Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for obtaining precise information about the local bonding of materials, but difficult to interpret without a well-vetted dataset of reference spectra. The ability to predict NMR parameters and connect them to three-dimensional local environments is critical for understanding more complex, long-range interactions. New computational methods have revealed structural information available from29Si solid-state NMR by generating computed reference spectra for solids. Such predictions are useful for the identification of new silicon-containing compounds, and serve as a starting point for determination of the local environments present in amorphous structures. In this study, we have used 42 silicon sites as a benchmarking set to compare experimentally reported29Si solid-state NMR spectra with those computed by CASTEP-NMR and Vienna Ab Initio Simulation Program (VASP). Data-driven approaches enable us to identify the source of discrepancies across a range of experimental and computational results. The information from NMR (in the form of an NMR tensor) has been validated, and in some cases corrected, in an effort to catalog these for the local spectroscopy database infrastructure (LSDI), where over 10,00029Si NMR tensors for crystalline materials have been computed. Knowledge of specific tensor values can serve as the basis for executing NMR experiments with precision, optimizing conditions to capture the elements accurately. The ability to predict and compare experimental observables from a wide range of structures can aid researchers in their chemical assignments and structure determination, since the computed values enables the extension beyond tables of typical chemical shift (or shielding) ranges.
- Award ID(s):
- 1743701
- NSF-PAR ID:
- 10076537
- Date Published:
- Journal Name:
- Materials
- Volume:
- 11
- Issue:
- 9
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 1646
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Silicon nitride (Si3N4) is a promising substrate for high-power electronics due to its superior mechanical properties and potential outstanding thermal conductivity (κ). As experiments keep pushing the upper limit of κ of Si3N4, it is believed that it can reach 450 W/mK, similar to SiC, based on classical models and molecular dynamics simulations. In this work, we reveal from first principles that the theoretical κ upper limits of β-Si3N4 are only 169 and 57 W/mK along the c and a axes at room temperature, respectively. Those of α-Si3N4 are about 116 and 87 W/mK, respectively. The predicted temperature-dependent κ matches well with the highest available experimental data, which supports the accuracy of our calculations, and suggests that the κ upper limit of Si3N4 has already been reached in the experiment. Compared to other promising semiconductors (e.g., SiC, AlN, and GaN), Si3N4 has a much lower κ than expected even though the chemical bonding and mechanical strengths are close or even stronger. We find the underlying reason is that Si3N4 has much lower phonon lifetimes and mean free paths (<0.5 μm) due to the larger three-phonon scattering phase space and stronger anharmonicity. Interestingly, we find that the larger unit cell (with more basis atoms) that leads to a smaller fraction of acoustic phonons is not the reason for lower κ. Grain size-dependent κ indicates that the grain boundary scattering plays a negligible role in most experimental samples. This work clarifies the theoretical κ upper limits of Si3N4 and can guide experimental research.
-
null (Ed.)The origin in deshielding of 29 Si NMR chemical shifts in R 3 Si–X, where X = H, OMe, Cl, OTf, [CH 6 B 11 X 6 ], toluene, and O X (O X = surface oxygen), as well as i Pr 3 Si + and Mes 3 Si + were studied using DFT methods. At the M06-L/6-31G(d,p) level of theory the geometry optimized structures agree well with those obtained experimentally. The trends in 29 Si NMR chemical shift also reproduce experimental trends; i Pr 3 Si–H has the most shielded 29 Si NMR chemical shift and free i Pr 3 Si + or isolable Mes 3 Si + have the most deshielded 29 Si NMR chemical shift. Natural localized molecular orbital (NLMO) analysis of the contributions to paramagnetic shielding ( σ p ) in these compounds shows that Si–R (R = alkyl, H) bonding orbitals are the major contributors to deshielding in this series. The Si–R bonding orbitals are coupled to the empty p-orbital in i Pr 3 Si + or Mes 3 Si + , or to the orbital in R 3 Si–X. This trend also applies to surface bound R 3 Si–O X . This model also explains chemical shift trends in recently isolated t Bu 2 SiH 2 + , t BuSiH 2 + , and SiH 3 + that show more shielded 29 Si NMR signals than R 3 Si + species. There is no correlation between isotropic 29 Si NMR chemical shift and charge at silicon.more » « less
-
more » « less
Abstract 2D van der Waals (vdW) magnets open landmark horizons in the development of innovative spintronic device architectures. However, their fabrication with large scale poses challenges due to high synthesis temperatures (>500 °C) and difficulties in integrating them with standard complementary metal‐oxide semiconductor (CMOS) technology on amorphous substrates such as silicon oxide (SiO2) and silicon nitride (SiN
x ). Here, a seeded growth technique for crystallizing CrTe2films on amorphous SiNx /Si and SiO2/Si substrates with a low thermal budget is presented. This fabrication process optimizes large‐scale, granular atomic layers on amorphous substrates, yielding a substantial coercivity of 11.5 kilo‐oersted, attributed to weak intergranular exchange coupling. Field‐driven Néel‐type stripe domain dynamics explain the amplified coercivity. Moreover, the granular CrTe2devices on Si wafers display significantly enhanced magnetoresistance, more than doubling that of single‐crystalline counterparts. Current‐assisted magnetization switching, enabled by a substantial spin–orbit torque with a large spin Hall angle (85) and spin Hall conductivity (1.02 × 107ℏ/2e Ω⁻¹ m⁻¹), is also demonstrated. These observations underscore the proficiency in manipulating crystallinity within integrated 2D magnetic films on Si wafers, paving the way for large‐scale batch manufacturing of practical magnetoelectronic and spintronic devices, heralding a new era of technological innovation. -
more » « less
ABSTRACT We report isotope data for C, N, Al, Si, and S of 33 presolar SiC and Si3N4 grains (0.3–1.6 $\mu$m) of Type X, C, D, and N from the Murchison CM2 meteorite of likely core-collapse supernova (CCSN) origin which we discuss together with data of six SiC X grains from an earlier study. The isotope data are discussed in the context of hydrogen ingestion supernova (SN) models. We have modified previously used ad-hoc mixing schemes in that we considered (i) heterogeneous H ingestion into the He shell of the pre-SN star, (ii) a variable C-N fractionation for the condensation of SiC grains in the SN ejecta, and (iii) smaller mass units for better fine-tuning. With our modified ad-hoc mixing approach over small scales (0.2–0.4 M⊙), with major contributions from the O-rich O/nova zone, we find remarkably good fits (within a few per cent) for 12C/13C, 26Al/27Al, and 29Si/28Si ratios. The 14N/15N ratio of SiC grains can be well matched if variable C-N fractionation is considered. However, the Si3N4 isotope data point to overproduction of 15N in hydrogen ingestion CCSN models and lower C-N fractionation during SiC condensation than applied here. Our ad-hoc mixing approach based on current CCSN models suggests that the O-rich O/nova zone, which uniquely combines explosive H- and He-burning signatures, is favourable for SiC and Si3N4 formation. The effective range of C/O abundance variations in the He shell triggered by H ingestion events in the massive star progenitor is currently not well constrained and needs further investigation.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/ma11091646
