More Like this

1. Chemical Structure Analysis of Carbon-Doped Silicon Oxide Thin Films by Plasma-Enhanced Chemical Vapor Deposition of Tetrakis(Trimethylsilyloxy)Silane Precursor

   https://doi.org/10.1115/IMECE2021-72026  

   Comeaux, Jacob; Wirth, William B; Courville, Justin; Luo, Lingyiqian; Yan, Hui; Jang, Seonhee (November 2021, American Society of Mechanical Engineers)

   Abstract Carbon-doped silicon oxide (CDO) thin films as low dielectric constant materials were deposited on both n-type silicon (Si) (100) and indium tin oxide coated polyethylene naphthalate (ITO/PEN) substrates, using the plasma-enhanced chemical vapor deposition of tetrakis(trimethylsilyoxy)silane (TTMSS) precursor. Chemical structures of the CDO films were analyzed by using FTIR (Fourier transformation infrared) spectroscopy and XPS (X-ray photoelectron spectroscopy). The chemical bonds related with hydrocarbon and Si–O were the main characteristics of the CDO films. The prominent peaks from the FTIR spectra included Si–O–Si stretching, Si–CH3 bending, Si–(CH3)x stretching, and CHx stretching modes. XPS spectra composed of the O1s, C1s, and Si2p electron orbitals were used to quantitatively analyze the elemental composition of the CDO films. The growth mechanisms of CDO films were dependent on the substrate type. For the ITO/PEN substrate, the lack of Si atoms on the ITO surface made difficulty in forming initial Si–O bonds, resulting in insufficient Si–O–Si structure. In comparison, the CDO films could grow easily on Si substrates due to pre-existing Si–O bonds on the surface. The chemical structures of the CDO films are expected to affect electrical and mechanical performances. 

   more » « less
2. Silicon carbide (SiC) derived from agricultural waste potentially competitive with silicon anodes

   https://doi.org/10.1039/D2GC00645F  

   Yu, M.; Temeche, E.; Indris, S.; Lai, W.; Laine, R. M. (April 2022, Green chemistry)

   Biomass-derived materials offer low carbon approaches to energy storage. High surface area SiC w/wo 13 wt% hard carbon (SiC/HC, SiC/O), derived from carbothermal reduction of silica depleted rice hull ash (SDRHA), can function as Li+ battery anodes. Galvanostatic cycling of SiC/HC and SiC/O shows capacity increases eventually to >950 mA h g−1 (Li1.2–1.4SiC) and >740 mA h g−1 (Li1.1SiC), respectively, after 600 cycles. Post-mortem investigation via XRD and 29Si MAS NMR reveals partial phase transformation from 3C- to 6H-SiC, with no significant changes in unit cell size. SEMs show cycled electrodes maintain their integrity, implying almost no volume expansion on lithiation/delithiation, contrasting with >300% volume changes in Si anodes on lithiation. Significant void space is needed to compensate for these volume changes with Si in contrast to SiC anodes suggesting nearly competitive capacities. 6Li MAS NMR and XPS show no evidence of LixSi, with Li preferring all-C environments supported by computational modeling. Modeling also supports deviation from the 3C phase at high Li contents with minimal volume changes. 

   more » « less
3. Catalytic behavior of hexaphenyldisiloxane in the synthesis of pyrite FeS ₂

   https://doi.org/10.1039/D0CC03397A  

   Todd, Paul K.; Martinolich, Andrew J.; Neilson, James R. (August 2020, Chemical Communications)

   null (Ed.)

   Functional small molecules afford opportunities to direct solid-state inorganic reactions at low temperatures. Here, we use catalytic amounts of organosilicon molecules to influence the metathesis reaction: FeCl 2 + Na 2 S 2 → 2NaCl + FeS 2 . Specifically, hexaphenyldisiloxane ((C 6 H 5 ) 6 Si 2 O) is shown to increase pyrite yields in metathesis reactions performed at 150 °C. In situ synchrotron X-ray diffraction (SXRD) paired with differential scanning calorimetry (DSC) reveals that diffusion-limited intermediates are circumvented in the presence of (C 6 H 5 ) 6 Si 2 O. Control reactions suggest that the observed change in the reaction pathway is imparted by the Si–O functional group. 1 H NMR supports catalytic behavior, as (C 6 H 5 ) 6 Si 2 O is unchanged ex post facto . Taken together, we hypothesize that the polar Si–O functional group coordinates to iron chloride species when NaCl and Na 2 S 4 form, forming an unidentified, transient intermediate. Further exploration of targeted small molecules in these metathesis reaction provides new strategies in controlling inorganic materials synthesis at low-temperatures. 

   more » « less
4. Atomic Layer Deposition of Nickel Using Ni(dmamb)2 and ZnO Adhesion Layer Without Plasma

   https://doi.org/10.1007/s41871-024-00238-5  

   Baker, Kaiya; Brown, Hayden; Gebre, Fisseha; Xu, Jiajun (September 2024, Nanomanufacturing and Metrology)

   Abstract In this study, a novel deposition technique that utilizes diethylzinc (C₄H₁₀ZnO) with H₂O to form a ZnO adhesion layer was proposed. This technique was followed by the deposition of vaporized nickel(II) 1-dimethylamino-2-methyl-2-butoxide (Ni(dmamb)₂) and H₂gas to facilitate the deposit of uniform layers of nickel on the ZnO adhesion layer using atomic layer deposition. Deposition temperatures ranged from 220 to 300 °C. Thickness, composition, and crystallographic structure results were analyzed using spectroscopic ellipsometry, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), respectively. An average growth rate of approximately 0.0105 angstroms per cycle at 260 °C was observed via ellipsometry. Uniform deposition of ZnO with less than 1% of Ni was displayed by utilizing the elemental analysis function via SEM, thereby providing high-quality images. XPS revealed ionizations consistent with nickel and ZnO through the kinetic and binding energies of each detected electron. XRD provided supplemental information regarding the validity of ZnO by exhibiting crystalline attributes, revealing the presence of its hexagonal wurtzite structure. 

   more » « less
5. Unexpected alkyl isomerization at the silicon ligand of an unsaturated Rh complex: combined experiment and theory

   https://doi.org/10.1039/D3DT02087H  

   Abeynayake, Niroshani S; Le, Nghia; Sanchez-Lecuona, Gabriela; Donnadieu, Bruno; Webster, Charles Edwin; Montiel-Palma, Virginia (November 2023, Dalton Transactions)

   The formation of dimer [(μ-Cl)Rh-(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)(o-C6H4CH2SiiPrnPr))]2 (Rh-3) with an n-propyl group on one of the silicon atoms as a minor product was affected by the reaction of [RhCl(COD)]2 with proligand PhP(o-C6H4CH2SiHiPr2)2, L1. The major product of the reaction was monomeric 14-electron Rh(III) complex [ClRh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2)] (Rh-1). Computations revealed that the monomer–dimer equilibrium is shifted toward the monomer with four isopropyl substituents on the two Si atoms of the ligand as in Rh-1; conversely, the dimer is favored with only one n-propyl as in Rh-3, and with less bulky alkyl substituents such as in [ClRh(κ3(P,Si,Si)PhP(o-C6H4CH2SiMe2)2]2 (Rh-2). Computations on the mechanism of formation of Rh-3 directly from [RhCl(COD)]2 are in agreement with the experimental findings and it is found to be less energetic than if stemming from Rh-1. Additionally, a Si–O–Si complex, [μ-Cl-Rh{κ3(P,Si,C)PPh(o-C6H4CH2SiiPrO SiiPr2CH-o-C6H4)}]2, Rh-4, is generated from the reaction of Rh-1 with adventitious water as a result of intramolecular C–H activation. 

   more » « less