. The average diameter of the particles is 231.0 nm, and the particle size distribution curve is close to the normal distribution curve. The BET surface area is 174.02 m2·g−1 after recrystallization. The Li+ adsorption process of TiO2@AlLi–LDH can be described by the pseudo–second–order model, and the adsorption capacity is 11.54 mg·g−1. The structure of TiO2@AlLi–LDH was destroyed because of the reaction between Mg2+ and CO32−. The presence of Na+ significantly reduces the Li+ adsorption ability of TiO2@AlLi–LDH without destroying the structure. The separation coefficient of Mg2+/Li+ is 4269.76 when the initial mass ratio of Mg2+/Li+ is 350.20, and the separation coefficient of Na+/Li+ is 226.20 when the initial mass ratio of Na+/Li+ is 329.40. The Li+ adsorption amount of TiO2@AlLi–LDH in Qarhan salt lake brine is 5.66 mg·g−1, suggesting potential for industrial application.