Models of nanoparticles movement,collision, and friction in chemical mechanical polishing (CMP)

Nanoparticles have been widely used in polishing slurry such as chemical mechanical polishing (CMP) process. The movement of nanoparticles in polishing slurry and the interaction between nanoparticles and solid surface are very important to obtain an atomic smooth surface in CMP process. Polishing slurry contains abrasive nanoparticles (with the size range of about 10–100 nm) and chemical reagents. Abrasive nanoparticles and hydrodynamic pressure are considered to cause the polishing effect. Nanoparticles behavior in the slurry with power-law viscosity shows great effect on the wafer surface in polishing process. CMP is now a standard process of integrated circuit manufacturing at nanoscale. Various models can dynamically predict the evolution of surface topography for any time point during CMP. To research, using a combination of individual nanoscale friction measurements for CMP of SiO₂, in an analytical model, to sum these effects, and the results scale CMP experiments, can guide the research and validate the model. CMP endpoint measurements, such as those from motor current traces, enable verification of model predictions, relating to friction and wear in CMP and surface topography evolution for different types of CMP processes and patterned chips. In this article, we explore models of the microscopic frictional force based on the surface topography and present both experimental and theoretical studies on the movement of nanoparticles in polishing slurry and collision between nanoparticles, as well as between the particles and solid surfaces in time of process CMP. Experimental results have proved that the nanoparticle size and slurry properties have great effects on the polishing results. The effects of the nanoparticle size and the slurry film thickness are also discussed.     

Effects of total CH4/Ar gas pressure on the structures and field electron emission properties of carbon nanomaterials grown by plasma-enhanced chemical vapor deposition

The effects of total CH₄/Ar gas pressure on the growth of carbon nanomaterials on Si (1 0 0) substrate covered with CoO nanoparticles, using plasma-enhanced chemical vapor deposition (PECVD), were investigated. The structures of obtained products were correlated with the total gas pressure and changed from pure carbon nanotubes (CNTs) through hybrid CNTs/graphene sheets (GSs), to pure GSs as the total gas pressure changed from 20 to 4 Torr. The total gas pressure influenced the density of hydrogen radicals and Ar ions in chamber, which in turn determined the degree of how CoO nanoparticles were deoxidized and ion bombardment energy that governed the final carbon nanomaterials. Moreover, the obtained hybrid CNTs/GSs exhibited a lower turn-on field (1.4 V/μm) emission, compared to either 2.7 V/μm for pure CNTs or 2.2 V/μm for pure GSs, at current density of 10 μA/cm².     

Particle emissions from laboratory activities involving carbon nanotubes

This site study was conducted in a chemical laboratory to evaluate nanomaterial emissions from 20–30-nm-diameter bundles of single-walled carbon nanotubes (CNTs) during product development activities. Direct-reading instruments were used to monitor the tasks in real time, and airborne particles were collected using various methods to characterize released nanomaterials using electron microscopy and elemental carbon (EC) analyses. CNT clusters and a few high-aspect-ratio particles were identified as being released from some activities. The EC concentration (0.87 μg/m³) at the source of probe sonication was found to be higher than other activities including weighing, mixing, centrifugation, coating, and cutting. Various sampling methods all indicated different levels of CNTs from the activities; however, the sonication process was found to release the highest amounts of CNTs. It can be cautiously concluded that the task of probe sonication possibly released nanomaterials into the laboratory and posed a risk of surface contamination. Based on these results, the sonication of CNT suspension should be covered or conducted inside a ventilated enclosure with proper filtration or a glovebox to minimize the potential of exposure.     

Particle release and control of worker exposure during laboratory-scale synthesis,handling and simulated spills of manufactured nanomaterials in fume hoods

Fume hoods are one of the most common types of equipment applied to reduce the potential of particle exposure in laboratory environments. A number of previous studies have shown particle release during work with nanomaterials under fume hoods. Here, we assessed laboratory workers’ inhalation exposure during synthesis and handling of CuO, TiO₂ and ZnO in a fume hood. In addition, we tested the capacity of a fume hood to prevent particle release to laboratory air during simulated spillage of different powders (silica fume, zirconia TZ-3Y and TiO₂). Airborne particle concentrations were measured in near field, far field, and in the breathing zone of the worker. Handling CuO nanoparticles increased the concentration of small particles (<?58 nm) inside the fume hood (up to 1?×?10⁵ cm^?3). Synthesis, handling and packaging of ZnO and TiO₂ nanoparticles did not result in detectable particle release to the laboratory air. Simulated powder spills showed a systematic increase in the particle concentrations inside the fume hood with increasing amount of material and drop height. Despite powder spills were sometimes observed to eject into the laboratory room, the spill events were rarely associated with notable release of particles from the fume hood. Overall, this study shows that a fume hood generally offers sufficient exposure control during synthesis and handling of nanomaterials. An appropriate fume hood with adequate sash height and face velocity prevents 98.3% of particles release into the surrounding environment. Care should still be made to consider spills and high cleanliness to prevent exposure via resuspension and inadvertent exposure by secondary routes.     

Excitation of high energy levels under laser exposure of suspensions of nanoparticles in liquids

Laser exposure of suspensions of nanoparticles in liquids leads to excitation of high energy levels in both liquid and nanoparticle material. The emission spectrum of the colloidal solution under exposure of a suspension metallic nanoparticles in water to radiation of a Nd:YAG laser of a picosecond range of pulse duration is discussed. Excitation of nuclear energy levels and neutron release is experimentally studied on the model system of transmutation of Hg into Au that occurs under exposure of Hg nanodrops suspended in D₂O. The proposed mechanism involves: (i) emission of X-ray photons by Hg nanoparticles upon laser exposure, leading to neutron release from D₂O, (ii) initiation of Hg → Au transmutation by the capture of neutrons. The effect of transmutation is more pronounced using ¹⁹⁶Hg isotope instead of Hg of natural isotope composition. The influence of laser pulse duration on the degree of transmutation (from fs through ns range) is discussed.     

Surface modification of ceria nanoparticles and their chemical mechanical polishing behavior on glass substrate

To improve their chemical mechanical polishing (CMP) performance, ceria nanoparticles were surface modified with γ-aminopropyltriethoxysilane (APS) through silanization reaction with their surface hydroxyl group. The compositions, structures and dispersibility of the modified ceria particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), laser particle size analyzer, zeta potential measurement and stability test, respectively. The results indicated that APS had been successfully grafted onto the surface of ceria nanoparticles, which led to the modified ceria nanoparticles with better dispersibility and stability than unmodified ceria particles in aqueous fluids. Then, CMP performance of the modified ceria nanoparticles on glass substrate was investigated. Experimental results showed that the modified ceria particles exhibited lower material removal rate (MRR) but much better surface quality than unmodified ceria particles, which may be explained by the hardness reduction of ceria particles, the enhancement of lubrication of the particles and substrate surfaces, and the elimination of the agglomeration among the ceria particles.     

Results of potential exposure assessments during the maintenance and cleanout of deposition equipment

This study is a compilation of results obtained during the cleanout of deposition equipment such as chemical vapor deposition or physical vapor deposition The measurement campaigns aimed to evaluate the potential exposure to nanoaerosols in the occupational environment and were conducted in the workspace. The characterization of aerosols includes measurements of the concentration using condensation particle counters and measurements of the size distribution using fast mobility particle sizer, scanning mobility particle sizer, and electrical low pressure impactor (ELPI). Particles were sampled using collection membranes placed on the ELPIs stages. The samples were analyzed with an SEM?CEDS to provide information including size, shape, agglomeration state, and the chemical composition of the particles. The majority of the time, no emission of nanoparticles (NPs) was measured during the use of the molecular deposition equipment or when opening the chambers, mainly due to the enclosed processes. On the other hand, the maintenance of the equipment, and especially the cleanout step, could induce high concentrations of NPs in the workplace following certain processes. Values of around 1 million particles/cm³ were detected with a size distribution including a high concentration of particles around 10?nm.     

Size-fractionated characterization and quantification of nanoparticle release rates from a consumer spray product containing engineered nanoparticles

This study describes methods developed for reliable quantification of size- and element-specific release of engineered nanoparticles (ENP) from consumer spray products. A modified glove box setup was designed to allow controlled spray experiments in a particle-minimized environment. Time dependence of the particle size distribution in a size range of 10–500 nm and ENP release rates were studied using a scanning mobility particle sizer (SMPS). In parallel, the aerosol was transferred to a size-calibrated electrostatic TEM sampler. The deposited particles were investigated using electron microscopy techniques in combination with image processing software. This approach enables the chemical and morphological characterization as well as quantification of released nanoparticles from a spray product. The differentiation of solid ENP from the released nano-sized droplets was achieved by applying a thermo-desorbing unit. After optimization, the setup was applied to investigate different spray situations using both pump and gas propellant spray dispensers for a commercially available water-based nano-silver spray. The pump spray situation showed no measurable nanoparticle release, whereas in the case of the gas spray, a significant release was observed. From the results it can be assumed that the homogeneously distributed ENP from the original dispersion grow in size and change morphology during and after the spray process but still exist as nanometer particles of size <100 nm. Furthermore, it seems that the release of ENP correlates with the generated aerosol droplet size distribution produced by the spray vessel type used. This is the first study presenting results concerning the release of ENP from spray products.     

Secondary ion species containing nitrogen atoms from plasma-enhanced chemical vapor deposited silicon oxide films on silicon

Secondary ion species from plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Comparative studies of PECVD SiO₂ films prepared using a mixture of SiH₄/N₂O reaction gas at 400 °C with thermally oxidized SiO₂ films grown at 900 °C were carried out in the mid-range mass spectra from 95 to 165 amu. Small amounts of ion species containing nitrogen atoms, including Si₂O₂N⁺, Si₃O₂N⁺and Si₃O₃N⁺, were detected in the SiO₂ bulk from the PECVD SiO₂ films. Furthermore, large amounts of Si₃O₂N⁺ and Si₂O₃N⁻ were found at the interface between silicon and the SiO₂ films. Depth analysis showed that the intensity peak shapes of these ion species containing nitrogen atoms at the interface were closely coincident with those of Si₃O₃⁺ corrected by subtracting the influence of the SiO₂ matrix. The variation in the spectra of these ion species clearly indicates that two types of structures of oxynitride exist for the PECVD SiO₂ films in the SiO₂ bulk films and at the interface. These are likely produced by the reaction of reactive gas with SiO₂ and silicon surfaces where dangling bonds of silicon may exist in the different form.     

Analysis of intensities of positive and negative ion species from silicon dioxide films using time-of-flight secondary ion mass spectrometry and electronegativity of fragments

Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of ²⁸Si⁺ and ²⁸Si⁻ ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) × 10³ K of the sputtered region bombarded with pulsed 22 kV Au₃⁺ primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of Si_nO_m fragments, and a slight shift to negative polarity for PECVD SiO₂ compared to thermally oxidized SiO₂ films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO₂ by those for thermally oxidized SiO₂ films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiO_m (m = 1, 2) and Si₂O_m (m = 1-4) fragments for PECVD SiO₂ films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO₂ films compared to the thermally oxidized SiO₂ films.     

Modeling of ion-assisted deposition using BCA computer simulation

Abstract

TRIM type binary collision approximation event store codes have employed to simulate collisional effects which occur during ion-beam or plasma assisted deposition of thin films.

Calculations can been performed using simplifying rate equation models, into which yields obtained from static TRIM simulations are inserted. Alternatively, the dynamic-composition code TRIDYN allows direct and complete simulations of the time-dependent processes.

Results are shown for different processes of ion-beam assisted deposition (IBAD), ion-beam mixing (IBM) post-treatment, and plasma-enhanced chemical vapour deposition (PECVD). Simulations of the formation of boron nitride films deposited from evaporated boron and energetic nitrogen show an excellent agreement with experimental results for nitrogen concentrations below the stoichiometric limit. For high N/B flux ratios, non-collisional mechanisms (ion-induced outdiffusion, surface trapping of outdiffusing nitrogen) have been included in the simulations, again producing good agreement with the experimental results. The ion-induced interface mixing of boron films on iron substrates is compared to experimental adhesion studies both for Ar⁺ post-treatment and Ar⁺ bombardment during deposition, demonstrating that the final adhesion is also influenced by other than purely collisional mechanisms. A special version of TRIDYN is used to treat the ion-induced densification of carbon films grown during simultaneous Ne⁺ bombardment, with reasonable agreement with experimental results. Finally, simple models are evaluated for the growth, composition and structure of C:H films grown in methane plasmas. The hydrogen content of the films decreases with increasing ion energy due to ion-induced release of hydrogen. Attempts to understand their bonding structure, in terms of the sp³/sp² ratio, on the basis of ion-induced preferential displacement, fail with respect to the energy dependence.     

Nano reduction coupled with encapsulation as a novel technique for utilising millet proteins as future foods

Crocin (saffron bioactive) loaded protein nanoparticles were prepared from three underutilised cereal varieties viz., sorghum (SPCN), foxtail millet (FPCN) and pearl millet (PPCN) using ultrasonication technique. The particle size of crocin loaded protein complex was attained in the nano range with reduced polydispersity index and negative zeta potential. The encapsulation efficiency of crocin in protein nanoparticles was found to be 83.78% (FPCN), 78.74 % (SPCN) and 70.01% (PPCN). The topographical images of crocin loaded protein nano complex was revealed using field emission-scanning electron microscopy (FE-SEM). The attenuated total reflectance fourier transform infra-spectroscopy (ATR-FTIR) analysis showed the characteristic peaks of crocin at 956, 1700 and 3350 cm⁻¹ in protein-crocin nanocomplex as a confirmatory test for nanoencapsulation. The antimicrobial activity of crocin loaded protein nanocomplex against three strains (Escherichia coli, Staphylococcus aureus and Fusarium oxysporium) were also evaluated. In vitro release studies showed higher content of crocin released in simulated intestinal conditions ensuring its controlled release at target site. Bioactivity (anti-cancerous and anti-hypertensive) of crocin upon in-vitro digestion were well retained indicating that protein nanoparticles can act as an effective wall material. Our results suggest that protein nanoparticles prepared in this study can act as an effective oral delivery vehicle for crocin that could be used for development of functional foods.     

21.0%‐efficient co‐diffused screen printed n‐type silicon solar cell with rear‐side boron emitter

Plasma enhanced chemical vapor deposition (PECVD) is applied to deposit boron silicate glasses (BSG) acting as boron diffusion source during the fabrication of n‐type silicon solar cells. We characterize the resulting boron‐diffused emitter after boron drive‐in from PECVD BSG by measuring the sheet resistances R_sheet,B and saturation current densities J_0,B. For process optimization, we vary the PECVD deposition parameters such as the gas flows of the precursor gases silane and diborane and the PECVD BSG layer thickness. We find an optimum gas flow ratio of SiH₄/B₂H₆= 8% and layer thickness of 40 nm. After boron drive in from these PECVD BSG diffusion sources, a low J_0,B values of 21 fA/cm² is reached for R_sheet,B = 70 Ω/□. The optimized PECVD BSG layers together with a co‐diffusion process are implemented into the fabrication process of passivated emitter and rear totally diffused (PERT) back junction (BJ) cells on n‐type silicon. An independently confirmed energy conversion efficiency of 21.0% is achieved on 15.6 × 15.6 cm² cell area with a simplified process flow. This is the highest efficiency reported for a co‐diffused n‐type PERT BJ cell using PECVD BSG as diffusion source. A loss analysis shows a small contribution of 0.13 mW/cm² of the boron diffusion to the recombination loss proving the high quality of this diffusion source. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Polishing behavior of PS/CeO2 hybrid microspheres with controlled shell thickness on silicon dioxide CMP

Organic-inorganic composite microspheres with PS as a core and CeO₂ nanoparticles as a shell were synthesized by in situ decomposition reaction of Ce(NO₃)₃ on the surfaces of PS microspheres prepared through soap-free emulsion polymerization. The shell thickness of the composite microspheres could be turned by varying the concentration of Ce(NO₃)₃ in the reaction solution. The whole process required neither surface treatment for PS microspheres nor additional surfactant or stabilizer. The as-synthesized PS/CeO₂ composite microsphere samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Oxide chemical mechanical polishing (CMP) performance of the PS/CeO₂ composite abrasives with different shell thickness was characterized by atomic force microscopy (AFM). The results indicated that the as-prepared core-shell structured composite microspheres (220-260 nm in diameter) possessed thin shell (10-30 nm) composed of CeO₂ nanoparticles (particle diameter of 5-10 nm), and the final CeO₂ contents of the composite microspheres ranged from 10 to 50 wt%. A possible mechanism for the formation of PS/CeO₂ composite microspheres was discussed also. The CMP test results confirmed that the novel core-shell structured composite abrasives are useful to improve oxide CMP performance. In addition, there is an obvious effect of shell thickness of the composite abrasives on oxide CMP performance.     

Use of a silver ion selective electrode to assess mechanisms responsible for biological effects of silver nanoparticles

For a detailed analysis of the biological effects of silver nanoparticles, discrimination between effects related to the nano-scale size of the particles and effects of released silver ions is required. Silver ions are either present in the initial particle dispersion or released by the nanoparticles over time. The aim of this study is to monitor the free silver ion activity {Ag⁺} in the presence of silver nanoparticles using a silver ion selective electrode. Therefore, silver in the form of silver nanoparticles, 4.2 ± 1.4 nm and 2–30 nm in size, or silver nitrate was added to cell culture media in the absence or presence of A549 cells as a model for human type II alveolar epithelial cells. The free silver ion activity measured after the addition of silver nanoparticles was determined by the initial ionic silver content. The p {Ag⁺} values indicated that the cell culture media decrease the free silver ion activity due to binding of silver ions by constituents of the media. In the presence of A549 cells, the free silver ion activity was further reduced. The morphology of A549 cells, cultivated in DME medium containing 9.1% (v/v) FBS, was affected by adding AgNO₃ at concentrations of ≥30 μM after 24 h. In comparison, silver nanoparticles up to a concentration of 200 μM Ag did not affect cellular morphology. Our experiments indicate that the effect of silver nanoparticles is mainly mediated by silver ions. An effect of silver on cellular morphology was observed at p {Ag⁺} ≤ 9.2.     

Kinetic aspects of the silver ion release from antimicrobial polyamide/silver nanocomposites

Spherical silver nanoparticles were grown in situ in different polyamides by a thermal reduction of silver acetate during melt processing of the polymers. Most of the particles have a diameter of about 20 nm. The absolute amount as well as the kinetics of the silver ion release from the various polyamide/silver nanocomposites differ strongly, although the filler content in all materials is the same (1.5 wt. %) and the morphologies of the silver particles are not very different. One result of the investigations was that the absolute amount of the long-term silver ion release increases exponentially with the maximum water absorption of the polymers used as matrix materials, because silver ions are formed from elemental silver particles in the presence of water, only. Moreover, it was also found that the long-term silver ion release increases with a growing diffusion coefficient of water in the polymer. The water absorption properties of the polymers govern the kinetics of the silver ion release, too: for strong hydrophilic polyamides like PA6 or PA6.6, which are plasticized by water, the silver ion release is a zero-order process. For nanocomposites with less hydrophilic polyamides like a cycloaliphatic polyamide or a P12 modified with polytetrahydrofurane (PA12-poly-THF), the silver ion release is governed by diffusion. As expected from the efficacy of the silver ion release, PA6, PA6.6, PA12 and PA12 modified with polytetrahydrofurane and a cycloaliphatic polyamide filled with 1.5 wt. % of silver nanoparticles are active against Escherichia coli. But, only nanocomposites with PA6, PA6.6 and P12-poly-THF as matrix materials are suitable as long-term biocidal materials. PACS 68.35.bm; 68.35.Fx; 68.37.Lp     

Ageing of plasma-mediated coatings with embedded silver nanoparticles on stainless steel: An XPS and ToF-SIMS investigation

Nanocomposite thin films (∼170 nm), composed of silver nanoparticles enclosed in an organosilicon matrix, were deposited onto stainless steel, with the aim of preventing biofilm formation. The film deposition was carried out under cold plasma conditions, combining radiofrequency (RF) glow discharge fed with argon and hexamethyldisiloxane and simultaneous silver sputtering. XPS and ToF-SIMS were used to characterize Ag-organosilicon films in native form and after ageing in saline solution (NaCl 0.15 M), in order to further correlate their lifetime with their anti-fouling properties. Two coatings with significantly different silver contents (7.5% and 20.3%) were tested. Surface analysis confirmed the presence of metallic silver in the pristine coating and revealed significant modifications after immersion in the saline solution. Two different ageing mechanisms were observed, depending on the initial silver concentration in the film. For the sample exhibiting the low silver content (7.5%), the metal amount decreased at the surface in contact with the solution, due to the release of silver from the coating. As a result, after a 2-day exposure, silver nanoparticles located at the extreme surface were entirely released, whereas silver is still present in the inner part of the film. The coating thickness was not modified during ageing. In contrast, for the high silver content film (20.3%), the thickness decreased with immersion time, due to significant silver release and matrix erosion, assigned to a percolation-like effect. However, after 18 days of immersion, the delamination process stopped and a thin strongly bounded layer remained on the stainless steel surface.     

Ceria concentration effect on chemical mechanical polishing of optical glass

It was found material removal rate (MRR) sharply increased from 250 to 675 nm/min as the concentration decreased from 1 to 0.25 wt% in optical glass chemical mechanical polishing (CMP) using ceria slurries. Scanning electron microscopy was employed to characterize the ceria abrasive used in the slurry. Atomic force microscopy results showed good surface had been got after CMP. Schematic diagrams of the CMP process were shown. Furthermore, the absorption spectra indicated a sudden change from Ce⁴⁺ to Ce³⁺ of the ceria surface when the concentration decreased, which revealed a quantum origin of the phenomenon.     

Ion bombardment of amorphous silicon films during plasma-enhanced chemical vapor deposition in an rf discharge

The characteristics of ion and electron fluxes to the surface of a growing silicon film are investigated in various rf discharge regimes in silane at frequencies of 13.56 MHz and 58 MHz in plasma-enhanced chemical vapor-deposition (PECVD) apparatus. The energy spectra of the ions and electrons bombarding the growing film are measured. The electronic properties of films grown under various degrees of ion bombardment are studied. The correlation of these properties with the ion parameters in the rf discharge plasma during film growth is discussed. Zh. Tekh. Fiz. 68, 52–59 (February 1998)     

The influence of surface-active substances on the crystallization process and magnetic properties of goethite nanoparticles

To prevent the process of aggregation and growth of ??-FeOOH nanoparticles, during chemical syntheses various surface-active substances (SASs) with a concentration of 3 g/dm³ were added into the solution. The applied SASs were: cetylpyridinium chloride (CPC), sodium dodecyl sulphate (SDS), and complexone EDTA. Using various methods it was found that SAS molecules have a dual effect on the obtained nanoparticles: on one hand SAS application increases the number of small ??-FeOOH nanoparticles with sizes of 2?C5nm. On the other hand, SAS molecules react with surface atoms of the nanoparticles and form additional compounds.