Selective etching mechanism of silicon oxide against silicon by hydrogen fluoride: a density functional theory study.

Selective etching of silicon oxide (SiO2) against silicon (Si) using anhydrous hydrogen fluoride (HF) vapor has been used for semiconductor device fabrication. We studied the underlying mechanism of the selective etching by density functional theory (DFT) calculation. We constructed surface slab models of SiO2 or Si with different degrees of fluorination and simulated the four steps of fluorination. The calculations show relatively low activation energies of 0.72-0.79 eV for the four steps of fluorination of SiO2, which are close to ∼0.69 eV observed in the experiment. The four-membered ring structure of -Si-O-H-F- in all transition states stabilized the system, resulting in relatively low activation energies. Thus, continuous etching of SiO2 by HF is plausible at near-room temperature. In contrast, the fluorinations of Si showed relatively high activation energies ranging from 1.22 to 1.56 eV due to the less stable transition state geometries. Thus, negligible etching of silicon by HF is expected by the near-room temperature process. Our calculation results explain well the experimental observation of the selective etching of SiO2 against Si by HF vapor.

Correction: Solid-state nitrogen-doped carbon nanoparticles with tunable emission prepared by a microwave-assisted method.

[This corrects the article DOI: 10.1039/D1RA07290K.].

Solid-state nitrogen-doped carbon nanoparticles with tunable emission prepared by a microwave-assisted method.

Tunable emissive solid-state carbon nanoparticles (CNPs) have been successfully synthesized by a facile synthesis through microwave irradiation. Modulating microwave interaction with the sample to generate abrupt localized heating is a long-term challenge to tailor the photoluminescence properties of CNPs. This study systematically revealed that the sample temperature through microwave irradiation plays a crucial role in controlling the photoluminescence properties over other reaction conditions, such as irradiation time and microwave duty cycle. When the sample temperature reached 155 °C in less than three minutes, the CNP sample exhibited a green-yellowish emission with the highest quantum yield (QY) of 14.6%. Time-dependent density functional theory (TD-DFT) study revealed that the tunable photoluminescence properties of the CNPs can possibly be ascribed to their nitrogen concentrations, which were dictated by the sample temperature during irradiation. This study opens up a promising route for the well-controlled synthesis of luminescent CNPs through microwave irradiation.

Effect of H2SO4/H2O2 pre-treatment on electrochemical properties of exfoliated graphite prepared by an electro-exfoliation method.

The effect of pre-treating graphite sheets in a H2SO4/H2O2 solution before electro-exfoliation is reported. It was revealed that the volume fraction of H2SO4 to H2O2 during pre-treatment could control the degree of exfoliation of the resulting exfoliated graphite (EG). X-ray diffraction (XRD), Raman, and Fourier transform infrared (FTIR) spectroscopy analyses have suggested that EG produced by first pre-treating the graphite sheet in H2SO4/H2O2 solution with the H2SO4 : H2O2 volume fraction of 95 : 5 demonstrates the highest exfoliation degree. This sample also demonstrated excellent electrochemical properties with good electrical conductivity (36.22 S cm-1) and relatively low charge transfer resistance (R ct) of 21.35 Ω. This sample also showed the highest specific capacitance of all samples, i.e., 71.95 F g-1 at 1 mV s-1 when measured at a voltage range of -0.9 to 0 V. Further measurement at an extended potential window down to -1.4 V revealed the superior specific capacitance value of 150.69 F g-1. The superior morphology characteristics and the excellent electrical properties of the obtained EG are several reasons behind its exceptional properties. The pre-treatment of graphite sheets in H2SO4/H2O2 solution allegedly leads to easier and faster exfoliation. The faster exfoliation is allegedly able to prevent massive oxidation, which frequently induces the formation of graphite/graphene oxide (GO) in a prolonged process. However, too large H2O2 volume fraction involved during pre-treatment seems to cause excessive expansion and frail structure of the graphite sheets, which leads to an early breakdown of the structure during electrochemical exfoliation and prohibits layer by layer exfoliation.

Simultaneous ultraviolet and first near-infrared window absorption of luminescent carbon dots/PVA composite film.

Liquid Carbon Dots (CDs) were successfully synthesized by hydrothermal method using urea and citric acid as raw materials. TEM images confirmed that the CDs have a spherical shape with a homogeneous distribution. The as-prepared liquid CDs could absorb ultraviolet (UV) and first near infra-red (NIR) window simultaneously. However, the photoluminescence (PL) of the liquid CDs was damaged by their quenching effect. To overcome this issue, the liquid CDs were dispersed in poly(vinyl) alcohol (PVA) to fabricate the composite film. Herein, the dual-peak absorption properties of the CDs/PVA composite films were investigated for the first time. The composite films could maintain the simultaneous UV and first NIR window absorption property even after being preheated up to 200 °C, implying that the structure of CDs was well retained during the transition from the liquid to films. Daylight treatment for seven days produced minimum changes in the UV-vis and PL spectra, which indicates that the CDs/PVA film has more stable optical properties than the liquid CDs.