Impact of sintering temperature on phase composition,microstructure, and porosification behavior of LTCC substrates

Phase development and changes in crystalline composition of LTCC material during the sintering process were investigated using in-situ X-ray diffraction (XRD) measurements. CeramTape GC was chosen as the chemically simplest model system composed of alumina particles and glass for the investigations. The chemical characterization and microstructural analyses of the tapes sintered with some representative firing profiles were performed by techniques such as (scanning) transmission electron microscope, energy-dispersive X-ray spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and XRD. Moreover, the porosification behavior of LTCC substrates fired at different peak temperatures was studied. These investigations are important for the subsequent wet chemical etching, representing an approach which allows to reduce locally the permittivity of LTCC tapes. Treatment with a KOH solution shows non-selective etching behavior for all substrates. In addition, highly porous silica structures corresponding to Ca and Al depletion from the anorthite phase were observed in all samples after etching treatment.     

Impact of additives and processing on microstructure and dielectric properties of willemite ceramics for LTCC terahertz applications

The paper presents the fabrication procedure, microstructure and dielectric properties of the low temperature cofired ceramics (LTCC) based on Zn₂SiO₄ doped with AlF₃, CaB₄O₇, Li₂TiO₃ and MgTiO₃. The heating microscope studies and differential thermal analysis were used for characterization of the behavior of the green tapes and ceramic samples during heating up to high temperatures. The microstructure and composition were analyzed by scanning electron microscopy, X-ray energy dispersive spectroscopy and XRD method. The dielectric properties were investigated in three frequency regions: 100 Hz–2 MHz, 90–140 GHz and 0.15–3 THz. The developed materials are promising candidates for the LTCC submillimeter wave applications due to a low sintering temperature of 900–980 °C, good compatibility with silver pastes and good dielectric properties – a low dielectric permittivity of 6–6.8, a relatively low dissipation factor of 0.005–0.008 at 1 THz, and a weak temperature dependence of dielectric permittivity.     

Spherical ferroelectric PbZr0.52Ti0.48O3 nanoparticles with high permittivity: Switchable dielectric phase transition with temperature

The spherical ferroelectric PbZr_0.52Ti_0.48O₃ (PZT 52/48) nanoparticles are prepared via simple and environment friendly high temperature solid state method. The crystal structure and morphology of these particles are characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM). XRD analysis and selected area electron diffraction (SAED) pattern of PZT particles revealed its crystalline nature. The energy involved in the synthesis especially during the initiation and termination processes for the formation of PZT particles is found from the high temperature calorimetric study. These particles are spherical in nature with an average diameter of ≤20 nm. The bulk and surface chemical composition of these particles are investigated by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). XPS study reveals that the prepared PZT particles contain titanium ion in two different oxidation states namely Ti³⁺ and Ti⁴⁺. The PZT particles exhibit high permittivity with relatively low dielectric loss. From temperature dependent dielectric analysis, it is seen that there is a switchable dielectric phase transition at or above 80 °C.     

Surface doping of TiO2 powders via a gas–melt reaction using thermal plasma as an excitation source

Surface doping is an effective method to engineer and functionalize powder materials without modulating the internal crystal structure. This study proposed a facile technique for surface doping via a gas–melt reaction using thermal plasma as an excitation source. Doping molten titania (TiO₂) particles with La was preliminarily explored owing to the broad photocatalytic applications of TiO₂. Scanning electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy, transmission electron microscope, diffuse reflectance spectroscopy, photoluminescence spectroscopy and Fourier transform infrared spectroscopy were adopted to characterize the morphology, phase composite, chemical state, fine structure, and optical property of the doped TiO₂ powder, respectively. Results indicated that molten TiO₂ doped with La solidified into spherical particles under the effect of surface tension. No modification of the internal crystal structure was indicated in the XRD patterns, except that the diffraction peak of rutile TiO₂ (110) shifted to low angles after surface doping with La. The obtained TiO₂ powder exhibited sensitivity to sunlight and near-infrared light, and a La/Ti atomic ratio of 19.4% was achieved. The diffusivity D_i of La in molten TiO₂ ranged from 10⁻⁸ m²/s to 10⁻⁷ m²/s, as determined from the gas–melt reaction.     

Indirect charge transfer of holes via surface states in ZnO nanowires for photoelectrocatalytic applications

In this work, ZnO nanowires with high aspect ratio were obtained by fast and simple electrochemical anodization. Morphological, structural and photoelectrochemical characteristics of the synthesized ZnO nanowires were evaluated by using different techniques: field emission scanning electron microscopy, atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–VIS spectroscopy, Mott-Schottky analysis and photoelectrochemical impedance spectroscopy. The synthesized ZnO nanowires presented high roughness and high crystallinity. Besides, surface defects were identified in the sample. The value of the donor density (N_D) was in the order of 10¹⁹ cm^?3 in the dark and 10²⁰ cm^?3 under illumination. In addition, the ZnO nanowires presented good photosensibility, with a photocurrent density response 85 times higher than a ZnO compact layer, and lower resistance to charge transfer. The charge transfer processes taking place at the ZnO/electrolyte interface were studied, since these processes strongly influence the photoelectrocatalytic efficiency of the material. According to the results, the charge transfer of holes in the synthesized ZnO nanowires occurs indirectly via surface states. In this regard, surface states may be an important feature for photoelectrocatalytic applications since they could provide lower onset voltages and higher anodic current densities.     

Anodisation of a Nb-Zr alloy

Anodisation of a Nb-Zr alloy was studied in ammonium sulphate and hydrochloric acid electrolytes using electrochemical and surface analysis methods. Using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry, a value of ε_r=27 was estimated for the relative permittivity and of 0.4 V nm⁻¹ for the electrical field in the oxide film. Annealing of a mechanically polished disc sample to 600 °C for 14 h in UHV resulted in a fourfold surface enrichment of zirconium. This enrichment remained after anodisation in the sulphate solution, but could be removed with an anodisation in hydrochloric acid. Auger electron spectroscopy was used to estimate the thickness and composition of the anodic oxides. The film thickness measurements suggested a logarithmic growth law. The surface concentration of zirconium at the outer film surface of heat-treated samples decreased logarithmically when anodisation was performed in 1 M hydrochloric acid. No corresponding decrease in zirconium concentration was observed during immersion at open circuit.     

Synthesis and characterisation of La(Co1/2Ti1/2)O3

Single phase, dense La(Co_1/2Ti_1/2)O₃ (LCT) ceramics have been fabricated using conventional solid state synthesis. Samples were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and their dielectric properties were studied at radio and microwave frequencies. X-ray and electron diffraction conclusively revealed that LCT contained in-phase and antiphase rotations of the O-octahedra, consistent with and a⁻a⁻c⁺ tilt system in the Glazer classification. However, XRD indicated that the Co and Ti ions were disordered on the B-site whereas TEM and Raman spectroscopy exhibited reflections and modes which suggested that partial ordering may be present. Moreover, some Raman bands could only be explained by assuming that at least some of the octahedra exhibited a Jahn–Teller distortion. Dielectric measurements indicated that LCT is insulating with low dielectric loss, 0.0024 at 1 MHz and frequency independent relative permittivity, ε_r=25. A quality factor, Q×f_o=38,000 was obtained at microwave frequencies along with a temperature coefficient of the resonant frequency, TCF=−42 MK⁻¹.     

Spectroscopic studies of nanocrystalline diamond materials

The structural and electronic properties of nanocrystalline diamond films synthesized by a modified hot-filament chemical vapour deposition process were investigated by both bulk- and surface-sensitive techniques. Diffraction and microscopy data show the films to consist of diamond grains with an average crystallite size of about 10–15 nm and a root-mean-square roughness of similar size. Carbon core-level excitations in transmission electron energy-loss spectroscopy reveal an sp² content below 5%. The low energy loss spectra are quite similar to that of diamond crystal. The high sp³ content in the films was also confirmed by C 1s photoelectron plasmon energy loss features in X-ray photoemission experiments and by X-ray excited Auger-electron spectroscopy. We find that the hydrogen covered diamond surface gets contaminated after storage for several months under ambient conditions. Heating up to 500°C in vacuo is required to desorb the adsorbate layer.     

Measurements of loss tangent and relative permittivity of LTCC ceramics at varying temperatures and frequencies

Precise knowledge of microwave properties of LTCC materials is crucial for efficient design of microwave systems, especially for design of communication filters. In this paper relative permittivity ε_r and loss tangent tanδ of a variety of LTCC ceramics manufactured by Heraeus Circuit Materials Division are presented for frequencies of 3.3 and 5.5 GHz at room temperature and also for temperatures varying from −33 °C to 22 °C at a frequency of 3.3 GHz. The measurement system for microwave characterisation of LTCC materials was based on the split post dielectric resonator and the Transmission Mode Q-factor techniques with random uncertainty in ε_r and in tanδ better than 0.5 and 2.6% respectively.     

AC impedance spectroscopy study of the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution

The corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution at the corrosion potential (E_corr) was investigated using electrochemical impedance spectroscopy (EIS), environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The results showed that when the immersion time was less than 18th, general corrosion occurred on the surface and the main corrosion products were hydroxides and sulfates. The film coverage effect was the main mechanism for the corrosion process of AZ91 alloy. At this stage, the matrix had a better corrosion resistance. With the increasing immersion time, pitting occurred on the surface. At this stage, the corrosion process was controlled by three surface state variables: the area fraction θ₁ of the region controlled by the formation of Mg(OH)₂, the area fraction θ₂ of the region controlled by the precipitation of MgAl₂(SO₄)₄·2H₂O, and the metastable Mg⁺ concentration C_m.     

Easy synthesis of highly nitrogen-enriched graphitic carbon with a high hydrogen storage capacity at room temperature

An easy method for synthesizing highly nitrogen-enriched graphitic carbon was developed and its hydrogen storage capacity was explored. The synthesis method uses a solution-based, stepwise condensation reaction between cyanuric chloride and melamine at low temperature (e.g., 0, 25, and 120 °C) and ambient pressure using conventional glassware without the need for an autoclave vessel. The physical and chemical structure of the synthesized highly nitrogen-enriched graphitic carbon was investigated by powder X-ray diffraction, scanning and transmission electron microscopy, selected area electron diffraction, energy dispersive spectroscopy, elemental analysis, Fourier transform infrared spectroscopy, X-ray photoemission spectroscopy, and electron energy loss spectroscopy. The analyzes confirmed that the product has a highly crystalline nitrogen-enriched graphitic structure (d₀₀₂ = 0.324 nm) with a carbon-to-nitrogen ratio of 1:1.12 (>50 atomic% nitrogen content). The material was determined to have an excellent hydrogen storage capacity of 0.34 wt% at room temperature under 100 bar in spite of its low BET surface area of only ∼10 m²/g.     

Improving dielectric properties of poly(vinylidene fluoride) composites: effects of surface functionalization of exfoliated graphene

To investigate the effects of surface functionalization of exfoliated graphene (EG) on the crystalline form of β-phase and dielectric properties of poly(vinylidene fluoride) (PVDF), we prepared PVDF-based composites reinforced by different functionalized EG. The X-ray photoelectron spectroscopy results indicated that a wide variety of chemical functional groups such as C–OH, C–O–C, C=O, COOH and C–F could be introduced on the surface of modified EG. As confirmed by results of Fourier transform infrared spectrum and X-ray diffraction, the β-phase PVDF can be produced in the composites with the incorporation of functionalized EG. In the frequency ranging from 10² to 10⁷ Hz, the dielectric permittivity of PVDF composites shows an obvious increase owing to a variation of the carbonyl group (C=O) content. Among all the composites, the EG grafted with polymethyl methacrylate/PVDF composite has the highest dielectric permittivity and dielectric loss.     

Ultralow-permittivity glass /Al2O3 composite for LTCC applications

In the field of low temperature co-fired ceramic (LTCC), it remains a challenge to design the performance of LTCC with low permittivity less than 5. Here, a novel glass mixture of K-Al-B-Si-O (KABS) and Zn-B-Si-O (ZBS) is introduced as a sintering aid of alumina to obtain ultralow-permittivity glass/Al₂O₃ composite. Meanwhile, the factors of glass mixture component on microstructure, phase structure and dielectric properties of the composites are considered systematically. The crystal structure measured by X-ray diffraction (XRD) shows that pure crystalline phase of ZnAl₂O₄ spinel can be attained by tailoring the component of the glass mixture. In case of mass ratio of KABS: ZBS equal to 6:4, it favors to efficiently increase the sintering densification of composite, and significantly benefit the low dielectric loss, good mechanical and thermal performances. In detail, the optimal glass/ceramic composites sintered at 850 °C for 2 h exhibit the bulk density of 2.89 g/cm3, ε_r of 4.92 at 14 GHz and Q × f of 6873 GHZ, flexural strength of 202 MPa, thermal expansion coefficient of 5.5 ppm/°C. The above study provides an effective approach for preparing the novel composites as a promising candidate for LTCC applications.     

Effects of sintering temperature on the internal barrier layer capacitor (IBLC) structure in CaCu3Ti4O12 (CCTO) ceramics

The formation of the internal barrier layer capacitor (IBLC) structure in CaCu₃Ti₄O₁₂ (CCTO) ceramics was found to be facilitated by the ceramic heat treatment. Electrically insulating grain boundary (GB) and semi-conducting grain interior areas were characterized by impedance spectroscopy to monitor the evolution of the IBLC structure with increasing sintering temperature T_S (975–1100 °C). The intrinsic bulk and GB permittivity increased by factors of ≈2 and 300, respectively and the bulk resistivity decreased by a factor of ≈10³. These trends were accompanied by increased Cu segregation from the CCTO ceramics as detected by scanning electron microscopy and quantitative energy dispersive analysis of X-rays. The chemical changes due to possible Cu-loss in CCTO ceramics with increasing T_S are small and beyond the detection limits of X-ray absorption spectroscopy near Cu and Ti K-edges and Raman Spectroscopy.     

Bacterial adhesion on silicon-doped diamond-like carbon films

In this paper the surface properties of silicon-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate by a magnetron sputtering technique were investigated. X-ray photoelectron spectroscopy was applied to determine the surface chemical composition of the films. Atomic force microscopy was used for the determination of surface roughness and topography. The sp² contents in the films were determined with Auger electron spectroscopy, which were 67.1%, 34.2% and 25.0% for silicon contents 1%, 2% and 3.8%. The sp³/sp² ratio increases with increasing the silicon contents in the films. Contact angles of three test liquids on the films were obtained with a Dataphysics OCA-20 contact angle analyzer. Surface free energies of the films and their dispersive and polar components were calculated using van Oss acid–base approach. Staphylococcus aureus was used for bacterial adhesion test. The experimental results showed that bacterial adhesion decreased with increasing the silicon content or with increasing sp³/sp² ratio in the films.     

Effect of boric oxide doping on the stability and activity of a Cu–SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol

Stable and efficient B–Cu–SiO₂ catalysts for the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol were prepared through urea-assisted gelation followed by postimpregnation with boric acid. Auger electron spectroscopy and CO adsorption by in situ Fourier transform infrared spectroscopy revealed that the Cu⁺ species on the catalyst surface increased together with an increase in the amount of boric oxide dopant. X-ray diffraction and N₂O chemisorption indicated that a suitable amount of boric oxide doping tended to improve copper dispersion and retard the growth of copper particles during DMO hydrogenation. Catalytic stability was greatly enhanced in the B–Cu–SiO₂ catalyst with an optimized Cu/B atomic ratio of 6.6, because of the formation and preservation of appropriate distributions of Cu⁺ and Cu⁰ species on the catalyst surfaces. The effect of boric oxide was attributed to its relatively high affinity for electrons, which tended to lower the reducibility of the Cu⁺ species.     

Synthesis of LiBGeO4 using compositional design and its dielectric behaviors at RF and microwave frequencies

Borates are promising candidates as dielectric substrate materials in low temperature cofired ceramics technology (LTCC) due to their relative low sintering temperatures and relative permittivities compared to their counterparts. However, synthesizing borates having single-phase is still challenging because of the volatility and hydrophilicity of boron resources. In this work, a compositional design was utilized to synthesize single-phase LiBGeO₄ ceramics over a broad temperature range from 600 to 840 °C. Radio-frequency dielectric behaviours featured a strong temperature dependence, especially at high temperatures (>400 °C), which is related to the thermally activated polarizations. LiBGeO₄ ceramic sintered at 820 °C has optimum microwave dielectric properties with the relative permittivity (ε_r) of 6.28, a quality factor (Q × f) of 21,620 GHz, and a temperature coefficient of resonance frequency (τ_f) of -88.7 ppm/^°C. LiBGeO₄ also showed chemical inertness when cofired with silver (Ag), provided an evidence for its utilization in LTCC technology. Overall, this work provides a strategy for facile synthesis of phase pure borates, via the proposed two-step process to obtain stable boron resources.     

Graphical based characterisation and modelling of material gradients in porosified LTCC

The chemical composition of low temperature cofired ceramics (LTCC) allows to locally embed air into sintered substrates by a selective wet chemical etch process. Therefore, LTCC substrate with areas of low permittivity can be created without material combination. The presented graphical method of material component contrast images enables the evaluation of their most important material properties which are their component distribution, their porosification gradient and their residual bearing surface. The graphical method, including focused ion beam and scanning electron microscopy analyses, is applied to different commercially available LTCC types having two porosification states each. Derived mathematical models, which are suitable for finite element method implementation, allow the characterisation of the effective permittivity reduction while keeping a maximum residual surface area for, e.g., metallisation purposes. The shape of the optimum material distribution function features an ‘air pocket’ of small width and a depth being dependent on the application specific operating frequency.     

Bi-level surface modification of hard disk media by carbon using filtered cathodic vacuum arc: Reduced overcoat thickness without reduced corrosion performance

The corrosion performance of commercial hard disk media which was subjected to bi-level surface modification has been reported. The surface treatment was carried out by bombarding the surface of the magnetic media with C⁺ ions at 350 eV followed by 90 eV using filtered cathodic vacuum arc (FCVA). The energy and embedment depth of the impinging C⁺ ions were adjusted by applying an optimized bias to the substrate and simulated by a Stopping and Range of Ions in Matter (SRIM) code which predicted the formation of a graded atomically mixed layer at the carbon-media interface. Cross-section transmission electron microscopy (TEM) revealed the formation of a 1.8 nm dense nano-layered carbon overcoat structure on the surface of the media. Despite an ~ 33% reduction in the thickness, the bi-level surface modified disk showed corrosion performance similar to that of a commercially manufactured disk with a thicker carbon overcoat of 2.7 nm. This improvement in the corrosion/oxidation resistance per unit thickness can be attributed to the formation of a dense and highly sp³ bonded carbon layer, as revealed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. This study demonstrates the effectiveness of the bi-level surface modification technique in forming an ultra-thin yet protective overcoat for future hard disks with high areal densities.     

Surface structural features and optical analysis of nanostructured Cu-oxide thin film coatings coated via the sol-gel dip coating method

Nanostructured thin film coatings of copper oxide (Cu-oxide) were investigated to determine their physical structure, surface morphology, surface electronic bonding states, and optical properties. The Cu-oxide had been coated onto reflective aluminum substrates via a facile one-step sol–gel dip-coating route using a copper nitrate precursor. Characterizations were conducted using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), and ultra-violet visible (UV–Vis) spectroscopic methods, and representative sol-gel reactions using copper nitrate precursor were proposed. The XPS spectra confirmed the presence of copper oxide elements. Further exploration of the Cu2p3/2 peak in XPS spectra revealed that the electronic structure of the copper component consisted of tetrahedral Cu(I) and octahedral Cu(II) with the presence of octahedral Cu(II) enabling coatings to have high absorption levels across the solar spectrum. The deconvolution of the O1s spectra exhibited three curve-fitting components: the lattice O²⁻, surface oxygen, and subsurface O⁻ species. FESEM results showed that the coating surface was an agglomerated copper oxide nanoparticles structure forming a porous structure. The optical band-gap of Cu-oxide thin film coatings, via the Tauc plot, was 2.7 eV.