Chemical mechanical polishing of thin film diamond

The demonstration that Nanocrystalline Diamond (NCD) can retain the superior Young’s modulus (1100 GPa) of single crystal diamond twinned with its ability to be grown at low temperatures (<450 °C) has driven a revival into the growth and applications of NCD thin films. However, owing to the competitive growth of crystals the resulting film has a roughness that evolves with film thickness, preventing NCD films from reaching their full potential in devices where a smooth film is required. To reduce this roughness, films have been polished using Chemical Mechanical Polishing (CMP). A Logitech Tribo CMP tool equipped with a polyurethane/polyester polishing cloth and an alkaline colloidal silica polishing fluid has been used to polish NCD films. The resulting films have been characterised with Atomic Force Microscopy, Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy. Root mean square roughness values have been reduced from 18.3 nm to 1.7 nm over 25 μm², with roughness values as low as 0.42 nm over ∼0.25 μm². A polishing mechanism of wet oxidation of the surface, attachment of silica particles and subsequent shearing away of carbon has also been proposed.     

Thermo-mechanical behaviors and moisture absorption of silica nanoparticle reinforcement in epoxy resins

An investigation of the thermo-mechanical behavior of silica nanoparticle reinforcement in two epoxy systems consisting of diglycidyl ether of bisphenol F (DGEBF) and cycloaliphatic epoxy resins was conducted. Silica nanoparticles with an average particle size of 20 nm were used. The mechanical and thermal properties, including coefficient of thermal expansion (CTE), modulus (E), thermal stability, fracture toughness (K_IC), and moisture absorption, were measured and compared against theoretical models. It was revealed that the thermal properties of the epoxy resins improved with silica nanoparticles, indicative of a lower CTE due to the much lower CTE of the fillers, and furthermore, DGEBF achieved even lower CTE than the cycloaliphatic system at the same wt.% filler content. Equally as important, the moduli of the epoxy systems were increased by the addition of the fillers due to the large surface contact created by the silica nanoparticles and the much higher modulus of the filler than the bulk polymer. In general, the measured values of CTE and modulus were in good agreement with the theoretical model predictions. With the Kerner and Halpin-Tsai models, however, a slight deviation was observed at high wt.% of fillers. The addition of silica nanoparticles resulted in an undesirable reduction of glass transition temperature (T_g) of approximately 20 °C for the DGEBF system, however, the T_g was found to increase and improve for the cycloaliphatic system with silica nanoparticles by approximately 16 °C. Furthermore, the thermal stability improved with addition of silica nanoparticles where the decomposition temperature (T_d) increased by 10 °C for the DGEBF system and the char yield significantly improved at 600 °C. The moisture absorption was also reduced for both DGEBF and cycloaliphatic epoxies with filler content. Lastly, the highest fracture toughness was achieved with approximately 20 wt.% and 15 wt.% of silica nanoparticles in DGEBF and cycloaliphatic epoxy resins, respectively.     

Silica fume as porogent agent in geo-materials at low temperature

The synthesis of geopolymers based on alkaline polysialate was achieved at low temperature (～25–80 °C) by the alkaline activation of raw minerals and silica fume. The materials were prepared from a solution containing dehydroxylated kaolinite and alkaline hydroxide pellets dissolved in potassium silicate. Then the mixture was transferred to a polyethylene mold sealed with a top and placed in an oven at 70 °C for 24 h. For all geopolymer materials, following dissolution of the raw materials, a polycondensation reaction was used to form the amorphous solid, which was studied by FTIR-ATR spectroscopy. The in situ inorganic foam based on silica fume was synthesized from the in situ gaseous production of dihydrogen due to oxidation of free silicon (content in the silica fume) by water in alkaline medium, which was confirmed via TGA-MS experiments. This foam has potential as an insulating material for applications in building materials since the thermal measurement has a value of 0.22 W m^?1 K^?1.     

Plasma-activated direct bonding of patterned silicon-on-insulator wafers to diamond-coated wafers under vacuum

Direct wafer bonding requires the surfaces to have low surface roughness (R_a < 0.5 nm) as well as to be free of any particles or contaminants. Meeting these requirements for wafers patterned with lithography and dry etching presents a serious problem in terms of removal of photoresist residue and etch-related particles, which would require expensive additional equipment to be removed. In this study, we propose the use of chemical mechanical polishing (CMP) to be performed after all lithography and dry etch process steps involving several masks are completed. To reduce the adverse effect of any remaining slurry that might reside in the etched structures, we also propose to reduce the maximum annealing temperature from 550 °C down to 300 °C. The effect of lower annealing temperature on bonding is compensated using a sequential plasma activation with 60 s of O₂ followed by 90 s of N₂ on contacting surfaces made of silicon dioxide to achieve successful wafer bonding. Initial plasma activation with O₂ additionally serves as a final cleaning step whereas the following activation with N₂ for an extended duration is to fully activate the surface for direct bonding. This proposed technique can motivate the use of direct wafer bonding for microfabrication of advanced MEMS devices.     

Influence of surface treatments on topography and bond strength of densely-sintered zirconium-oxide ceramic

The aim of this study was to evaluate the effect of surface treatments on the roughness and bond strength of dental materials containing MDP to zirconium oxide ceramic. Forty square-shaped zirconium-oxide ceramic blocks (Lava Zirconia, 3M-ESPE) were treated as follows: (CT) polished only; (SB) sandblasting (110 µm aluminum oxide particles) or (SC) silica coating (110 µm particles). Roughness of treated surface was measured using a profilometer (Ra) and by atomic force microscope (AFM). Two resin luting agents were used after silane application: self-adhesive (Rely X U200, 3M-ESPE) and dual cure (Rely X Ultimate, 3M-ESPE). The samples were submitted to microshear bond strength test. The failure analysis was performed. Data were submitted to ANOVA and Tukey test (α=0.05). Bond strength results ranged from 20.44 (CT+Ultimate) to 34.37 MPa (SC+U200) after 24 h and from 12.03 (CT+Ultimate) to 27.44 MPa (SC+U200) after 12 months of storage with SC statistically superior to the other treatments. Mean values of roughness varied from 0.07 (CT) to 0.85 µm (SC). The both resin luting agents showed similar results to all surface treatment groups. Silica coating provided the best treatment of the ceramic surface.     

The properties of silica aerogels hybridized with SiO2 nanoparticles by ambient pressure drying

In this study, we report the chemical characteristics of silica aerogels that were produced by adding SiO₂ nanoparticles into silica aerogel by ambient pressure drying. We synthesized silica aerogel composites with different weight percentages of SiO₂ nanoparticles ranging from 0 wt% to 0.025 wt% of the total amount of solution. As the wt% of SiO₂ nanoparticles increased, the number of chemical bonds that formed during condensation of the silica aerogel increased because of the presence of surface hydroxyl groups, thus the particle size of the silica aerogels increased. Silica nanoparticle-doping of silica aerogels can be used to control the synthesis of nanocomplex structures.     

Characterization of silica-coated silver nanoparticles prepared by a reverse micelle and hydrolysis–condensation process

Described herein is the synthesis of individually silica-coated silver nanoparticles using a reverse micelle method followed by hydrolysis and condensation of tetraethoxysilane (TEOS). The size of a silica-coated silver nanoparticle can be controlled by changing the reaction time and the concentration of TEOS. By maintaining the size of a silver nanoparticle as a core particle at around 7 nm, the size of a silica-coated silver nanoparticle increased from 13 to 28 nm as the reaction time increased from 1 to 9 h due to an increase in silica thickness. The size of silica-coated silver nanoparticles also increased from 15 to 22 nm as the TEOS concentration increased from 7.8 to 40 mM. The size of a silica-coated silver nanoparticle can be accurately predicted using the rate of the hydrolysis reaction for TEOS. Neither the dispersion nor the film of silica-coated silver nanoparticles exhibited any peak shifting during surface plasmon resonance (SPR) at around 410 nm, whereas, without silica coating, the SPR peak of Ag film shifted to 466 nm.     

Atomic force microscopy observations of a single crystal diamond surface lifted-off via ion implantation

The microscopic surface morphology of “lifted-off” surfaces, produced via ion implantation was observed by atomic force microscopy. A polished single-crystal diamond substrate with an average surface roughness of less than 0.1 nm was used for precise observations. After the lift-off process, the lifted-off surface became rough with pits appearing. Hydrogen plasma treatment close to the chemical vapor deposition conditions for diamond (1150 °C, 160 Torr) completely removed these pits and the surface was subsequently covered by a strip-like structure consisting of atomic steps. The surface roughness, however, was not further influenced by the plasma treatment. The observed morphological evolution reflects the graphite/diamond interface formed by the lift-off.     

The influence of the surface texture of hydrogen-free tetrahedral amorphous carbon films on their wear performance

Hydrogen-free and predominantly tetrahedrally bonded amorphous carbon thin films (ta-C) are excellent coatings to protect surfaces from wear due to their low coefficient of friction and high hardness. Since these coatings may be several times harder than common engineering materials counterpart wear can be significant. Therefore the surface texture of the ta-C coating is critical to wear applications. While the surface roughness is an important factor, the paper shows that other surface texture parameters have to be considered as well to predict the wear performance of the coating. Wear data are compared of as deposited, polished and brushed ta-C coatings. The results show that typically referenced average values for the surface roughness such as R_a and R_z may prove insufficient to reliably predict the wear behavior of the coating. Additional parameters describing the surface texture such as the “Skewness” (R_sk) and “Kurtosis” (R_ku) can provide relevant information. For example, a brushed ta-C surface with an average roughness of R_a = 31 nm showed a tenfold improved wear performance over a polished ta-C surface with an average roughness of R_a = 10 nm. This phenomenon is explained by analyzing the R_sk and R_ku data, which prove to more closely capture the post-treatment specific changes to the surface texture of the coatings.     

Influence of silica fume on the microstructure of cement pastes: New insights from 1H NMR relaxometry

¹H NMR has been used to characterise white Portland cement paste incorporating 10 wt.% of silica fume. Samples were measured sealed throughout the hydration without sample drying. Paste compositions and C–S–H characteristics are calculated based on ¹H NMR signal intensities and relaxation analysis. The results are compared with a similar study of plain white cement paste. While the presence of silica fume has little influence on C–S–H densities, the chemical composition is impacted. After 28 days of sealed hydration, the Ca/(Si + Al) ratio of the C–S–H is 1.33 and the H₂O/(Si + Al) ratio is 1.10 when 10% of silica fume is added to the white cement. A densification of the C–S–H with time is observed. There are no major changes in capillary, C–S–H gel and interlayer pore sizes for the paste containing silica fume compared to the plain white cement paste. However, the gel/interlayer water ratio increases in the silica fume blend.     

Synthesis of silica cryogel-glass fiber blanket by vacuum drying

Silica cryogel-glass fiber composites with a high specific surface area and high mesoporosity were fabricated via a simple still original drying technique. By applying vacuum at ambient temperature, the system evolution has been monitored and represented in the water phase diagram. The ratio of solvent/silica loading significantly affected the porous structure and thermal insulating properties of the blanket. From the results of BET surface area, apparent density and porosity studies, the microstructures and specific surface areas of the composites were greatly affected by changing the silica amount in the sol. The microstructure of silica cryogel blanket exhibits a porous structure consisting of glass fibers of diameter ~7 μm interconnected with solid silica clusters (5–20 μm). Silica cryogel-glass fiber blankets with low densities from 0.13–0.24 g/cm³ and thermal conductivity as low as 0.02–0.035 W/mK were obtained using this cost effective, hazardous free and time saving method. The pH of the silica sol influenced the gelling property and the thermal conductivity of the composites.     

Mesoporous ZnO nanoclusters as an ultra-active photocatalyst

Morphology modulation of nanostructured materials are highly crucial for various applications including photocatalysis, drug delivery, etc. In this study, mesoporous zinc oxide (ZnO) nanoclusters (MZN) were synthesized via a simple, cost-effective, low-temperature wet chemical route and further sucessfully utilized for photodegradation of Rhodamine B (RhB). Firstly, polystyrene (PS) nanospheres (~300 nm) were prepared by polymerization of styrene in aqueous solvent. Then the MZN were achieved by formation of ZnO nanoparticles-shell over the surface of PS nanospheres via esterification of zinc acetate dihydrate in isopropyl alcohol followed by toluene dissolution of PS core. The as-synthesized MZN were spherically-shaped, porous in nature with a diameter of ~ 400 nm and composed of well-arranged highly-crystalline ZnO nanoparticles (~ 5 nm). The MZN also exhibited a high surface area of 78.3±5.4 m² g⁻¹ and an average pore diameter of ~26 nm. Furthermore, this unique structure demonstrates an expeditious photodegradation of RhB under UV illumination, monitored by UV–visible spectroscopy at different time intervals until the dye was completely degraded to colorless end products. Fast RhB decomposition was observed with a degradation rate of ~98% within initial 40 min which can be attributed to the porous nature, large specific surface area and excellent electron accepting features of the engineered nanoclusters.     

Influence of pozzolans and slag on the microstructure of partially carbonated cement paste by means of water vapour and nitrogen sorption experiments and BET calculations

The influence of water-to-binder ratio (0.33 to 0.50) and additions (fly ash, slag, silica fume) on the microstructure of partially carbonated cement pastes was studied by nitrogen sorption and static and dynamic water vapour sorption. The selected technique affects macropore condensation and accessibility of pores, while predrying influences removal of CSH interlayer water. BJH calculations showed the increased amount of capillary pores with higher water-to-cement ratio, and the decrease of micropores (< 2 nm), in pastes with 50% or more fly ash or slag. Paste with 10% SF showed a high amount of gel pores, related to the higher amount of CSH gel, calculated from adsorption at 23% RH. A linear relation was observed between BET specific surface and water-cement ratio. Thermogravimetric analysis illustrated the influence of water-cement ratio and pozzolanic materials on the portlandite content. Introduction of silica fume, increased the specific surface accessible to water, but not to nitrogen molecules.     

Gold nanoparticles on silica monospheres modified by amino groups

Silica monospheres with a diameter of 330 nm modified with aminosilane compounds of three different basicities have been prepared. Surface coverage of the silica with an organic compound leads to an increase of the point of zero charge (PZC) of the silica surface from 2.1 to 5.1, 6.5 and 7.2 values, depending on the amine used. From these silicas, gold-containing catalysts have been prepared by a deposition–precipitation method at the same pH as the PZC of the support. The best results have been obtained using 3-(Diethoxymethylsilyl) propylamine as a modifying agent, which has allowed obtaining a good dispersion of the gold particles with an average size of 3.8 nm.     

Synthesis of hollow mesoporous silica (HMS) nanoparticles as a candidate for sulfasalazine drug loading

Hollow mesoporous silica nanoparticles have emerged as attractive drug delivery carriers. In this work, we report successful synthesis of hollow mesoporous silica nanoparticles (HMSNs) using poly tert-butyl acrylate (PtBA) nanospheres as hard templates and CTAB as structure directing agent for loading sulfasalazine into its porous structure. The samples were synthesized using PtBA; sodium dodecyl sulfate (SDS) - in an aqueous solution of CTAB and tetraethylorthosilicate (TEOS) as the inorganic precursor. Two different methods were utilized to remove organic phases including calcination, and acidic/basic ethanolic solvent extraction approach. For the latter, microstructural studies using SEM and N₂ porosimetery revealed the formation of highly uniform mono-dispersed particles of sphere morphology (~ 130 nm) with the high specific surface area (1501 m²/g) and mean pore size of ~ 2.6 nm. However, rather deformed and aggregated sphere-like particles were obtained for the calcined samples. TEM examinations also confirmed the formation of 20–30 nm thick walls for the prepared HMSNs particles. Further, HMSN samples treated by solvent extraction method were functionalized by 3-aminopropyl triethoxysilane (APTS) compound for drug delivery. DTA/TG analysis showed that the total amount of loaded sulfasalazine drug was 5.1 wt%.     

Ultra-fine polishing of glass-ceramics by disaggregated and fractionated detonation nanodiamond

Ultra-fine polishing of glass-ceramics is extraordinarily difficult because of structure inconsistency, chemical inhomogeneity and high rigidity. Detonation nanodiamond particles(NDs) were disaggregated and fractionated by serial centrifuge separation to obtain four stable suspension with average sizes of 54.9 nm,103.8 nm,145.6 nm and 245.4 nm respectively. Those suspensions were then employed to polish glass-ceramics. The evolution of NDs has been carefully characterized by FTIR, Raman and XRD analysis and the finish surfaces of glass-ceramics were investigated with AFM. Results showed that disaggregation treatment modified only nanodiamond surface other than its structure. The amount of nitro-groups on NDs surface increased and the absolute value of ξ-potential was enhanced by least 6 times at the pH 4–5, which was propitious to disperse NDs in mild acidic solution and polish glass-ceramics. Coarse particles performed both higher removal rate and average roughness (Sa) than the finer one. By using the suspension with average size of 54.9 nm, a super smooth surface with Sa 0.208 nm (5 µm×5 µm) was achieved.     

Damage resistance and anticorrosion properties of nanosilica-filled epoxy-resin composite coatings

Silica nanoparticles surface-capped with diglycidyl ether of bisphenol A were dispersed in a solution of epoxy resin, hardener and acetone. The resultant suspension was then coated onto the surface of duplex stainless steel of type DSS 2205 and cured with temperature, generating a 50 μm thick silica/epoxy coating. Epoxy coating without nanosilica was also prepared as a reference in the same manner. Mechanical properties of these coatings were compared and characterized using the Vickers hardness test. Three-point bending test was performed in combination with acoustic emission to analyze the damage initiation and development in the coating. The effects of incorporating the silica particles on the surface characteristics and the corrosion resistance of the epoxy-coated steel were investigated with contact-angle and surface energy as well as by potentiodynamic polarization and electrochemical impedance spectroscopy in a 3.5 wt.% NaCl solution. Results indicate, that silica particles significantly improved the microstructure of the coating matrix, which was reflected in an increased damage resistance, reduced degree of delamination, increased surface roughness and induced hydrophobicity. The silica/epoxy coating was proven to serve as a successful barrier in a chloride-ion-rich environment with an enhanced anticorrosive performance, which was confirmed by the reduced corrosion rate.     

Surface microstructural changes of spark plasma sintered zirconia after grinding and annealing

Spark plasma sintered zirconia (3Y-TZP) specimens have been produced of 140 nm 372 nm and 753 nm grain sizes by sintering at 1250 °C, 1450 °C and 1600 °C, respectively. The sintered zirconia specimens were grinded using a diamond grinding disc with an average diamond particle size of about 60 µm, under a pressure of 0.9 MPa. The influence of grinding and annealing on the grain size has been analysed. It was shown that thermal etching after a ruff grinding of specimens at 1100 °C for one hour induced an irregular surface layer of about a few hundred nanometres in thickness of recrystallized nano-grains, independently of the initial grain size. However, if the ground specimens were exposed to higher temperature, e.g. annealing at 1575 °C for one hour, the nano-grain layer was not observed. The resulted grain size was similar to that achieved by the same heat treatments on carefully polished specimens. Therefore, by appropriate grinding and thermal etching treatments, nanograined surface layer can be obtained which increases the resistance to low temperature degradation.     

Silicon-On-Diamond layer integration by wafer bonding technology

In this study, Silicon-On-Diamond (SOD) micro-structures have been fabricated using either Smart Cut? or bonded and Etched-Back Silicon On Insulator (BESOI) technology. Thanks to the development of an innovative smoothening process, polycrystalline diamond layers (C*) can be integrated as a buried oxide layer offering new opportunities in terms of thermal management.We describe different technological process flow investigations leading to SOD by bonding C* layer in the stack. As starting material we used poly-crystalline thin diamond films in the 200 nm to 7000 nm range of thickness. The C* is deposited by Chemical Vapour Deposition assisted by Microwave Plasma (MPCVD) onto various 50 mm wafers such as Si, SOI and polycrystalline silicon carbide (pSiC). As the roughness of the diamond layer is not directly compatible with a wafer bonding integration, an innovative smoothening process in 3 steps has been developed and named “DPE” for Deposition, Planarization and Etching. Using the DPE process, the roughness of 5 µm thick diamond layer could be reduced from 50 to 3 nm RMS and down to 1.5 nm RMS for a thin 200 nm layer.In order to demonstrate the feasibility of a GaN on SOD micro-structure design for HEMT applications, layer transfers have been carried out by a bonding and thinning process from C*/Si bulk using oxide bonding layers. From thermal spreading efficiency consideration, new processes of fabrication of SOD/poly-SiC substrate are in progress involving BESOI or Si Smart Cut? technologies and poly-Si bonding layer starting from C*/poly-SiC.Pure SOD substrate were also fabricated by using C*/SOI and poly-Si bonding layer in a BESOI technology. A thin active silicon layer (70 nm) of 50 mm diameter onto a 140 nm thick diamond BOX layer has been transferred on 200 mm diameter Si substrate for future MOSFET's devices demonstrations. Significant progress has been done in diamond layer integration by wafer bonding.     

Production of silica aerogel microparticles loaded with ammonia borane by batch and semicontinuous supercritical drying techniques

Silica aerogel microparticles were prepared by supercritical drying and used as support for hydrogen-storing ammonia borane (AB). The formation of aerogel microparticles was done using two different processes: batch supercritical fluid extraction and a semicontinuous drying process. Silica aerogel microparticles with a surface area ranging from 400 to 800 m²/g, a volume of pores of 1 cm³/g, and a mean particle diameter ranging from 12 to 27 μm were produced using the two drying techniques. The particle size distribution (PSD) of the microparticles was influenced by shear rate, amount of catalyst, hydrophilic–hydrophobic solvent ratio and hydrophobic surface modification. In particular, irregular aerogel particles were obtained from hydrophilic gels, while regular, spherical particles with smooth surfaces were obtained from hydrophobic gels. AB was loaded into silica aerogel microparticles in concentrations ranging from 1% till 5% wt. Hydrogen release kinetics from the hydride-loaded aerogel was analyzed with a volumetric cell at 80 °C. By stabilization of AB into the silica aerogel microparticles, an improvement of the release rate of hydrogen from AB was observed.