Characterization of the Polishing‐Induced Contamination of Fused Silica Optics

In this work, the polishing‐induced contamination layer at the fused silica optics surface was studied with various interface analysis techniques: Secondary Ion Mass Spectroscopy (SIMS), Electron Probe Microanalysis (EPMA), X‐Ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma—Optical Emission Spectroscopy (ICP‐OES). Samples were prepared using an MRF polishing machine and cerium‐based slurry. The cerium and iron penetration and concentration were measured in the surface out of defects. Cerium is embedded at the surface in a 60 nm layer and concentrated at 1200 ppmw in this layer while iron concentration falls down at 30 nm. Spatial distribution and homogeneity of the pollution were also studied in the scratches and bevel using SIMS and EPMA techniques. We saw evidence that surface defects, such as scratches, are specific places that hold the pollutants. This overconcentration is also observed in the chamfer. These new insights into the polishing‐induced contamination of fused silica optics and it repartition have been obtained using various characterization methods. Advantages and disadvantages of each one are discussed.     

Chemistry and Formation of the Beilby Layer During Polishing of Fused Silica Glass

The chemical characteristics and the proposed formation mechanisms of the modified surface layer (called the Beilby layer) on polished fused silica glasses are described. Fused silica glass samples were polished using different slurries, polyurethane pads, and at different rotation rates. The concentration profiles of several key contaminants, such as Ce, K, and H, were measured in the near surface layer of the polished samples using Secondary Ion Mass Spectroscopy (SIMS). The penetration of K, originating from KOH used for pH control during polishing, decreased with increase in polishing material removal rate. In contrast, penetration of the Ce and H increased with increase in polishing removal rate. In addition, Ce penetration was largely independent of the other polishing parameters (e.g., particle size distribution and the properties of the polishing pad). The resulting K concentration depth profiles are described using a two‐step diffusion process: (1) steady‐state moving boundary diffusion (due to material removal during polishing) followed by (2) simple diffusion during ambient postpolishing storage. Using known alkali metal diffusion coefficients in fused silica glass, this diffusion model predicts concentration profiles that are consistent with the measured data at various polishing material removal rates. On the other hand, the observed Ce profiles are inconsistent with diffusion based transport. Rather we propose that Ce penetration is governed by the ratio of Ce–O–Si and Si–O–Si hydrolysis rates; where this ratio increases with interface temperature (which increases with polishing material removal rate) resulting in greater Ce penetration into the Beilby layer. Calculated Ce surface concentrations using this mechanism are in good agreement to the observed change in measured Ce surface concentrations with polishing material removal rate. These new insights into the chemistry of the Beilby layer, combined together with details of the single particle removal function during polishing, are used to develop a more detailed and quantitative picture of the polishing process and the formation of the Beilby layer.     

Ultra-smooth surface with 0.4 Å roughness on fused silica

Ultra-smooth surface with sub-nanometer roughness is of great significance in various fields, including Ring Laser Gyro (RLG), high-power laser apparatus, ultraviolet optical systems, and the semiconductor industry. However, the mechanism of the ultra-smooth polishing process remains to be studied, which is of great value for understanding and optimizing optical-fabrication methods. This paper establishes a relationship between surface densification characteristics and surface roughness in conventional polishing. Moreover, we conclude that the densification process created by the longitudinal pressure, which avoids non-uniformity, is beneficial to forming super-smooth surfaces in the conventional polishing methods. Under this guidance, we can stably fabricate ultra-smooth surfaces on fused silica with 0.4 Å roughness. This result overturns the mainstream view that the longitudinal pressure in polishing should be minimized. This conclusion is meaningful for the understanding of the ultra-smooth surface formation not only in conventional polishing but also in other optical-fabrication technologies.     

Numerical and experimental investigations on NANO-SIO2 jet polishing efficiency by different nozzle structures

This paper focuses on the fused silica material removal efficiency with different nozzle structures during nano-SiO₂ jet polishing. The removal function and flow field distribution are with different nozzle structures obtained from the numerical and experimental investigations. The results show that under the same conditions, the removal efficiency of single-slit nozzle is 2.55 times that of single-hole nozzle, and the removal efficiency of multi-slit nozzle is 1.65 times that of the single-slit nozzle. The optimal length and width of a single slit is 5 mm and 0.6 mm, respectively. Finally, the variation of surface roughness is obtained with slit nozzle structure. With the increase of removal depth, the surface roughness of fused silica decreased from 1.86 nm to 0.491 nm, which further verified that the slit nozzle can quickly achieve super-smooth machining of fused silica surface during nano-SiO₂ jet polishing.     

Microscopic Removal Function and the Relationship Between Slurry Particle Size Distribution and Workpiece Roughness During Pad Polishing

Various ceria and colloidal silica polishing slurries were used to polish fused silica glass workpieces on a polyurethane pad. Characterization of the slurries' particle size distribution (PSD) (using both ensemble light scattering and single particle counting techniques) and of the polished workpiece surface (using atomic force microscopy) was performed. The results show the final workpiece surface roughness is quantitatively correlated with the logarithmic slope of the distribution function for the largest particles at the exponential tail end of the PSD. Using the measured PSD, fraction of pad area making contact, and mechanical properties of the workpiece, slurry, and pad as input parameters, an Ensemble Hertzian Gap (EHG) polishing model was formulated to estimate each particle's penetration, load, and contact zone. The model is based on multiple Hertzian contact of slurry particles at the workpiece–pad interface in which the effective interface gap is determined through an elastic load balance. Separately, ceria particle static contact and single pass sliding experiments were performed showing ~1‐nm depth removal per pass (i.e., a plastic type removal). Also, nanoindentation measurements on fused silica were made to estimate the critical load at which plastic type removal starts to occur (P_crit~5 × 10^?5 N). Next the EHG model was extended to create simulated polished surfaces using the Monte Carlo method where each particle (with the calculated characteristics described above) slides and removes material from the silica surface in random directions. The polishing simulation utilized a constant depth removal mechanism (i.e., not scaling with particle size) of the elastic deformation zone cross section between the particle and silica surface, which was either 0.04 nm (for chemical removal) at low loads (<P_crit) or 1.0 nm (for plastic removal) at intermediate loads (>P_crit). The simulated surfaces quantitatively compare well with the measured rms roughness, power spectra, surface texture, absolute thickness material removal rate, and load dependence of removal rate.     

Nanoscratching of Optical Glass Surfaces Near the Elastic–Plastic Load Boundary to Mimic the Mechanics of Polishing Particles

The nanomechanical deformations on glass surfaces near the elastic–plastic load boundary have been measured on various glasses by nanoscratching using an atomic force microscope (AFM) to mimic the mechanical interactions of polishing particles during optical polishing. Nanoscratches were created in air and aqueous environments using a 150‐nm radius diamond‐coated tip on polished fused silica, borosilicate, and phosphate glass surfaces; the topology of the nanoscratches were then characterized by AFM. Using load ranges expected on slurry particles during glass polishing (0.05–200 μN), plastic‐type scratches were observed with depths in the nm range. Nanoscratching in air generally showed deeper & narrower scratches with more pileup compared to nanoscratching in water, especially on fused silica glass. The critical load needed to observe plastic deformation was determined to range from 0.2–1.2 μN for the three glasses. For phosphate glass, the load dependence of the removal depth was consistent with that expected from Hertzian mechanics. However, for fused silica and borosilicate glass in this load range, the deformation depth showed a weak dependence with load. Using a sub‐T_g annealing technique, material relaxation was observed on the nanoscratches, suggesting that a significant fraction of the deformation was due to densification on fused silica and borosilicate glass. Repeated nanoscratching at the same location was utilized for determining the effective incremental plastic removal depth. The incremental removal depth decreased with increase in number of passes, stabilizing after ~10 passes. In water, the removal depths were determined as 0.3–0.55 nm/pass for fused silica, 0.85 nm/pass for borosilicate glass, and 2.4 nm/pass for phosphate glass. The combined nanoscratching results were utilized to define the composite removal function (i.e., removal depth) for a single polishing particle as a function of load, spanning the chemical to the plastic removal regimes. This removal function serves as an important set of parameters in understanding material removal during polishing and the resulting workpiece surface roughness.     

Micron-size bubble defects in fused silica and its laser induced damage near 355 nm

In this paper, considering micro-bubble as a factor affecting the quality of optical components assembled in high-energy laser system, the behavior of small bubble inside high-temperature fused silica is investigated by two-phase flow theory. Furthermore, the effect of microbubbles as high-energy laser damage precursor is studied in detail. It is found that if micro-cracks or voids exist in fused silica during synthesis, basically spherical bubbles could be formed and hardly released. Thereafter, light intensity enhancement effect is evaluated at the initial stage of laser-induced damage. Both single and double bubbles attribute to laser energy intensification in a specific area. The Gaussian pulsed laser near 355 nm is utilized to test laser-induced damage thresholds (LIDTs), and the LIDTs of fused silica with unreleased micro-bubbles decrease from 9.7J/cm² to ∼7.0 J/cm². The surface damage morphologies and laser-induced material modifications due to micro-bubble are much more disastrous than those without defects. We propose that the Gaussian laser-induced damage morphologies are partitioned into three feature zones for fused silica with unreleased bubbles. The research in this paper provides underlying guidance for ameliorating the quality of fused silica and understanding laser-induced damage.     

High strength silica-based ceramics material for investment casting applications: Effects of adding nanosized alumina coatings

A nanosized alumina coating was synthesized on the surface of fused silica particles by electrostatic attraction. The effects of the coated fused silica particles on the cristobalite crystallization behavior, microstructure evolution, and flexural strength of silica-based ceramic cores were investigated. X-ray diffraction (XRD) was used to characterize phase transformations in the specimens, and the results indicated that the formed nanosized alumina coatings could retard cristobalite formation by inducing compressive stress on the fused silica particle surface. A mullite phase was also found due to the reaction of the nanosized alumina coating and the surface of the fused silica when the sintering temperature was increased to 1300 °C. Analysis using scanning electron microscopy equipped with energy dispersive spectrometry (SEM/EDS) suggested that alumina nanoparticles in the coated layer dispersed into a liquid phase and formed a barrier layer to impede the movement of the liquid phase, preventing the pore-filling process and increasing the open porosity of the ceramic specimens. Flexural strengths at room temperature were tested, indicating that increases in the sintering temperature of the specimens without coated fused silica powders had little effect on flexural strength. However, the flexural strength of the specimens with coated fused silica powders increased with increases in sintering temperature. The improvement in flexural strength was related to the reinforcement by sintering necks between particles and the improvement in the strength of the coated fused silica powder.     

Flame retardant mechanism of silica gel/silica

Various types of silica, silica gel, fumed silicas and fused silica were added to polypropylene and polyethylene oxide to determine their flame retardant effectiveness and mechanisms. Polypropylene was chosen as a non‐char‐forming thermoplastic and polyethylene oxide was chosen as a polar char‐forming (slight) thermoplastic. Flammability properties were measured in the cone calorimeter and the mass loss rate was measured in our radiative gasification device in nitrogen to exclude any gas phase oxidation reactions. The addition of low density, large surface area silicas, such as fumed silicas and silica gel to polypropylene and polyethylene oxide significantly reduced the heat release rate and mass loss rate. However, the addition of fused silica did not reduce the flammability properties as much as other silicas. The mechanism of reduction in flammability properties is based on the physical processes in the condensed phase instead of chemical reactions. The balance between the density and the surface area of the additive and polymer melt viscosity determines whether the additive accumulates near the sample surface or sinks through the polymer melt layer. Fumed silicas and silica gel used in this study accumulated near the surface to act as a thermal insulation layer and also to reduce the polymer concentration near the surface. However, fused silica used in this study mainly sank through the polymer melt layer and did not accumulate near the surface. The heat release and the mass loss rate of polypropylene decreased nearly proportionally with an increase in mass loading level of silica gel up to 20% mass fraction. Polyethylene oxide samples with fumed silicas and silica gel formed physically strong char/silica surface layers. This layer acted not only as thermal insulation to protect virgin polymer but also acted as a barrier against the migration of the thermal degradation products to the surface. Published in 2000 by John Wiley & Sons, Ltd.     

Laser damage threshold of Ge8As23S69 films irradiated under single- and multiple-pulse femtosecond laser

In this study, the single- and multiple-pulse laser-induced surface damage characteristics of the Ge₈As₂₃S₆₉ chalcogenide film under the femtosecond laser irradiation were experimentally investigated. The 1-on-1 and S-on-1 methods were utilized to measure the femtosecond laser damage by using single and multiple pulses, respectively. The femtosecond laser-induced damage threshold (LIDT) was obtained using linear regression method by measuring the damage morphology under different pulse energies and pulse numbers of the femtosecond laser. Results show that the LIDT of the film under single-pulse radiation is higher than that under multiple-pulse radiation because of accumulation and defect effects. For the single-pulse radiation, LIDT is attributed to the field enhancement effect, multiphoton ionization, and avalanche ionization. The single-pulse damage threshold of Ge₈As₂₃S₆₉ films is 232.548 mJ/cm². For the multiple-pulse radiation, the LIDT of the film decreases with increasing pulse number due to accumulation and defect effects.     

Fused silica with sub-angstrom roughness and minimal surface defects polished by ultrafine nano-CeO2

Surface quality of fused silica, particularly surface defect and surface roughness, is a key factor affecting the performance of high-power laser and short-wave optical instrument, and so on. Herein, the super smooth surface of fused silica with roughness of sub-angstrom level and exceedingly few submicron defects was achieved by using ultrafine nano-CeO₂ with primary particle size less than 4 nm, low secondary particle agglomeration strength, and high Ce³⁺ concentration. Furthermore, CeO₂ involve in polishing process in the form of primary particle was certified by experiment. Moreover, the cause for the generation of submicron defects on fused silica surface was investigated for the first time from the perspective of secondary particle agglomeration strength of CeO₂. The concentration of Ce³⁺ in CeO₂ was characterized by the redshift of the band-gap energy, and the analysis of material removal rate (MRR) and contact angle of polished fused silica shows that Ce³⁺ enhances MRR through increasing the silanol group on fused silica.     

Constitutive Law for the Densification of Fused Silica, with Applications in Polishing and Microgrinding

We discuss a constitutive model describing the permanent densification of fused silica under large applied pressures and shear stresses. The constitutive law is assumed to be rate-independent and uses a yield function coupling hydrostatic pressure and shear stress, a flow rule describing the evolution of permanent strains after initial densification, and a hardening rule describing the dependence of the incremental densification on the levels of applied stresses. Normality, or lack thereof, of the permanent strain increments to the current yield surface in stress space allows for various relative contributions of densification and shear flow in the ensuing deformation. The constitutive law accounts for multiaxial states of stress, since during polishing and grinding operations complex stress states, with large shear components due to friction and abrasion, occur in a thin surface layer due to the action of abrasive particles. We apply the constitutive law in estimating the extent of the densified layer during the mechanical interaction of an abrasive grain and a flat surface under polishing and grinding conditions. The grain is assumed to be spherical and in Hertz contact with the surface, or sharp and in point contact. The effect on the densified depth of stress relaxation due to densification is discussed.     

Influence of surface roughness and temperature on the oxidation behavior of ZrC/SiC samples

New composites were elaborated using ZrC and SiC powders and the Spark Plasma Sintering process. The samples were polished at 4 different levels in order to compare the influence of surface roughness and temperature (1400 and 1600 K) on the characteristics of the oxide layers. By XRD analysis, it was confirmed that polishing and temperature level provoked changes in the crystalline structure. SEM imaging coupled to EDS microanalysis showed that the oxide layer was made of zirconia grains with silica at the grain boundaries. Nano-indentation was used to analyze the influence of the initial surface roughness and temperature on the hardness of the oxide layer. At 1400 K, the initial polishing has favored the growth of a hard oxide layer, which could be probably correlated to the higher crystallinity of the oxide. At 1600 K, it seems that a rougher initial surface favors the hardness of the oxide layer, which could be correlated to a better adherence between the oxide layer and the substrate. Both phenomena (crystallinity and adherence) would be in competition to reduce the fragility of the oxide layer.     

液相法制备碳—碳复合材料Si—W涂层表面氧化层的结构

研究了一种液相法及其它方法制备的碳－碳复合材料多层防氧化涂层，并用ＸＲＤ，ＳＥＭ，Ｒａｍａｎ光谱和ＥＭＰＡ研究了液相法制备的Ｓｉ－Ｗ涂层表面氧化后的结构。研究结果表明；氧化后涂层表面生成石英玻璃，且由于Ｗ的高价氧化物进入玻璃的分子网络结构，使其能长时间保持稳定而不析晶。     

Preparations of silica slurry for wafer polishing via controlled growth of commercial silica seeds

Silica slurry in aqueous medium for wafer polishing was prepared by sol-gel reaction of silicon alkoxide utilizing commercial silica particles as seeds that were grown stepwise through intermittent additions of tetraethylorthosilicate (TEOS) as a silica precursor. Before the growth reaction, the commercial silica particles were pre-treated in the vibratory mill partially filled with zirconia ball and the sonicator to ensure good dispersion. The alcohol left after growth reaction was removed by vacuum distillation and repeated washings with distilled water followed by centrifugations. Then, the alcohol-free silica particles were redispersed in water. The dispersion stability of the silica slurries was examined by measuring surface charge of silica particles and rheological properties. Finally, wafer-polishing performance of the prepared silica slurries was considered by measuring the polishing (or removal) rate, and RMS (root mean square) roughness of the polished wafer surface. For the polishing, MEA (monoethanolamine) and TMAH (tetramethylammonium hydroxide) were used as polishing accelerators. The polishing result showed that the removal rate was nearly independent of the concentrations of MEA and TMAH in the range of 0.3-0.5 wt% and 100-500 ppm, respectively. One of the most interesting features is that hydrothermal treatment of the prepared silica slurries in autoclave increased the removal rate as high as ten times. Although the removal rate was increased by the increased size of the abrasive particle, surface roughness of the polished wafer surface was deteriorated.     

籽晶处理工艺对物理气相传输法生长SiC单晶的影响

将块体SiC单晶中切割下的晶片经研磨、抛光和腐蚀不同工艺处理后作为籽晶,用物理气相传输法生长SiC晶体,生长时间为10min。用光学显微镜观察晶片生长前后的形貌,讨论了不同处理工艺籽晶对晶体生长的影响。结果表明,研磨和抛光可以去除晶体切割时产生的凹坑和划痕,但残留的研磨变质层和抛光导致的机械损伤层可诱导晶片在高温晶体生长时产生多晶成核,腐蚀可以去除研磨和抛光时产生的机械损伤层,用腐蚀后的晶片作为籽晶,生长的晶体表面光滑,并且能够很好地复制籽晶的结构。     

Co-enhanced SiO2-BN ceramics for high-temperature dielectric applications

Two typical high-temperature dielectric materials, fused silica and BN, have been used to form a composite with an attempt to overcome their own drawbacks. In the resultant BN–SiO₂ composites, BN platelike grains were preferentially orientated by hot pressing and homogeneously distributed in the fused silica matrix. An evident co-operative enhancement has been achieved by the combination of the constituents. The sinterability and the thermal shock resistance of the BN materials were increased and the ablation surface temperature was decreased by the involvement of the fused silica. On the other hand, the strength, fracture toughness, and flame ablation resistance of the fused silica were increased due to the addition of BN. Furthermore, an amorphous Si–B–O–N structure was identified in the surface layer of the ablated composites, to which attention should be further paid in the development of new elevated temperature dielectric materials.     

Nano-scale surface of ZrO2 ceramics achieved efficiently by peanut-shaped and heart-shaped SiO2 abrasives through chemical mechanical polishing

Zirconia ceramics are regarded as the best development target for 5G mobile phone rear covers. However, it is necessary and urgent to improve the surface quality and processing efficiency of zirconia ceramics. Non-spherical silica abrasives were prepared by the KH550 induction method and were used in chemical mechanical polishing (CMP) of zirconia ceramics for the first time. While achieving low surface roughness of 1.9 nm, it has an efficient polishing rate of 0.31 μm/h which is superior to conventional abrasives. Silica particles are peanut-shaped and heart-shaped in the scanning electron microscopy image, and its distinctive morphology provides the possibility of its excellent polishing performance. X-ray photoelectron spectroscopy analysis shows that during the CMP process, silica abrasives and zirconia ceramic undergo a solid phase chemical reaction to form ZrSiO₄. At the same time, the contact wear model established in combination with the coefficient of friction indicates that the two-dimensional surface contact mode of non-spherical silica abrasives on the surface of zirconia ceramics greatly improves its mechanical effect.     

A Kind of Nanofluid Consisting of Surface-Functionalized Nanoparticles

A method of surface functionalization of silica nanoparticles was used to prepare a kind of stable nanofluid. The functionalization was achieved by grafting silanes directly to the surface of silica nanoparticles in silica solutions (both a commercial solution and a self-made silica solution were used). The functionalized nanoparticles were used to make nanofluids, in which well-dispersed nanoparticles can keep good stability. One of the unique characteristics of the nanofluids is that no deposition layer forms on the heated surface after a pool boiling process. The nanofluids have applicable prospect in thermal engineering fields with the phase-change heat transfer.     

Controlled material removal mode and depth of micro cracks in precision grinding of fused silica – A theoretical model and experimental verification

A critical function for crack propagation for the single grit scratching of fused silica is developed based on the fracture mechanics. The effects of original crack density on the surface, strain rate and grinding coolant are considered in the function. A theoretical model for controlled material removal mode and depth of micro cracks precision grinding is presented based on the critical function for crack propagation. It can be predicted by the model that the material removal mode in the grinding of fused silica with original cracks damage will change from a ductile mode to a semi-brittle mode, a full-brittle mode and a semi-brittle mode in sequence with the increasing single grit scratching depth. It was found that the micro crack damage depth of fused silica does not increase with the single grit scratching depth after a full brittle mode grinding and it is always smaller than that after a semi brittle mode grinding even with a smaller single grit scratching depth. These interesting results are explained by the fracture mechanics. The ductile mode grinding is a recognized desirable process of fabricating fused silica while the full-brittle grinding is also a feasible process for its shallow subsurface damage, high efficiency, low grinding force and energy consumption. Therefore, the depth of micro cracks after grinding can be controlled by choosing suitable grinding parameters. Grinding experiments are conducted on fused silica. The undeformed chip thickness of randomly distributed effective grits is simulated based on 3D reconstruction of wheel topography to reveal the relationship between the grinding parameters and the single grit scratching depth. Ground surface roughness, sub-surface damage (SSD) depth and grinding force are measured and discussed. It is shown that the model predictions correlate well with the experimental trend of grinding modes.