Epitaxial growth on nickel-plated diamond seeds at high pressure and high temperature

Epitaxial growth on nickel-plated diamond seeds at high pressure and high temperature (HPHT) was observed with graphite as carbon source. The thickness of the electroplating nickel film which acts as a catalyst/solvent ranges from 54.6 μm to 255.6 μm. The relationship between the Ni film thickness and diamond growth rate is investigated. When the nickel film thickness is from 90 μm to 129 μm, diamond crystals can nearly grow up to three times as large as the original seeds at ∼ 5.8 GPa and ∼ 1460 °C within 14 min. The mechanism of the crystal growth with nickel-plated diamond seeds under HPHT is discussed. The results and techniques might be useful for high quality saw-grade diamonds production and large diamond single crystal growth.     

Kitchen blender for producing high-quality few-layer graphene

The application of a kitchen blender for producing high-quality few-layer graphene (FLG) is demonstrated. The obtained FLG flakes, with an average thickness of ∼1.5 nm (∼20% ⩽ 1 nm), are high-quality and free of oxidation and basal-plane defects. With a rotating impeller, the kitchen blender can induce multiple fluid dynamics events which are featured by shear, turbulence, and collisions. These fluid dynamics events and their cooperative effects are responsible for the exfoliation mechanism, resulting in a gentle lateral-force-dominated way for graphite self-exfoliation through its lateral self-lubricating ability.     

Fine-patterning of sol-gel derived PZT film by a novel lift-off process using solution-processed metal oxide as a sacrificial layer

Sub-5 µm pattern of sol-gel derived lead-zirconium-titanate (PZT) film with a thickness of 80–390 nm was successfully prepared on Pt(111)/TiO_x/SiO₂/Si (100) substrate by a novel lift-off process using solution-processed metal oxides as a sacrificial layer. The process is simply divided into three steps: In-Zn-O (IZO) sacrificial layer spin-coating and patterning, PZT film formation followed by lift-off process. The results suggested that the IZO layer is effective in preventing PZT crystallization because of its thermal stability during PZT post-annealing, and its barrier-effects between the spin-coated PZT precursor and the Pt/TiO_x substrate. Consequently, the micro-pattern of lift-off PZT exhibited better properties than that formed by wet-etching. In particular, the lift-off PZT films possessed better ferroelectric properties, higher break-down voltage, and more well-defined shape than those of films patterned by conventional wet-etching. This lift-off process shows great promise for highly integrated devices due to its fine pattern-ability.     

Thickness effects on microwave properties of (Ba,Sr)TiO3 films for frequency agile technologies

We fabricated (Ba_0.6Sr_0.4)TiO₃ (BST) thin films of various thicknesses on sapphire (−1 1 2 0) substrates using metal-organic decomposition method. These films showed grain growth from 160 to 650 nm with an increase in the thickness from 90 to 1050 nm. At microwave frequencies, the measured capacitances of the planar capacitors decreased with the film thickness because the electro-magnetic field propagates across high permittivity BST films to the low permittivity sapphire substrate. However, we found that the BST-thin film permittivity remained large up to 90 nm thick, based on electro-magnetic field analysis using the finite element method. On the other hand, the BST thin film tunability decreased with the film thickness.     

Essential Macleod Program (EMP) simulated fabrication of high quality Zn:SnO2/Ag/Zn:SnO2 multilayer transparent conducting electrode on flexible substrates

In the quest of promising Indium free amorphous transparent conducting oxide (TCO), Zn-doped SnO₂/Ag/Zn-doped SnO₂ (OMO) multilayer films were prepared on flexible polyethylene terephthalate (PET) substrates by RF sputtering at room temperature (RT). Growth parameters were optimized by varying sputtering power and working pressure, to have high electrical conductivity and optical transmittance. Optimization of the thickness of each layer was done by Essential Macleod Program (EMP) simulation to get the higher transmission through OMO multilayer. The sheet resistance and transmittance of 3 at% Zn-doped SnO₂ thin film (30 nm) were 2.23 kΩ/□, (ρ ~ 8.92×10⁻³ Ω∙cm) and 81.3% (at λ ~ 550 nm), respectively. By using optimized thicknesses of Zn-doped SnO₂ (30 nm) and Ag (12 nm) and optimized growth condition Zn-doped SnO₂/Ag/Zn-doped SnO₂ multilayer thin films were deposited. The low sheet resistance of 7.2 Ω/□ and high optical transmittance of 85.1% in the 550 nm wavelength region was achieved with 72 nm multilayer film.     

Few-layer graphene by assisted-exfoliation of graphite with layered silicate

Few-layer graphene has been achieved in liquid dispersion from graphite by the assistance of titanosilicate JDF-L1, using ultrasound and methanol as dispersive media. After a sedimentation step, both the dispersed and the sedimented phases were collected and then the titanosilicate was removed by alkaline hydrothermal dissolution from the mixed materials to obtain few-layer graphene (FLG) and sedimented material, respectively. The production of smaller particles was confirmed by means of N₂ adsorption and zeta-potential measurements, so that the BET specific surface area increased from 20 m²/g of the raw graphite to 333 ± 22 m²/g in FLG. Raman spectroscopy shows a decrease in the ratio of intensities of the peaks G and 2D from 3.8 in the raw material to 2.5 in FLG. Particles as fine as 1.3 nm, corresponding to 4-layered FLG, were observed by AFM, while high-resolution TEM showed defect-free regions of graphene.     

Ferroelectric and dielectric properties of manganese-doped Na0.5Bi0.5TiO3 nanocrystalline thin films prepared by metal organic decomposition: A single-layer thickness-dependent study

2 at% Manganese-doped Na_0.5Bi_0.5TiO₃ (NBTMn) thin films with single-layer thicknesses ranging from 15 to 45 nm/l were deposited on the indium tin oxide/glass substrates by a metal organic decomposition process and spin coating technique. The influence of single-layer thickness on the crystal structure, surface morphology, insulating ability, ferroelectric and dielectric properties was mainly investigated. Compared with the other films, NBTMn film with a single-layer thickness of 30 nm/l exhibits the (110)-preferred orientation and dense structure. Also, it shows the enhanced ferroelectricity with a large remanent polarization (P_r) of 38 μC/cm² due to the preferred orientation and low leakage current density. Meanwhile, a high dielectric tunability of 39% for NBTMn with 30 nm/l can be observed by varying the measuring applied voltage and frequency. These results indicate that the suitable layer thickness is beneficial to improve the electrical performances of NBTMn thin film.     

Mechanical properties of PECVD thin ceramic films

Silicon dioxide (thickness 350 nm and 969 nm) and silicon nitride (thickness 218 nm) films deposited on silicon substrate using plasma enhanced chemical vapor deposition process were investigated using a Berkovich nanoindenter. The load-depth measurements revealed that the oxide films have lower modulus and hardness compared to the silicon substrate, where as the nitride film has a higher hardness and slightly lower modulus than the substrate. To delineate the substrate effect, a phenomenological model, that captures most of the ‘continuous stiffness measurement’ data, was proposed and then extended on both sides to determine the film and substrate properties. The modulus and hardness of the oxide film were around 53 GPa and 4–8 GPa where as those of the nitride film were around 150 GPa and 19 GPa, respectively. These values compare well with the measurements reported elsewhere in the literature.     

A high density of vertically-oriented graphenes for use in electric double layer capacitors

The growth, capacitance and frequency response of vertically-oriented graphenes grown by radio frequency plasma-enhanced chemical vapor deposition on nickel substrates and used as electrodes in electric double layer capacitors (EDLCs) are presented. The graphenes grown on the grain boundary of substrates show a faster growth rate, but less ordered structure than in the center of the nickel grain. At a few nanometers away from the grain boundaries the graphenes grow vertically at the rate of 70–80 nm per minute. The film height increased linearly with growth time from 700 nm (10 min sample) to 3.1 μm (40 min sample). Raman spectra show that the intensity ratio of the D band to G band gradually decreased with growth time to a value of 0.5, indicating that the crystalline order of the graphene increases with height. The specific capacitance of symmetric, parallel plate EDLC devices fabricated with these films was found to increase in a linear fashion with growth time up to values greater than 120 μF/cm² at 1 kHz. An impedance phase angle of ?45° was reached at 30 kHz. Specific capacitance normalized to growth height suggests that mechanisms other than double layer charge storage on planar surface area were operative.     

Ultraviolet pulsed laser crystallization of Ba0.8Sr0.2TiO3 films on LaNiO3-coated silicon substrates

In this work, Ba_0.8Sr_0.2TiO₃ (BST) films on LaNiO₃-buffered SiO₂/Si (LNO/SiO₂/Si) substrates were crystallized by pulsed laser irradiation. Solution-derived amorphous barium–strontium–titanate precursor layers were crystallized with a KrF excimer laser in oxygen ambient at fluences ranging from 50 to 75 mJ cm⁻². With the substrate temperature set to 500 °C, the number of pulses and film thickness were varied until high-quality crystallinity could be achieved. It was found that films with a thickness of 40 nm are fully crystallized with a uniaxial {00l} orientation which is predetermined by the LaNiO₃ orientation. On the other hand, for 160 nm thick films, crystallization was observed after 12,000 pulses in the 70 nm close to the surface, while the rest of the film remained amorphous. The large temperature difference between the film surface and interface due to the low thermal conductivity of the amorphous BST is suggested as the origin of this behavior. Films thicker than 80 nm cracked on crystallization due to the stress caused by the different thermal expansion coefficients of film and substrate, as well as the large temperature variations within the BST film.     

Direct preparation of silver nanoparticles and thin films in CO2-expanded hexane

Small, uniform and suspended silver nanoparticles were directly prepared in CO₂-expanded hexane by reducing a synthesized metal precursor, silver isostearate, with hydrogen but without introducing additional capping agents. By increasing CO₂ pressure, the suspended silver nanoparticles could be further deposited on a solid substrate to form silver thin film via gas antisolvent and the subsequent supercritical drying processes. The silver thin films prepared by the aforementioned method possessed a uniform thickness of about 150 nm without surface cracking and low electrical resistivity (5.64 × 10⁻⁶ Ω cm) after applying an annealing process. Due to the deposition of nano-sized silver particles, the annealing temperature could be as low as 175 °C that is lower than the softening points of many transparent polymeric substrates used for fabrication of flexible conductive films.     

Transparent and high infrared reflection film having sandwich structure of SiO2/Al:ZnO/SiO2

New transparent and high infrared reflection films having the sandwich structure of SiO₂/Al:ZnO(AZO)/SiO₂ were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO₂ (110 nm)/AZO (860 nm)/SiO₂ (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO₂ film can diminish the interference coloring and increase transparency; the inner SiO₂ film improves the adhesion of the coating to the glass substrate and prevents Ca²⁺ and Na⁺ in the glass substrate from entering the AZO film.     

Morphology,structure and density evolution of carbon nano-structures deposited by N-IR pulsed laser ablation of graphite

Carbon films were deposited by pulsed laser ablation on Si <100> substrates, heated at temperatures increasing from RT to 800 °C, from a pure graphite target, operating in vacuum (~ 10^− 4 Pa). The laser ablation was performed by an Nd:YAG laser, operating in the near IR wavelength (λ = 1064 nm).Micro-Raman and grazing incidence X-ray diffraction analysis (GI-XRD) established the progressive formation of ordered nano-sized graphitic structures, increasing substrate temperature. The surface morphology is characterised by macroscopic roughness (SEM, AFM) while the low temperature samples are characterised by very smooth surface. The film density, evaluated by X-ray reflectivity measurements, is also affected by the substrate temperature. This structural property modification induces relevant variation on the emission properties of carbon films, as evidenced by Field Emission measurements. The film structure and texturing is also strongly related to laser wavelength: the low energy associated to the IR laser radiation (1.17 eV) causes an early aromatic cluster formation at T = 400 °C associated to a sensible increase in the aromatic plane stacking distance (d₀₀₂ ~ 0.39 nm), compared to graphite. These density decrease shows a direct correlation with the electron emission properties. Roughness and presence of voids play a negative role both on the threshold electric field E_th and enhancement factor (β) The density decreasing and graphitic layer widening are notably to be ascribed to the very fast out-of-equilibrium growth and to the presence of large activated carbon species in the “plume”.     

Magnetron sputter deposition of hafnium nitride coating on high density graphite and niobium substrates

Hafnium nitride (HfN) is a refractory compound considered to be a suitable material for reaction barriers. The present paper deals with the preparation of HfN thin films by reactive magnetron sputtering on high density (HD) graphite and niobium substrates. Deposition process parameters have been optimised with Si(100) substrate in order to get HfN coating of 3 μm thickness. The optimised parameters were used to deposit HfN on HD graphite and on niobium substrates. The results showed that HfN coating with a thickness of 2.8 μm was successfully deposited on HD graphite and niobium substrates. The presence of HfN was confirmed by glancing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy (XPS). XRD studies on HfN coating on Si(100), HD graphite and Nb substrates showed nanocrystalline grains of size 130, 55 and 46 Å, respectively. The surface morphology of HfN coating on HD graphite and niobium by atomic force microscope (AFM) and scanning electron microscope (SEM) showed that nanoparticles are getting agglomerated into clusters. The HfN coating on niobium substrate exhibited good adhesion compared to that on HD graphite as studied by microscratch test. The thermal stress generated in the sputter deposited HfN coating on HD graphite and niobium substrates were calculated by analytical formula for thermal stress. The tensile and highly compressive stresses observed in the HfN coating on niobium and HD graphite, respectively, indicated a lower adhesive strength of the coating on the later than that of the former.     

Coating of nano-sized ionically conductive Sr and Ca doped LaMnO3 films by sol–gel route

In this study, Sr and Ca doped LaMnO₃ thin ceramic films were coated on Al₂O₃ substrates by using a sol–gel route as the cathode material for SOFC. Nitrate precursors were used for the preparation of the thin film coating solution, and methanol and acetyl acetone were also used as the solvent and chelating agent, respectively. After the solution was prepared, an Al₂O₃ single crystal substrate was dipped into the solution. Then it was fired at 500 °C and annealed at 1025 °C for the crystallization. Coated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), focused ion beam (FIB) and atomic force microscopy (AFM). Conductivity of the coated films was measured by the four probe Van der Pauw method. XRD, SEM, AFM and FIB characterizations of the coated film showed that the LaMnO₃ phase was formed, surface of the films was uniform and had homogenously distributed pores sized about 10 nm, mean grain size was about 60–80 nm and the film thickness was about 180 nm. The specific resistivity of the film was calculated to be 0.524 Ω m.     

Nanoindentation of nano-Al/Si3N4 multilayers with Vickers and Brinell indenters

The mechanical properties of ceramics films at the sub-micron, even nanometer length scale have attracted increased attention due to the high-speed development of microelectronic technology. In this work, nano-indentation hardness as a function of the different individual layer thickness has been measured and investigated in the sputtered Al/Si₃N₄ multilayers with different indenters (Vickers and Brinell). For this ceramics/metal multilayers system, the hardness of the multilayers increases with decreasing individual layer thickness from 500 nm to 100 nm and from 50 nm to 10 nm, indicating a significant size effect. At the same time, changes in the deformation behavior may be controlled by different deformation mechanisms for submicron scale and nanometer scale.     

Preparation of ultrathin PZT films by a chemical solution deposition method from a polymeric citrate precursor

Ultrathin PZT film was prepared using a chemical solution deposition method from polymeric citrate precursors. The PZT solution was spin-coated on an amorphous silica layer formed on a Si(1 0 0) substrate. The films were thermally treated from the substrate side with a low heating rate (1°/min) up to 700 °C and finally annealed for 10 h. Ultrathin PZT films without microstructural instability were prepared in spite of high temperature and long annealing time. AFM and HRTEM investigations revealed the formation of a well-developed dense microstructure consisting of spherical crystallites (4–7 nm). Low roughness (2.2 nm) of a ～26 nm thick layer was obtained for a two-layered PZT film. The grazing incidence X-ray diffraction (GIXRD) measurements confirmed the polycrystalline structure of ultrathin PZT films. Also, GIXRD and electron energy dispersive X-ray (EDS) analysis showed that compositional variations were smaller than expected, in spite of the long annealing time.     

Extreme insulating ultrathin diamond films for SOD applications: From coalescence modelling to synthesis

The synthesis of diamond films with extreme insulating properties is of great interest for most diamond film applications in nanoelectronics. SOD (Silicon-On-Diamond) is a promising alternative to standard SOI (Silicon-On-Insulator) because of the high heat-spreading capability of diamond material. Current Fully Depleted MOS processing technologies require a thickness of the dielectric buried layer of 150 nm. Synthesis of polycrystalline diamond films is already well documented. Nonetheless, the difficulties here are to keep their high thermal conductivity and their high electrical resistivity in spite of the reduction of the diamond layer thickness. This study aims at the fine control of both the nucleation density and the growth process to enable the fabrication of optimized fully covered diamond films as thin as possible.A mathematical model describing the coalescence was used to determine the surface coverage of the diamond film according to the linear growth of the diamond nanocrystals for different nucleation densities. The model gives information on the nucleation density needed to obtain a covering diamond film within ultrathin diamond layer thickness. To corroborate the coalescence model, diamond layers with different surface coverages were characterized. Our work led to ultrathin diamond layers (thickness below 140 nm) exhibiting electrical resistivities above 2 × 10¹³ Ω cm.     

Long-term stability of a horizontally-aligned carbon nanotube field emission cathode coated with a metallic glass thin film

A horizontally-aligned carbon nanotube (HACNT) field emission cathode was coated with a metallic glass thin film (MGTF) to improve the stability of the field emission properties. HACNT field emission cathodes have previously been fabricated on glass substrates using composite plating and crack-formation techniques. A carbon nanotubes/nickel (CNTs/Ni) composite film is deposited onto a glass substrate at 80 °C by the composite plating technique alone. Cracks are then formed in the CNT/Ni composite film during 30 min heating at 300 °C, and HACNTs are exposed in the cracks. The field emission properties of the HACNT field emission cathode show a low turn-on electric field E_on of about 2.3 V/μm, a low threshold electric field E_th of about 4.7 V/μm at an emission current density of 1 mA/cm², and a stability time of 78 h. The degradation of the HACNT field emission cathode is prevented by using a MGTF-coating technique and superior long-term stability (i.e. >125 h, with 5 nm MGTF; >270 h, with 10 nm MGTF) for the MGTF/HACNT field emission cathode is achieved.