Monolayer Doping of Silicon through Grafting a Tailored Molecular Phosphorus Precursor onto Oxide-Passivated Silicon Surfaces

Alphazan, Thibault; Mathey, Laurent; Schwarzwälder, Martin; Lin, Tsung-Han; Rossini, Aaron J.; Wischert, Raphaël; Enyedi, Virginie; Fontaine, Hervé; Veillerot, M.; Lesage, Anne; Emsley, Lyndon; Veyre, Laurent; Martín, F.; Thieuleux, Chloé; Copéret, Christophe

doi:10.1021/acs.chemmater.5b04291

Cited by 52 publications

(45 citation statements)

References 60 publications

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“…The absence of additional 8 correlations at 1.7 and 4.9 ppm support the attribution of the other isopropoxy ligand to be bound to a silicon rather than vanadium. This interpretation is further supported by the difference of chemical shift since alkoxide ligands bound to d 0 transition-metals are often greatly deshielded, 37,38 because of the presence of low lying empty d orbitals on the metal that modify the electronic structures of bonded ligands. 39 This observation is in line with elemental analysis results which indicated a C:V ratio of 5.5 as mentioned before, thus confirming that approximately 2 isopropoxide ligands remain on the silica surface.…”

mentioning

confidence: 94%

Proton-Detected Multidimensional Solid-State NMR Enables Precise Characterization of Vanadium Surface Species at Natural Abundance

Mance

Comas‐Vives

Copéret

2019

J. Phys. Chem. Lett.

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Heterogeneous catalysts fulfill vital roles in industrial process, however due to the nature of the catalytic surfaces typically containing either a low abundance of active sites and being amorphous in nature leads difficulties when attempting to study the structure of the active sites. In this work we show how making use of fast MAS ssNMR probes allows to efficiently detect well resolved 1 H detected spectra of heterogeneous catalysts. This approach was applied to study the structure of surface species resulting from the grafting of VO(OiPr)3 onto a partially dehydroxylated silica using the surface organometallic chemistry approach. The use of the 1 H sensitivity enabled to detect various hetero-and homo-nuclear correlation spectra in order to study the structure of this system and to resolve the structure of the grafted vanadium complex. More specifically, VO(OiPr)3 grafts through both protonolysis and opening of siloxane bridges to generate a bis-grafted species, in contrast to most other alkoxides.

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confidence: 94%

Proton-Detected Multidimensional Solid-State NMR Enables Precise Characterization of Vanadium Surface Species at Natural Abundance

Mance

Comas‐Vives

Copéret

2019

J. Phys. Chem. Lett.

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“…In that respect, we have demonstrated that the surface chemistry of a silica layer on passivated silicon wafers is analogous to that of high surface area silica nanoparticles and that identical surface species were found upon immobilization of molecules on both supports. 17,18 …”

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confidence: 99%

Magnetic Memory from Site Isolated Dy(III) on Silica Materials

et al. 2017

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Achieving magnetic remanence at single isolated metal sites dispersed at the surface of a solid matrix has been envisioned as a key step toward information storage and processing in the smallest unit of matter. Here, we show that isolated Dy(III) sites distributed at the surface of silica nanoparticles, prepared with a simple and scalable two-step process, show magnetic remanence and display a hysteresis loop open at liquid 4He temperature, in contrast to the molecular precursor which does not display any magnetic memory. This singular behavior is achieved through the controlled grafting of a tailored Dy(III) siloxide complex on partially dehydroxylated silica nanoparticles followed by thermal annealing. This approach allows control of the density and the structure of isolated, “bare” Dy(III) sites bound to the silica surface. During the process, all organic fragments are removed, leaving the surface as the sole ligand, promoting magnetic remanence.

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“…There are very few theoretical studies on the POSS structures. B3LYP, which is an accurate and well known method, is widely used for the POSS studies . Skelton compared MP2, B3LYP, and wB97XD methods for the interaction of POSS with CO 2 , N 2 , O 2 , CO, CH 4 , He, and H 2 O by keeping the cage structure fixed.…”

Section: Poss Models and Calculation Methodsmentioning

confidence: 99%

Density functional theory study of interactions between carbon dioxide and functionalized polyhedral oligomeric silsesquioxanes

Tezsevin

Demirtas

Önal

et al. 2017

Int J of Quantum Chemistry

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Polyhedral Oligomeric Silsesquioxanes (POSS) are cage‐structured inorganic–organic hybrid materials which can be used in various industrial applications. It is recently discovered that POSS structures with certain functional groups can be solubilized in supercritical CO2 allowing their applications in environmentally benign supercritical processing of materials. In this theoretical study, nature and energetics of the interactions of octatrifluoropropyl POSS, octatrifluoromethyl POSS, and octamethyl POSS with CO2 are investigated according to the principles of density functional theory (DFT) by use of Gaussian 09 software. Simulations show that CO2‐octamethyl POSS pair has hydrogen bonding between the O atom of CO2 and the H atom of the methyl group, and CO2‐octatrifluoromethyl POSS pair has interactions between the C atom of CO2 and the F atom of the trifluoromethyl group. CO2‐octatrifluoropropyl POSS pair is found to have both interaction types. The octamethyl, the octatrifluoromethyl and the octatrifluoropropyl POSS structures have interaction energies of −2.18 kcal/mol, −3.10 kcal/mol, and −3.77 kcal/mol, respectively. This shows that the presence of Lewis acid–Lewis base interaction between C and F instead of hydrogen bonding between O and H atoms enhances the interaction of the molecule with CO2, while the presence of both interactions between the octatrifluoropropyl POSS‐CO2 pair makes the intermolecular interaction even stronger.

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Monolayer Doping of Silicon through Grafting a Tailored Molecular Phosphorus Precursor onto Oxide-Passivated Silicon Surfaces

Cited by 52 publications

References 60 publications

Proton-Detected Multidimensional Solid-State NMR Enables Precise Characterization of Vanadium Surface Species at Natural Abundance

Proton-Detected Multidimensional Solid-State NMR Enables Precise Characterization of Vanadium Surface Species at Natural Abundance

Magnetic Memory from Site Isolated Dy(III) on Silica Materials

Density functional theory study of interactions between carbon dioxide and functionalized polyhedral oligomeric silsesquioxanes

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