Colossal permittivity in (In1/2Nb1/2)xTi1−xO2 ceramics prepared by a glycine nitrate process

(In + Nb) co-doped TiO₂ nanoparticles with very low dopant concentrations were prepared using a glycine nitrate process. A pure rutile—TiO₂ phase with a dense microstructure and homogeneous dispersion of dopants was achieved. By doping TiO₂ with 1.5% (In + Nb) ions, a very high dielectric permittivity of ε′ = 42,376 and low loss tangents of tanδ = 0.06 (at room temperature) were achieved. The large conduction activation energy at the grain boundary decreased with decreasing dopant concentration. The colossal permittivity was primarily attributed to the internal barrier layer capacitor (IBLC) effect. The dominant effect of interfacial polarization at the non–Ohmic sample–electrode contact was observed when the dopant concentration was ≤1.0 mol%. Interestingly, the sample–electrode contact and resistive–outer surface layer effects, i.e., surface barrier layer capacitor (SBLC) effect, has also an effect on the colossal dielectric response in (In + Nb) co-doped TiO₂ ceramics.     

High energy-storage performance of lead-free Ba0.4Sr0.6TiO3–Sr0.7Bi0.2TiO3 relaxor-ferroelectric ceramics with ultrafine grain size

Relaxor-ferroelectric (RFE) ceramics possess slender ferroelectric hysteresis loop and low remnant polarization (P_r). They have great potential to provide excellent energy-storage performance as dielectric energy-storage materials. Herein, a lead-free 0.8Ba_0.4Sr_0.6TiO₃–0.2Sr_0.7Bi_0.2TiO₃ (0.8BST–0.2SBT) RFE ceramic with high energy-storage performance has been realized successfully. The addition of Bi³⁺ and increase in Sr²⁺content at the A site of the BST can effectively inhibit the growth of grains for high breakdown strength (E_b). As a result, an ultrafine average grain size of 0.7 μm was obtained in 0.8BST–0.2SBT RFE ceramic, affording a high E_b of 300 kV/cm. Further investigation revealed that the mutual conversion of short-range polar nanoregions and long-range-ordered ferroelectric domains upon application and withdrawal of a 300 kV/cm applied electric field resulted in a high maximum polarization (P_max) of 31 μC/cm² and a low P_r of 2.5 μC/cm². Hence, the 0.8BST–0.2SBT RFE ceramic simultaneously exhibited a high recoverable energy-storage density of 3.3 J/cm³ and a high energy-storage efficiency of 85% at 300 kV/cm. Additionally, a good energy-storage performance was reported over a temperature range of 50°C-120 °C and frequency from 10 to 1000 Hz, making the 0.8BST-0.2SBT RFE ceramic a potential lead-free dielectric energy-storage material.     

Enhancement in the photocatalytic and antimicrobial properties of ZnO nanoparticles by structural variations and energy bandgap tuning through Fe and Co co-doping

In this study, pure ZnO and iron (Fe) and cobalt (Co) co-doped ZnO nanoparticles were synthesized by varying Fe and Co concentrations using the co-precipitation method. The physical properties of as-prepared samples were investigated through XRD, FTIR, SEM, and UV–vis spectroscopy. X-ray diffraction confirmed the strong influence of Fe and Co ions on structural parameters without disturbing the basic ZnO hexagonal structure. The microstructural study was executed by using the Scherrer, W–H, and SSP methods. FTIR confirmed the presence of Zn–O, and Zn–M–O (M = Fe, Co) vibrational modes, which further confirmed the successful incorporation of dopants ions. The energy bandgap (E_g) extracted from UV–vis spectra has shown red-shift (3.37–2.7 eV) for decreasing Fe contents, whereas blue-shift (3.37–3.39 eV) for increasing Co concentration. SEM was used to investigate surface morphology, which represents the high rate of agglomeration. The photocatalytic test was performed on grown samples against various dyes and also observed the effects of varying concentrations of Fe and Co ions. The maximum degradation efficiency (98.8%) at 6%Fe and 4%Co under direct sunlight in 60 min against methylene blue (MB) was achieved. The photocatalytic activity of optimized concentration (6%Fe and 4%Co) was further tested against cresol red (CR), methyl orange (MO), safranin-O (SO), rhodamine-B (RhB), and methyl red (MR) dyes. The maximum degradation efficiency against MR dye (96.0%) was observed. The antibacterial test against Staphylococcus aureus and Klebsiella pneumoniae bacterial strains have shown that co-doped ZnO nanoparticles have a higher activity as compared to pristine ZnO, and furthermore, the sample with 6%Fe and 4%Co concentration exposed the highest antibacterial actively for both bacterial strains.     

Stable anatase phase with a bandgap in visible light region by a charge compensated Ga–V (1:1) co-doping in TiO2

A series of charge compensated Ga–V co-doped TiO₂ samples (Ti_(1-x)(Ga_0.5V_0.5)_xO₂) have been synthesized by a modified sol-gel process. X-ray diffraction pattern shows that the anatase to rutile (A→R) onset temperature (T_O) shifts to a higher temperature, whereas the complete phase transformation temperature (T_C) shifts to a low-temperature region as compared to pure TiO₂, due to Ga–V incorporation. Ga–V co-doping helps in the transformation of some smaller sized Ti⁴⁺ to a relatively larger Ti³⁺. In the anatase phase, oxygen content also increases with increasing doping concentration, which along with the larger size of Ti³⁺ results in lattice expansion and thereby delays the T_O. In the rutile phase, oxygen vacancy increases with increasing doping concentration, which results in lattice contraction and accelerates phase transition. Grain growth process is hindered in the anatase phase (crystallites size reduces from ~15 nm (x = 0.00) to 8 nm (0.10)), whereas it is accelerated in the rutile phase as compared to pure TiO₂. In both phases bandgap (E_g) reduces to the visible light region (anatase: E_g = 3.16 eV (x = 0.00) to 2.19 eV (x = 0.10) and rutile: 3.08 eV (x = 0.00) to 2.18 eV (x = 0.10)) in all co-doped samples. The tail of the absorption edge reveals lattice distortion and increase of Urbach energy proofs the same due to co-doping. All these changes (grain growth, phase transition, and optical properties) are due to lattice distortion created by the combined effect of substitution, interstitials, and oxygen vacancies due to Ga–V incorporation in TiO₂.     

Electrospun Sn-doped TiO2: Synthesis,structural, optical and catalytic performance as a function of Sn loading and calcination temperatures

A series of tin (Sn)-doped titania (TiO₂) composites were prepared by electrospinning and then calcined at temperatures of 500 °C, 600 °C, and 700 °C. The morpho-structural and optical properties of the resulting composites were assesed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. In this way, the effect of the dopant amounts and calcination temperatures on the composition, morphology, band gap energy (E_g) of the prepared composites was established, as well as their photocatalytic activity towards ciprofloxacin (CIP) photodegradation. The kinetics of ciprofloxacin photodecomposition reactions was analyzed. Herein, it is reported that the nanostructured material based on ([1.5%]Sn:TiO₂) sintered at 500 °C shows a remarkable photocatalytic activity with a removal efficiency of about 100% and a rate constant of 9.685 × 10^?2 min^?1. The photocatalytic stability of this material was evaluated by reusability tests with five cycles under identical conditions for CIP photodegradation. In-depth structural investigations were undertaken to explain this remarkable photocatalytic activity towards water decontamination.     

Visible light-responsive photocatalytic-based sustainable construction material for environmental remediation

The present study proposes a unique idea of utilizing cementitious materials incorporating iron-rich industrial waste products (IWPs) to support nano-photocatalyst like Titanium dioxide (TiO₂) to fabricate a visibly active Fe–TiO₂ composite exhibiting antibacterial property. The novelty of the present study lies in formulating a natural doping concept over the conventional techniques to facilitate the photocatalytic properties of the proposed sustainable construction material. To assess the structural performance of the prepared cementitious material, i.e., cement mortar, different physical (porosity, water absorption, and density) and mechanical (compressive strength, flexural strength, and split tensile strength) properties were performed. The results show that the cement mortar mixture FB5F having 15% (10% FA and 5% BS) proportion of conventional cement performed better in terms of workability and durability than other mix designs. Also, the stability and potency of the Fe–TiO₂ composite were analyzed using FESEM, EDS, elemental mapping, UV–vis DRS, and XRD. The characterization tests confirmed the iron-titanium (ITO) bond formation with shifting TiO₂ from UV to visible light spectrum (E_g = 2.52 eV). The Fe–TiO₂ composite was also subjected to an antibacterial check using an aliquot of E. coli bacterial suspension. The composite attained an E. Coli count of about 0.541 log reduction at the end of 45 min and thus, exhibited bacterial disinfection quality. Thus, the Fe–TiO₂ composite material proposes an eco-friendly concept which satisfies the requirement for a sustainable and low carbon footprint future which can additionally be used to treat different indoor and outdoor organic contaminants.     

Electrospun porous carbon nanofibers/TiO2 composite coated over carbon cloth- A flexible electrode for capacitive deionization

The combination of porous carbon matrix and metal oxide is trending for capacitive deionization (CDI) due to their synergistic electrochemical behaviour and properties. In this research, a flexible electrode based on electrospun porous carbon nanofibers and TiO₂ nanoparticles (particle size ～7 nm) i.e., PCNFs/TiO₂ composite coated over carbon cloth is developed. A facile in-situ activation procedure using sacrificial polymer is adopted over typical chemical activation treatment to synthesize PCNFs/TiO₂ composite. PCNFs/TiO₂ composite is prepared in two steps, possessing a high specific surface area of ～343 m² g^?1 and pore volume of 0.038 cm³ g^?1. Interestingly, CDI unit assembled with PCNFs/TiO₂ composite based flexible electrodes delivers the large salt electrosorption capacity of 204.8 mg g^?1 at voltage 1.2 V in a salt solution of concentration 500 ppm and conductivity 880 μS cm^?1. The excellent adsorption capacity retention of 96.4% up to ten adsorption-regeneration cycles can be a tempting option for future flexible CDI applications.     

Synthesis of TiO2(B)/SnO2 composite materials as an anode for lithium-ion batteries

A TiO₂(B) nanosheets/SnO₂ nanoparticles composite was prepared by the hydrothermal and chemical bath deposition (CBD) methods, and its electrochemical properties were investigated for use as the anode material of a lithium-ion battery. The as-prepared composites consisted of monoclinic-phase TiO₂(B) nanosheets and cassiterite structure SnO₂ nanoparticles, in which SnO₂ nanoparticles were uniformly decorated on the TiO₂(B) nanosheets. The TiO₂(B)/SnO₂ composites showed a higher reversible capacity and better durability than that of the pure TiO₂(B) for use as a battery anode. The composite electrodes exhibiting a high initial discharge capacity of 2239.1 mAh g⁻¹ and a discharge capacity of more than 868.7 mAh g⁻¹ could be maintained after 50 cycles at 0.1 C in a voltage range of 1.0–3.0 V at room temperature. The results suggest that TiO₂(B) nanosheets coated with SnO₂ could be suitable for use as a stable anode material for lithium-ion batteries. In addition, the coulombic efficiency of the nanosheets remains at an average of 93.1% for the 3rd–50th cycles.     

Decomposition of nonionic surfactant on a nitrogen-doped photocatalyst under visible-light irradiation

A visible-light-active N-containing TiO₂ photocatalysts were prepared from crude amorphous titanium dioxide by heating amorphous TiO₂ in gaseous NH₃ atmosphere. The calcination temperatures ranged from 200 to 1000 °C, respectively. UV–vis/DR spectra indicated that the N-doped catalysts prepared at temperatures <400 °C absorbed only UV light (E_g = 3.3 eV), whereas samples prepared at temperatures ≥400 °C absorbed both, UV (E_g = 3.10–3.31 eV) and vis (E_g = 2.54–2.66 eV) light. The chemical structure of the modified photocatalysts was investigated using FT-IR/DRS spectroscopy. All the spectra exhibited bands indicating nitrogen presence in the catalysts structure. The photocatalytic activity of the investigated catalysts was determined on a basis of a decomposition rate of nonionic surfactant (polyoxyethylenenonylphenol ether, Rokafenol N9). The most photoactive catalysts were those calcinated at 300, 500 and 600 °C. For the catalysts heated at temperatures of 500 and 600 °C Rokafenol N9 removal was equal to 61 and 60%, whereas TOC removal amounted to 40 and 35%, respectively. In case of the catalyst calcinated at 300 °C surfactant was degraded by 54% and TOC was removed by 35%. The phase composition of the most active photocatalysts was as follows: (a) catalyst calcinated at 300 °C—49.1% of amorphous TiO₂, 47.4% of anatase and 3.5% of rutile; (b) catalyst calcinated at 500 °C—7.1% of amorphous TiO₂, 89.4% of anatase and 3.5% of rutile; (c) catalyst calcinated at 600 °C—94.2% of anatase and 5.8% of rutile.     

Colossal dielectric permittivity in (Al+Nb) co-doped Ba0.4Sr0.6TiO3 ceramics

Stimulated by the outstanding colossal permittivity behavior achieved in trivalent and pentavalent cations co-doped rutile TiO₂ ceramics, the co-doping effects on the dielectric behavior of Ba_0.4Sr_0.6TiO₃ ceramics were further explored. In this work, (Al + Nb) co-doped Ba_0.4Sr_0.6TiO₃ ceramics were synthesized via a standard solid state ceramic route. The structural evolution was analyzed using X-ray diffraction patterns and Raman spectra. Dense microstructures with no apparent change of grain morphology were observed from the scanning electron microscopy. A huge enhancement of dielectric permittivity was obtained with 1 mol% (Al + Nb) doping and excellent dielectric performances (ε_r ∼ 20,000, tanδ ∼ 0.06 at 1 kHz) were achieved after further heat treatment. The formation of electron pinned defect dipoles localized in grains may account for the optimization of dielectric behaviors and the corresponding chemical valence states were confirmed from the XPS results.     

Electrochemical performance of Li4Ti5O12 anode materials synthesized using a spray-drying method

In this study, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) anode materials were synthesized from two titanium sources (P25 TiO₂, 100% anatase TiO₂) using a spray-drying method and subsequent calcination at various temperatures. The electrochemical performance of both a Li/LTO half cell and a LiNi_0.5Mn_1.5O₄/LTO (LNMO/LTO) full cell were investigated. The electrochemical performance of the LTO material prepared from P25 TiO₂ was superior to that of the LTO prepared from 100% anatase TiO₂. After modification of LTO material with AlPO₄, the LTO coated with 2 wt% of AlPO₄ (denoted “2%AlPO₄-LTO”) provided the best performances. The specific (delithiation) capacities of the 2%AlPO₄-LTO anode material was 189.7 mA h g⁻¹ at 0.1C/0.1C, 184.5 mA h g⁻¹ at 1C/1C, 178.8 mA h g⁻¹ at 5C/5C, and 173.1 mA h g⁻¹ at 10C/10C. From long-term cycling stability tests, the specific capacity at the first cycle and the capacity retention after cycling were 185.5 mA h g⁻¹ and 98.06%, respectively, after 200 cycles at 1C/1C and 182.1 mA h g⁻¹ and 99.18%, respectively, after 100 cycles at 1C/10C. For the LNMO/2%AlPO₄-LTO full cell, the average specific capacity (delithiation) and coulombic efficiency after the first five cycles were 164.8 mA h g⁻¹ and 93.30%, respectively, at 0.1C/0.1C. The specific capacities at higher C-rates were 156.1 mA h g⁻¹ at 0.2C/0.2C, 135.7 mA h g⁻¹ at 1C/1C, 97.5 mA h g⁻¹ at 3C/3C, and 46.5 mA h g⁻¹ at 5C/5C. After twenty-five cycles, the C-rate returned to 1C/1C and the specific capacity, coulombic efficiency, and capacity retention were maintained at 134.1 mA h g⁻¹, 99.17%, and 98.82%, respectively.     

Hydrogen evolution over sol-gel prepared visible-light-responsive Ag2O/SrAl2O4/CNT ternary photocatalyst

Photocatalytic hydrogen production over ceramic oxide photocatalysts is a promising technique for green energy production. However, most ceramics with large bandgap energies (E_g) do not operate in visible light. In this study, we present a sol-gel-based process for the preparation of SrAl₂O₄ nanoparticles coupled with precise amounts of Ag₂O and supported with carbon nanotubes (CNTs) to form Ag₂O/SrAl₂O₄/CNT ternary nanocomposites. The characterization of the prepared photocatalysts using various methods revealed a visible-light response in the presence of 0.5–4.0 wt% Ag₂O and 4.0% CNTs. The 3.0 wt% Ag₂O/SrAl₂O₄/4.0% CNT photocatapyst exhibited visible-light absorbance edge at 481 nm and E_g of 2.49 eV compared to 4.64 eV for SrAl₂O₄/4.0% CNT. Hydrogen evolution rate in the 10% glycerol/water system and Pt cocatalyst utilizing 3.0 wt% Ag₂O/SrAl₂O₄/4.0% CNT was 455.5 μmol g^?1h^?1 at an optimized dosage of 1.6 gL^?1 with commendable recyclability. The improved performance is attributed to the effective visible-light response and enhanced photocharge mobility because of the addition of a precise amount of Ag₂O and CNTs.     

Effect of TiO2 nanoparticles on the antibacterial and physical properties of polyethylene-based film

TiO₂ nanoparticles and their application in packaging systems have attracted a lot of attention because of its antimicrobial activity. In this work, effect of TiO₂ nanoparticles on the antibacterial and physical properties of polyethylene (PE)-based film was investigated. Results indicated that the antibacterial activity of TiO₂-incorporated PE films should be due to the killing effect property of TiO₂ nanoparticles against microorganisms. The TiO₂-incorporated PE film exhibited more effective antibacterial activity for Staphylococcus aureus. The antibacterial activity to inactivate Escherichia coli or S. aureus was improved by UV irradiation. The inhibition ratio of TiO₂-incorporated PE films sample irradiated for 60 min by UV light was improved significantly, which were 89.3% for E. coli and 95.2% for S. aureus, respectively, compared to that of TiO₂-PE film without UV irradiation. The analysis of physical properties revealed that TiO₂ nanoparticles increased the tensile strength and elongation at break of PE-based film. The climate resistance of nano-TiO₂ films is greatly enhanced, compared to that of the blank PE film. Water vapor transmission increased from 18.1 to 24.6 g/m²·24 h with the incorporation of TiO₂ nanoparticles. Results revealed that PE based film incorporating with TiO₂ nanoparticles have a good potential to be used as active food packaging system.     

Dielectric properties of (Y0.2Eu0.2Er0.2Dy0.2Lu0.2)3(AlxFe1-x)5O12 high-entropy garnet ceramics

A new kind of novel high-entropy rare earth garnet ceramics (HEREGCs, (Y_0.2Eu_0.2Er_0.2Dy_0.2Lu_0.2)₃(Al_xFe_1-x)₅O₁₂ (x = 0.4–0.6)) was designed and successfully synthesized by solid state reaction method. With the increase of Al content, the relative dielectric constant (ε_r′) at 100 Hz decreases from 4 × 104 to 1 × 102, while the dielectric loss (tanδ) increases from 0.93 to 2.65. The activation energy of grain boundary electrical conductivity (E_gb) and grain electrical conductivity (E_g) are fitted according to Arrhenius’ law, which indicate that the increase of difference between E_gb and E_g lead to the enhancement of dielectric properties. Our results provide the underlying insights needed to guide the study of colossal dielectric materials.     

Piezoelectric performance of 0.5BaZr0.2Ti0.8O3-0.5Ba1-xCaxTiO3 at triple phase point

0.5BaZr_0.2Ti_0.8O₃-0.5Ba_1-xCa_xTiO₃ ceramic samples with x = 15–35% have been fabricated to investigate the composition-driven phase evolution, ferroelectric, and piezoelectric properties. X-ray diffraction and temperature-dependent permittivity studies reveal the structural phase transition from the rhombohedral (R) to R + orthorhombic (O) and then O + tetragonal (T) having a tricritical triple phase points consisting of the R + O + T at x = 29.6%. The average grain size tends to increase with x but there is an exception of reducing grain size for x = 29.6%. The triple phase point displays the outstanding properties, such as minimum relaxation time (τ = 6.4 ms), large piezoelectric response (d₃₃ = 543 pC/N), high saturation polarization (P_S = 16.5 μC/cm²), small coercive field (E_c = 0.6 kV/cm), and high dielectric permittivity, over 8700 peaking at 21,765. These parameters reduce drastically at the O/R and O/T phase boundaries. Our studies indicate the important role of multiphase coexistence for enhancing the piezoelectric properties.     

Enhanced piezoelectric property and promoted depolarization temperature in Fe doped Bi1/2(Na0.8K0.2)1/2TiO3 lead-free ceramics

Piezoelectric sensors and energy harvesters require piezoelectric materials with large piezoelectric responses and good thermal stability. However, a commonly accepted concept is that the promotion of depolarization temperature of Bi_1/2Na_1/2TiO₃-based lead-free ceramics is usually companied by deterioration of piezoelectric properties. In the present study, the effects of acceptor-Fe doping on piezoelectric property and thermal depolarization behavior of Bi_1/2(Na_0.8K_0.2)_1/2TiO₃ ceramics are investigated. Fe doping at an appropriate level (≤ 3.0%) improves piezoelectric property and thermal stability simultaneously, due to the stabilization of long-range ferroelectric order. Piezoelectric constant d₃₃ increases from 125 pC/N to 148 pC/N with Fe amount of 3.0%, and then decreases. The depolarization temperature T_d is promoted continuously with Fe addition, from 76 °C for the undoped sample to 118 °C for the sample with Fe amount of 5.0%. It is proposed that the piezoelectric property and thermal stability can be simultaneously improved by stabilizing the long-range ferroelectric order in Bi_1/2Na_1/2TiO₃-based systems with obvious relaxor character. This work provides a new insight into the improvement of Bi_1/2Na_1/2TiO₃-based lead-free piezoelectric ceramics.     

Synthesis of SnO2@MnO2@graphite nanosheet with high reversibility and stable structure as a high-performance anode material for lithium-ion batteries

In this study, SnO₂@MnO₂@graphite (SMG) anode material is prepared via a facile ball-milling approach combined with hydrothermal treatment. SnO₂ and MnO₂ nanoparticles are evenly dispersed on numerous sheet-like graphite. MnO₂ can not only play a catalytic role for facilitating the conversion reaction of Sn/Li₂O to SnO₂, but also as a barrier to impede the coarsening of Sn in the composite. Meanwhile, graphite nanosheets could serve as an ideal volume expansion buffer and good electron conductor. Consequently, the SMG anode delivers superior reversible capacity of 1048.5 mAhg⁻¹, ideal rate capability of 522.2 mAhg⁻¹ at 5.0 A g^-1 and stable long-life cyclic performance of 814.8 mAhg⁻¹ at 1.0 A g^-1 after 1000 cycles. This result indicates that the incorporation of MnO₂, graphite nanosheet and SnO₂ have a great potential in enhancing the performance of SnO₂-based anode for battery applications.     

Morphological,structural and ellipsometric investigations of Cr doped TiO2 thin films prepared by sol–gel and spin coating

Pure and chromium doped titanium dioxide (TiO₂) thin films at different atomic percentages (0.5%, 1.3% and 2.9%) have been elaborated on ITO/Glass substrates by sol–gel and spin–coating methods using titanium (IV) isopropoxide as a precursor. The surface morphology of films was investigated by scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM), the structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission microscopy (HRTEM). SEM and HRTEM show homogenous and polycrystalline films. XRD patterns indicate a phase transition from anatase to anatase-rutile leading to expand the absorption band of TiO₂ molecules around 520 cm⁻¹ in FTIR spectra. The optical constants such as the refractive index (n), the extinction coefficient (K) and the band gap (E_g) as well as the film thickness are determined using spectroscopic ellipsometry technique and Fourouhi–Blommer dispersion model. Results show three major changes; (i) the thickness of pure TiO₂ layer is 54 nm, which linearly decreases when the layer is doped with chromium and reaches 33 nm for a doping concentration of 2.9%, (ii) the band gap energy (E_g) is also linearly reduced from 3.24 eV to 2.80 eV when the Cr-doping agent increases, and, (iii) a phase transition from anatase to anatase-rutile is observed causing an increase in values of n(λ) for wavelength greater than 350 nm.     

Effect of TiO2 nanoparticles on the horizontal hardness properties of Sn-3.0Ag-0.5Cu-1.0TiO2 composite solder

The improvement in the hardness of Sn-3.0Ag-0.5Cu solder alloy reinforced with 1.0 wt % TiO₂ nanoparticles was evaluated by nanoindentation. A specific indentation array was performed on four different horizontal cross sections of the composite solder with different heights and diameters, in order to verify the mixing homogeneity of TiO₂ nanoparticles within the Sn-3.0Ag-0.5Cu solder paste during the ball milling process. The phase analysis indicated successful blending of the Sn-3.0Ag-0.5Cu with the TiO₂ nanoparticles. According the scanning electron microscopy micrographs, presence of the TiO₂ nanoparticles reduced the size of the Cu₆Sn₅ and Ag₃Sn intermetallic compound phases. Incorporation of the 1.0 wt % TiO₂ nanoparticles improved the hardness values up to 26.2% than that of pure SAC305. The hardness values increased gradually from the top cross sections towards adjacent to the solder/substrate interface. The mechanism of the hardness improvement attained by the TiO₂ nanoparticles addition were also investigated on the horizontal cross sections of the samples.     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.