Ar ions and oxygen plasma interactions of amine terminated organosilicate glass: A combined experimental and <i>ab initio</i> simulations study

Kazi, Haseeb; Rimsza, Jessica; Du, Jincheng; Kelber, Jeffry A.

doi:10.1116/1.4890119

Cited by 13 publications

(6 citation statements)

References 27 publications

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“…26,27 Activation energies vary with solution compositions, temperature, and the use of bulk or powdered samples. 28,29 Energy barriers are lower than the Si-O bond energies of 5-6 eV 30 indicating the important role that water plays in lowering energy barriers. Criscenti et al 19 attempted to identify a connection between the connectedness of the silicon and stability of related siloxane bonds but did not find a clear relationships, indicating the complexity of the silica dissolution mechanisms.…”

Section: First-principles-based Simulations Of Glass-water Interactionsmentioning

confidence: 99%

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Rimsza

2017

npj Mater Degrad

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Computer simulations at the atomistic scale play an increasing important role in understanding the structure features, and the structure-property relationships of glass and amorphous materials. In this paper, we reviewed atomistic simulation methods ranging from first principles calculations and ab initio molecular dynamics (AIMD) simulations, to classical molecular dynamics (MD), and meso-scale kinetic Monte Carlo (KMC) simulations and their applications to study the reactions and interactions of inorganic glasses with water and the dissolution behaviors of inorganic glasses. Particularly, the use of these simulation methods in understanding the reaction mechanisms of water with oxide glasses, water-glass interfaces, hydrated porous silica gels formation, the structure and properties of multicomponent glasses, and microstructure evolution are reviewed. The advantages and disadvantageous of these simulation methods are discussed and the current challenges and future direction of atomistic simulations in glass dissolution presented.npj Materials Degradation (2017) 1:16 ; doi:10.1038/s41529-017-0017-yThe corrosion or degradation of glasses in aqueous solutions are critical in a number of engineering and technological processes ranging from microelectronic packaging, glass reaction chambers, and the immobilization of nuclear waste materials, as well as in healthcare and biomedical fields such as dissolution of inhaled glass fibers and bioactive glasses for biomedical applications. In particular, immobilizing radioactive waste in borosilicate glasses is widely accepted as a preferred method to treat nuclear waste materials generated from civilian and military sources. This process, also known as vitrification, is a critical component of the cycle of nuclear energy to combat global environmental and energy challenges. Researchers from around the world have extensively invested in understanding glass corrosion in an effort to predict the long-term stability and release rate radionuclides to the environment during nuclear waste storage. 1,2Various mechanisms for glass corrosion have been proposed and despite intensive experimental investigations with advanced characterization techniques results are unclear. It is generally accepted that the corrosion of glass consists of a set of complex processes including hydration, hydrolysis, and ion-exchange that are coupled during glass dissolution. The initial stage is interdiffusion of proton or hydronium ions from the solution with sodium or other alkali ions in the glass.3 This is followed by the hydrophilic attack of water on the Si-O-Si or Si-O-Al linkages that lead to hydroxylation of the silicate glass network. The remaining hydrolyzed glass skeleton then undergoes condensation and repolymerization to form the hydrated nanoporous silica rich gel layer which can be protective, decreasing dissolution to a residual rate. [4][5][6] The morphology of the gel layer, such as thickness, pore structure, and chemical composition, depends on the original glass composition and the pH...

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Section: First-principles-based Simulations Of Glass-water Interactionsmentioning

confidence: 99%

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Rimsza

2017

npj Mater Degrad

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“…[66][67][68] The loss of such terminal organic groups in low-k a-SiOC:H dielectrics typically results in the formation of new chemical bonds and a more SiO 2 like composition. 69,70 These effects are most commonly observed as "sidewall damage" resulting from plasma etch and ashing processes that convert to SiO 2 the sidewalls of trenches etched into the low-k a-SiOC:H dielectric. This "sidewall damage" becomes readily apparent after dilute HF cleans where the SiO 2 damage layer is selectively etched away resulting in a widening of the formed trench and undercut of any overlying hard mask materials.…”

Section: Absorbance (Au)mentioning

confidence: 99%

Nanoscale Chemical-Mechanical Characterization of Nanoelectronic Low-kDielectric/Cu Interconnects

Lo¹,

Dazzi

Marcott³

et al. 2015

ECS J. Solid State Sci. Technol.

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Combined nanoscale chemical and mechanical property characterization has largely been limited by the inability to extend chemical structure identification techniques such as infrared (IR) absorption spectroscopy into the nanometer regime due to diffraction limitations. The recent development of atomic force microscope (AFM) based IR spectroscopy (AFM-IR) has now enabled infrared chemical spectroscopy with resolution well below the diffraction limit. However, the combination of AFM-IR with other AFM based techniques to achieve nanoscale chemical structure-mechanical property characterization has yet to be demonstrated. In this regard, we have combined AFM-IR chemical and contact resonance AFM (CR-AFM) mechanical measurements in the investigation of low dielectric constant (low-k) / Cu damascene structures fabricated using a 90 nm interconnect process technology. We show that the combined AFM-IR and CR-AFM results can be utilized to perform nanoscale chemical-mechanical characterization of both the nano-patterned metal and the low-k dielectric whose mechanical properties are sensitive to chemical modification by the interconnect fabrication process. The continued drive to seek and exploit new materials and phenomena at nanometer dimensions has increased the demand for metrologies capable of characterizing both chemical structure and physical properties at the nanoscale. The nanoelectronics industry in particular has identified metrologies capable of performing nanoscale structureproperty measurements on new materials and devices as an area of critical need in their industry technology roadmap.1,2 Such requirements for nanoscale physical property characterization have readily been met by the development of a range of scanned probe techniques capable of assessing the thermal, 3,4 mechanical, 5,6 and electrical 7,8 properties of materials at the nanoscale. 9 However, the development of nanoscale chemical structure metrologies has been hindered by the difficulty of scaling popular micron-scale techniques such as infrared (IR) absorption spectroscopy [10][11][12] into the nanometer regime due to diffraction limits defined by the Rayleigh equation.13,14 To overcome these limitations, a number of approaches combining optical spectroscopy with scanned probe microscopy (SPM) have been proposed and demonstrated. [13][14][15][16][17][18][19][20] Of these, the atomic force microscope (AFM) IR technique, which is based on photothermally induced resonance (PTIR), 21,22 has recently garnered significant interest due to a demonstrated spatial resolution of 25-100 nm, and a close correlation to micron-scale Fourier transform infrared (FTIR) spectroscopy. 13,14 This combination has resulted in the utilization of AFM-IR in a number of biological, 23-25 polymeric, 26-28 and semiconductor [29][30][31] applications. However, AFM-IR and related techniques have yet to be routinely combined with other AFM based techniques to achieve the ultimate goal of nanoscale structure-property characterization. In this regard, we provide a compelling...

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“…The differences between the computational Si-C values reported here and the experimental value of 1.97Å maybe the result the relative weakness of the Si-CH3 bond compared to the Si-O bonds which are present, in contrast to the hexamethydisilane where each Si is bonded to three methyl groups and the neighboring silicon atom [46]. Previous DFT studies on TMCTS (trimethylcylictrisiloxane) molecule identified a Si-CH3 bond length of 1.89Å when the Si coordination environment contains two bridging oxygen, one hydrogen, and a methyl group, demonstrating a slight Si-C bond lengthening with an increase in the number of bridging oxygen [6]. Furthermore, the bulk silica surface may cause lengthening of the Si-CH3 bond and may factor in the slightly longer Si-CH3 bond length.…”

Section: Pair Distribution Functions (Pdf) Analysismentioning

confidence: 96%

“…For dense silica experimental methods including NMR (nuclear magnetic resonance) and electron diffraction have been effective in providing some insight into the coordination environments, bond lengths, and bond angles [5]. The addition of light organic elements to the nanoporous silica to form OSG generates an increasingly complex system which has undergone limited experimental analysis, with the expectation of FTIR which has provide information on various bond concentrations [6,7].…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulations of nanoporous organosilicate glasses using Reactive Force Field (ReaxFF)

Rimsza

Deng

2016

Journal of Non-Crystalline Solids

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The structure and properties of nanoporous organosilicate glass (OSG) structure models with 30-70% porosities and different pore morphologies were simulated using molecular dynamics simulations with Reactive Force Field (ReaxFF) potential. The OSG structures were created from nanoporous silica structures generated using classical molecular dynamics (MD) simulations with partial charge pairwise potentials and a subsequent step of adding hydroxide and methyl groups to the dangling bonds and coordination defects. The nanoporous OSG systems were then fully relaxed using molecular dynamics simulations with ReaxFF and detailed structure analysis performed and properties calculated. Analysis of the OSG systems indicated that the structural features (bond distances and angles) as well as the Qn distribution of the nanoporous silica backbone structure are consistent with the features of dense silica and that the geometry of the added methyl groups are experimentally accurate, even after ReaxFF relaxation. The elastic modulus of the nanoporous silica was calculated and found to be 24-31 GPa for system with 30% porosity and 0.5-2.5 GPa for those with 70% porosity, consistent with previously reported experimental results.

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Ar ions and oxygen plasma interactions of amine terminated organosilicate glass: A combined experimental and ab initio simulations study

Cited by 13 publications

References 27 publications

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Nanoscale Chemical-Mechanical Characterization of Nanoelectronic Low-kDielectric/Cu Interconnects

Molecular dynamics simulations of nanoporous organosilicate glasses using Reactive Force Field (ReaxFF)

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