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Octyl hydroxamic acid (OHA) was investigated as an inhibitor in H 2 O 2 -based alkaline silica dispersions for the polishing of cobalt (Co) films for interconnect applications. A combination of experiments and density functional theory (DFT) was used to investigate the inhibition effect and the mechanism of OHA on the Co surface. On the basis of the experiments, it can be proven that OHA has an inhibition effect on Co, which came from the inhibition of the cathodic reaction. The X-ray photoelectron spectroscopy (XPS) experiments show that the adsorption of OHA weakened the oxidation of the Co surface and protected the Co surface from corrosion. On the basis of the calculations, it can be proven that the OHA ketone (ion) is most likely to react with the Co surface, and it can adsorb on the Co surface by Co-O bonds. This study provides important microscopic insights for understanding the corrosion protection of Co interconnect metals and helps to explain the corrosion inhibition mechanism of the organic-metal interface during the CMP process.

Copper-to-copper (Cu-to-Cu) direct bonding is a promising approach to replace traditional solder joints in three-dimensional integrated circuits (3D ICs) packaging. It has been commonly conducted at a temperature over 300 °C, which is detrimental to integrated electronic devices. In this study, highly (111)-oriented nanotwinned (nt) Cu films were fabricated and polished using chemical mechanical planarization (CMP) and electropolishing. We successfully bonded and remained columnar nt-Cu microstructure at a low temperature of 150 °C thanks to the rapid diffusion of Cu on (111) surface. We employed a new microstructural method to characterize quantitatively the interfacial bonding quality using cross-sectional and plan-view microstructural analyses. We discovered that CMP nt-Cu bonding quality was greater than that of electropolished nt-Cu ones. The CMP nt-Cu films possessed extremely low surface roughness and were virtually free of pre-existing interface voids. Thus, the bonding time of such CMP nt-Cu films could be significantly shortened to 10 min. We expect that these findings may offer a pathway to reduce the thermal budget and manufacturing cost of the current 3D ICs packaging technology.

Based on a previous work where we investigated the effect of conditioner type and downforce on the evolution of pad surface micro-texture during break-in, we have chosen certain break-in conditions to carry out subsequent blanket SiO 2 wafer polishing studies. Two different conditioner discs were used in conjunction with up to two different conditioning downforces. For each disc-downforce combination, mini-marathons were run using SiO 2 wafers. Prior to polishing, each pad was broken-in for 30 min with one of the conditioner-downforce combinations. The goal of this study was to polish wafers after this break-in to see how the polishing process behaved immediately after break-in. One of the discs used in this study produced similar micro-texture results at both downforces, which echoed the results seen in the mini-marathon. When comparing the different polishing results obtained from breaking-in the pad with the different discs used in this study, the coefficient of friction (COF) and SiO 2 removal rate (RR) were uncorrelated in all cases. However, the use of different discs resulted in different COF and RR trends. The uncorrelated COF and RR, as well as the differing trends, were explained by pad micro-texture results (i.e. the differing amount of fractured, poorly supported pad asperity summits).

Run-to-run (R2R) control is widely used in semiconductor manufacturing systems to minimize the process drift, shift and variability. The R2R controller adjusts control actions or recipes in a supervisory manner after each batch. This paper provides a comprehensive literature review of R2R control methods for the batch process. First, the principles of major R2R controllers are introduced and analyzed, such as exponentially weighted moving average (EWMA), double exponentially weighted moving average (d-EWMA), model predictive control (MPC), optimizing adaptive quality controller (OAQC), artificial neural network (ANN). Besides, simulation examples with different R2R controllers are made to compare the robustness and adaptability. Then, several case studies concerning a chemical mechanical planarization (CMP) process, a multi-input and multi-output (MIMO) system of the furnace process control and the management of blood glucose (BG) are presented. Finally, the paper concludes with some recommendations and directions for the future research., (Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.)

We investigated the possibility of employing refractive index (RI) measurements for inline incoming slurry control at the point of use (POU), as an alternative to the widespread densitometry method. As such, it became necessary to determine if RI could detect smaller changes in slurry composition and, therefore, provide a tighter control. Three industrially-relevant silica-based slurries, namely, Fujimi PL-7106, Klebosol 1501-50, and CMC W7801, were characterized using both densitometry and RI measurements. Initial solutions of the three slurries were prepared and increasingly small amounts of ultrapurified water (UPW) were added to study the change in slurry properties. Results showed that both density and RI decreased linearly with the addition of water for all three slurries, with the 1501-50 being the most sensitive to water addition. A linear correlation between the two properties was found, with R² values that exceeded 0.95 in all cases. Furthermore, the approximate limit of detection of both metrology tools was estimated based on the slope of the fitting line and resolution. When compared to densitometry, RI was found to be the far superior method for detecting smaller changes in water concentration.

A simple one-pot method is reported for the fabrication of uniform wrinkled silica nanoparticles (WSNs). Rapid cooling of reactants at the appropriate moment during synthesis allowed the separation of nucleation and growth stages, resulting in uniform particles. The factors affecting particle size and interwrinkle distance were also investigated. WSNs with particle sizes of 65-400 nm, interwrinkle distances of 10-33 nm, and surface areas up to 617 m 2 g -1 were fabricated. Furthermore, our results demonstrate the advantages of WSNs over comparable nonporous silica nanospheres and fumed silica-based products as an abrasive material in chemical mechanical planarization processes.

Chemical mechanical planarization (CMP) is a widely used technique for the manufacturing of integrated circuit chips in the semiconductor industry. The process generates large amounts of waste containing engineered particles, chemical additives, and chemo-mechanically removed compounds. The environmental and health effects associated with the release of CMP materials are largely unknown and have recently become of significant concern. Using a zebrafish embryo assay, we established toxicity profiles of individual CMP particle abrasives (SiO 2 and CeO 2 ), chemical additives (hydrogen peroxide, proline, glycine, nicotinic acid, and benzotriazole), as well as three model representative slurries and their resulting waste. These materials were characterized before and after use in a typical CMP process in order to assess changes that may affect their toxicological profile and alter their surface chemistry due to polishing. Toxicity outcome in zebrafish is discussed in relation with the physicochemical characteristics of the abrasive particles and with the type and concentration profile of the slurry components pre and post-polishing, as well as the interactions between particle abrasives and additives. This work provides toxicological information of realistic CMP slurries and their polishing waste, and can be used as a guideline to predict the impact of these materials in the environment., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The ubiquitous use of engineered nanomaterials-particulate materials measuring approximately 1-100 nanometers (nm) on their smallest axis, intentionally engineered to express novel properties-in semiconductor fabrication poses unique issues for protecting worker health and safety. Use of new substances or substances in a new form may present hazards that have yet to be characterized for their acute or chronic health effects. Uncharacterized or emerging occupational health hazards may exist when there is insufficient validated hazard data available to make a decision on potential hazard and risk to exposed workers under condition of use. To advance the knowledge of potential worker exposure to engineered nanomaterials, the National Institute for Occupational Safety and Health Nanotechnology Field Studies Team conducted an on-site field evaluation in collaboration with on-site researchers at a semiconductor research and development facility on April 18-21, 2011. The Nanomaterial Exposure Assessment Technique (2.0) was used to perform a complete exposure assessment. A combination of filter-based sampling and direct-reading instruments was used to identify, characterize, and quantify the potential for worker inhalation exposure to airborne alumina and amorphous silica nanoparticles associated with th e chemical mechanical planarization wafer polishing process. Engineering controls and work practices were evaluated to characterize tasks that might contribute to potential exposures and to assess existing engineering controls. Metal oxide structures were identified in all sampling areas, as individual nanoparticles and agglomerates ranging in size from 60 nm to >1,000 nm, with varying structure morphology, from long and narrow to compact. Filter-based samples indicated very little aerosolized material in task areas or worker breathing zone. Direct-reading instrument data indicated increased particle counts relative to background in the wastewater treatment area; however, particle counts were very low overall, indicating a well-controlled working environment. Recommendations for employees handling or potentially exposed to engineered nanomaterials include hazard communication, standard operating procedures, conservative ventilation systems, and prevention through design in locations where engineered nanomaterials are used or stored, and routine air sampling for occupational exposure assessment and analysis., Competing Interests: The authors declare no conflict of interest.

This occupational exposure assessment study characterized potential inhalation exposures of workers to engineered nanomaterials associated with chemical mechanical planarization wafer polishing processes in a semiconductor research and development facility. Air sampling methodology was designed to capture airborne metal oxide nanoparticles for characterization. The research team obtained air samples in the fab and subfab areas using a combination of filter-based capture methods to determine particle morphology and elemental composition and real-time direct-reading instruments to determine airborne particle counts. Filter-based samples were analyzed by electron microscopy and energy-dispersive x-ray spectroscopy while real-time particle counting data underwent statistical analysis. Sampling was conducted during worker tasks associated with preventive maintenance and quality control that were identified as having medium to high potential for inhalation exposure based on qualitative assessments. For each sampling event, data was collected for comparison between the background, task area, and personal breathing zone. Sampling conducted over nine months included five discrete sampling series events in coordination with on-site employees under real working conditions. The number of filter-based samples captured was: eight from worker personal breathing zones; seven from task areas; and five from backgrounds. A complementary suite of direct-reading instruments collected data for seven sample collection periods in the task area and six in the background. Engineered nanomaterials of interest (Si, Al, Ce) were identified in filter-based samples from all areas of collection, existing as agglomerates (>500 nm) and nanoparticles (100-500 nm). Particle counts showed an increase in number concentration above background during a subset of the job tasks, but particle counts in the task areas were otherwise not significantly higher than background. Additional data is needed to support further statistical analysis and determine trends; however, this initial investigation suggests that nanoparticles used or generated by the wafer polishing process become aerosolized and may be accessible for inhalation exposures by workers performing tasks in the subfab and fab. Additional research is needed to further quantify the degree of exposure and link these findings to related hazard research.

Continued expansion of the nanotechnology industry has necessitated the self-assessment of manufacturing processes, specifically in regards to understanding the health related aspects following exposure to nanomaterials. There exists a growing concern over potential occupational exposure in the semiconductor industry where Al2O3, CeO2 and SiO2 nanoparticles are commonly featured as part of the chemical mechanical planarization (CMP) process. Chronic exposure to toxicants can result not only in acute cytotoxicity but also initiation of a chronic inflammatory state associated with diverse pathologies. In the current investigation, pristine nanoparticles and CMP slurry formulations of Al2O3, SiO2 and CeO2 were employed to assess their ability to induce cytotoxicity, inflammatory responses and reactive oxygen species in a mouse alveolar macrophage cell model. The pristine nanoparticles and slurries were not intrinsically cytotoxic and did not generate free radicals but were found to act as scavengers in the presence of an oxidant stimulant. Al2O3 and SiO2 nanoparticles increased levels of pro-inflammatory cytokines while pristine SiO2 nanoparticles induced generation of F2-Isoprostanes. In co-treatment studies, the pristine nanomaterials modulated the response to the inflammatory stimulant lipopolysaccharide. The studies have established that pristine nanoparticles and slurries do not impact the cells in a similar way indicating that they should not be used as slurry substitutes in toxicity evaluations. Further, we have defined how an alveolar cell line, which would likely be the first challenged upon nanomaterial aerosolization, responds to diverse mixtures of nanomaterials. Moreover, our findings reinforce the importance of using multiple analytic methods to define the redox state of the cell following exposure to commonly used industrial nanomaterials and toxicants., (Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.)

The modern semiconductor industry relies heavily on a process known as chemical mechanical planarization, which uses physical and chemical processes to remove excess material from the surface of silicon wafers during microchip fabrication. This process results in large volumes of wastewater containing dissolved metals including copper (Cu(2+)), which must then be filtered and treated before release into municipal waste systems. We have investigated the potential use of bacterial and fungal biomass as an alternative to the currently used ion-exchange resins for the adsorption of dissolved Cu(2+) from high-throughput industrial waste streams. A library of candidate microorganisms, including Lactobacillus casei and Pichia pastoris, was screened for ability to bind Cu(2+) from solution and to form static biofilm communities within packed-bed adsorption columns. The binding efficiency of these biomass-based adsorption columns was assessed under various flow conditions and compared to that of industrially used ion-exchange resins. We demonstrated the potential to regenerate the biomass within the adsorption columns through the use of a hydrochloric acid wash, and subsequently reuse the columns for additional copper binding. While the binding efficiency and capacity of the developed L. casei/P. pastoris biomass filters was inferior to ion-exchange resin, the potential for repeated reuse of these filters, coupled with the advantages of a more sustainable "green" adsorption process, make this technique an attractive candidate for use in industrial-scale CMP wastewater treatment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Engineered nanomaterials (ENMs) are currently employed by many industries and have different physical and chemical properties from their bulk counterparts that may confer different toxicity. Nanoparticles used or generated in semiconductor manufacturing have the potential to enter the municipal waste stream via wastewater and their ultimate fate in the ecosystem is currently unknown. This study investigates the fate of ENMs used in chemical mechanical planarization (CMP), a polishing process repeatedly utilized in semiconductor manufacturing. Wastewater sampling was conducted throughout the wastewater treatment (WWT) process at the fabrication plant's on-site wastewater treatment facility. The goal of this study was to assess whether the WWT processes resulted in size-dependent filtration of particles in the nanoscale regime by analyzing samples using scanning electron microscopy (SEM). Statistical analysis demonstrated no significant differences in particle size between sampling points, indicating low or no selectivity of WWT methods for nanoparticles based on size. All nanoparticles appeared to be of similar morphology (near-spherical), with a high variability in particle size. EDX verified nanoparticles composition of silicon- and/or aluminum-oxide. Nanoparticle sizing data compared between sampling points, including the final sampling point before discharge from the facility, suggested that nanoparticles could be released to the municipal waste stream from industrial sources., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This study characterized potential inhalation exposures of workers to nanometal oxides associated with industrial wastewater treatment processes in a semiconductor research and development facility. Exposure assessment methodology was designed to capture aerosolized engineered nanomaterials associated with the chemical mechanical planarization wafer polishing process that were accessible for worker contact via inhalation in the on-site wastewater treatment facility. The research team conducted air sampling using a combination of filter-based capture methods for particle identification and characterization and real-time direct-reading instruments for semi-quantitation of particle number concentration. Filter-based samples were analyzed using electron microscopy and energy-dispersive x-ray spectroscopy while real-time particle counting data underwent statistical analysis. Sampling conducted over 14 months included 5 discrete sampling series events for 7 job tasks in coordination with on-site employees. The number of filter-based samples captured for analysis by electron microscopy was: 5 from personal breathing zone, 4 from task areas, and 3 from the background. Direct-reading instruments collected data for 5 sample collection periods in the task area and the background, and 2 extended background collection periods. Engineered nanomaterials of interest (Si, Al, Ce) were identified by electron microscopy in filter-based samples from all areas of collection, existing as agglomerates (>500 nm) and nanoparticles (100 nm-500 nm). Particle counts showed an increase in number concentration during and after selected tasks above background. While additional data is needed to support further statistical analysis and determine trends, this initial investigation suggests that nanoparticles used or generated by chemical mechanical planarization become aerosolized and may be accessible for inhalation exposures by workers in wastewater treatment facilities. Additional research is needed to further quantify the level of exposure and determine the potential human health impacts.

The aggregation rate and mechanism of 150 nm alumina particles in 1mM KNO3 with various additives used in chemical mechanical planarization of copper were investigated. The pH of each suspension was ∼8 such that the aggregation rate was slow enough to be measured and analyzed over ∼120 min. In general, an initial exponential growth was observed for most suspensions indicating reaction-limited aggregation. After aggregate sizes increase to >500 nm, the rate followed a power law suggesting diffusion-limited aggregation. Stability ratios and fractal dimension numbers were also calculated to further elucidate the aggregation mechanism., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The aggregation behavior for 150 nm alumina particles suspended in 1 mM KNO3 solutions with various additives used in chemical mechanical planarization of copper was investigated. Three behaviors were observed: no aggregation, reversible aggregation where large agglomerates formed almost instantaneously, and steady aggregation where particle sizes grew over the duration of the measurement. In general steady aggregation occurred at high pH for all suspensions, while no aggregation occurred at acidic pH, except with suspensions with sodium dodecyl sulfate, where reversible aggregation was observed. No aggregation was observed at near neutral pH for all suspensions. Zeta potential and isoelectric points for each suspension were also measured., (Copyright © 2013 Elsevier Inc. All rights reserved.)