Activating Single-Atom Ni Site via First-Shell Si Modulation Boosts Oxygen Reduction Reaction.

Atomically dispersed nitrogen-coordinated 3d transition-metal site on carbon support (M-NC) are promising alternatives to Pt group metal-based catalysts toward oxygen reduction reaction (ORR). However, despite the excellent activities of most of M-NC catalysts, such as Fe-NC, Co-NC et al., their durability is far from satisfactory due to Fenton reaction. Herein, this work reports a novel Si-doped Ni-NC catalyst (Ni-SiNC) that possesses high activity and excellent stability. X-ray absorption fine structure and aberration-corrected transmission electron microscopy uncover that the single-atom Ni site is coordinated with one Si atom and three N atoms, constructing Ni-Si1 N3  moiety. The Ni-SiNC catalyst exhibits a half-wave potential (E1/2 ) of 0.866 V versus RHE, with a distinguished long-term durability in alkaline media of only 10 mV negative shift in E1/2  after 35 000 cycles, which is also validated in Zn-air battery. Density functional theory calculations reveal that the Ni-Si1 N3  moiety facilitates ORR kinetics through optimizing the adsorption of intermediates.

Superior Performances of Self-Driven Near-Infrared Photodetectors Based on the SnTe:Si/Si Heterostructure Boosted by Bulk Photovoltaic Effect.

The upsurge of new materials that can be used for near-infrared (NIR) photodetectors operated without cooling is crucial. As a novel material with a small bandgap of ≈0.28 eV, the topological crystalline insulator SnTe has attracted considerable attention. Herein, this work demonstrates self-driven NIR photodetectors based on SnTe/Si and SnTe:Si/Si heterostructures. The SnTe/Si heterostructure has a high detectivity D* of 3.3 × 1012 Jones. By Si doping, the SnTe:Si/Si heterostructure reduces the dark current density and increases the photocurrent by ≈1 order of magnitude simultaneously, which improves the detectivity D* by ≈2 orders of magnitude up to 1.59 × 1014 Jones. Further theoretical analysis indicates that the improved device performance may be ascribed to the bulk photovoltaic effect (BPVE), in which doped Si atoms break the inversion symmetry and thus enable the generation of additional photocurrents beyond the heterostructure. In addition, the external quantum efficiency (EQE) measured at room temperature at 850 nm increases by a factor of 7.5 times, from 38.5% to 289%. A high responsivity of 1979 mA W-1 without bias and fast rising time of 8 µs are also observed. The significantly improved photodetection achieved by the Si doping is of great interest and may provide a novel strategy for superior photodetectors.

Si Donor Incorporation in GaN Nanowires.

With increasing interest in GaN based devices, the control and evaluation of doping are becoming more and more important. We have studied the structural and electrical properties of a series of Si-doped GaN nanowires (NWs) grown by molecular beam epitaxy (MBE) with a typical dimension of 2-3 µm in length and 20-200 nm in radius. In particular, high resolution energy dispersive X-ray spectroscopy (EDX) has illustrated a higher Si incorporation in NWs than that in two-dimensional (2D) layers and Si segregation at the edge of the NW with the highest doping. Moreover, direct transport measurements on single NWs have shown a controlled doping with resistivity from 10(2) to 10(-3) Ω·cm, and a carrier concentration from 10(17) to 10(20) cm(-3). Field effect transistor (FET) measurements combined with finite element simulation by NextNano(3) software have put in evidence the high mobility of carriers in the nonintentionally doped (NID) NWs.

Si Doping Enables Activity and Stability Enhancement on Atomically Dispersed Fe-Nx /C Electrocatalysts for Oxygen Reduction in Acid.

Fe-N-C represents the most promising non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) in fuel cells, but often suffers from poor stability in acid due to the dissolution of metal sites and the poor oxidation resistance of carbon substrates. In this work, silicon-doped iron-nitrogen-carbon (Si/Fe-N-C) catalysts were developed by in situ silicon doping and metal-polymer coordination. It was found that Si doping could not only promote the density of Fe-Nx /C active sites but also elevated the content of graphitic carbon through catalytic graphitization. The best-performing Si/Fe-N-C exhibited a half-wave potential of 0.817 V vs. reversible hydrogen electrode in 0.5 m H2 SO4 , outperforming that of undoped Fe-N-C and most of the reported Fe-N-C catalysts. It also exhibited significantly enhanced stability at elevated temperature (≥60 °C). This work provides a new way to develop non-precious metal ORR catalysts with improved activity and stability in acidic media.

Growth Mechanism and Kinetics of Diamond in Liquid Gallium from Quantum Mechanics Molecular Dynamics Simulations.

Ruoff and co-workers recently demonstrated low-temperature (1193 K) homoepitaxial diamond growth from liquid gallium solvent. To develop an atomistic mechanism for diamond growth underlying this remarkable demonstration, we carried out density functional theory-based molecular dynamics (DFT-MD) simulations to examine the mechanism of single-crystal diamond growth on various low-index crystallographic diamond surfaces (100), (110), and (111) in liquid Ga with CH4. We find that carbon linear chains form in liquid Ga and then react with the growing diamond surface, leading first to the formation of carbon rings on the surface and then initiation of diamond growth. Our simulations find faster growth on the (110) surface than on the (100) or (111) surfaces, suggesting the (110) surface as a plausible growth surface in liquid Ga. For (110) surface growth, we predict the optimum growth temperature to be ∼1300 K, arising from a balance between the kinetics of forming carbon chains dissolved in Ga and the stability of carbon rings on the growing surface. We find that the rate-determining step for diamond growth is dehydrogenation of the growing hydrogenated (110) surface of diamond. Inspired by the recent experimental studies by Ruoff and co-workers demonstrating that Si accelerates diamond growth in Ga, we show that addition of Si into liquid Ga significantly increases the rate of dehydrogenating the growing surface. Extrapolating from the DFT-MD predicted rates at 2800 to 3500 K, we predict the growth rate at the experimental growth temperature of 1193 K, leading to rates in reasonable agreement with the experiment. These fundamental mechanisms should provide guidance in optimizing low-temperature diamond growth.

Demonstration of MOCVD-grown Ga2O3 power MOSFETs on sapphire with in-situ Si-doped by tetraethyl orthosilicate (TEOS).

In this work, we demonstrated Ga2O3-based power MOSFETs grown on c-plane sapphire substrates using in-situ TEOS doping for the first time. The ß-Ga2O3:Si epitaxial layers were formed by the metalorganic chemical vapor deposition (MOCVD) with a TEOS as a dopant source. The depletion-mode Ga2O3 power MOSFETs are fabricated and characterized, showing the increase of the current, transconductance, and breakdown voltage at 150 °C. In addition, the sample with the TEOS flow rate of 20 sccm exhibited a breakdown voltage of more than 400 V at RT and 150 °C, indicating that the in-situ Si doping by TEOS in MOCVD is a promising method for Ga2O3 power MOSFETs.

Efficient Si Doping Promoting Thermoelectric Performance of Yb-Filled CoSb3-Based Skutterudites.

Nanocomposites have become a widely popular way to assist in the enhancement of thermoelectric performance for filled skutterudites. Herein, we unveil the distinctive effect of Si doping on the classic Yb0.3Co4Sb12. On the one hand, the reduced Yb filling fraction is accompanied by the in-situ precipitated CoSi nanoparticles, which not only enhances the power factor in the intermediate-low temperature range but also reduces electronic thermal conductivity for decreasing the carrier concentration. On the other hand, CoSi nanoparticles intensively disrupt the phonon transport, hiding the increased lattice thermal conductivity due to reduced Yb filling fraction. Although the residual YbSb2 second phases have an adverse effect on the thermoelectric properties, the integration effects achieve a peak ZT value of 1.37 at 823 K and increase ZTave by 21% for the Yb0.3Co4Sb12/0.1Si sample.

Si-doped Al2O3 nanosheet supported Pd for catalytic combustion of propane: effects of Si doping on morphology, thermal stability, and water resistance.

Catalytic combustion of propane as typical light alkanes was important for the purification of industrial VOCs and automobile hydrocarbon emissions. Si-doped Al2O3 nanosheet was synthesized by a hydrothermal method, and effects of Si content on the morphology and thermal stability of Al2O3 were investigated. The doping of SiO2 could tune the thickness of Al2O3 nanosheets and significantly improve its thermal stability, the θ phase was still maintained, and the specific surface area was as high as 56.3 m2 g-1 after calcination at 1200 °C. And then the Si-doped Al2O3 nanosheets were used as support of Pd catalysts (Pd/Si-Al2O3 nanosheets) for catalytic combustion of propane, especially Pd/3.6Si-Al2O3 nanosheets, which presented high activity, stability, and resistance to sintering and H2O due to the promotion of Si on the thermal stability of Al2O3 and the stabilization (dispersion, isolation, and strong interaction) of PdOx species.

Detection of Si doping in the AlN/GaN MQW using Super X - EDS measurements.

A multiple-quantum-well structure consisting of 40 periods of AlN/GaN:Si was investigated using a transmission electron microscope equipped with energy-dispersive X-ray spectroscopy. The thicknesses of the AlN barriers and the GaN quantum wells were 4 nm and 6 nm, respectively. The QW layers were doped with Si to a concentration of 1.3×1019cm-3 (0.012 % at). The procedure for quantifying such a doping level using AlN as a standard is presented. The EDS results (0.013 % at) are compared with secondary ion mass spectrometry measurements (0.05 % at).

Oscillations of As Concentration and Electron-to-Hole Ratio in Si-Doped GaAs Nanowires.

III-V nanowires grown by the vapor-liquid-solid method often show self-regulated oscillations of group V concentration in a catalyst droplet over the monolayer growth cycle. We investigate theoretically how this effect influences the electron-to-hole ratio in Si-doped GaAs nanowires. Several factors influencing the As depletion in the vapor-liquid-solid nanowire growth are considered, including the time-scale separation between the steps of island growth and refill, the "stopping effect" at very low As concentrations, and the maximum As concentration at nucleation and desorption. It is shown that the As depletion effect is stronger for slower nanowire elongation rates and faster for island growth relative to refill. Larger concentration oscillations suppress the electron-to-hole ratio and substantially enhance the tendency for the p-type Si doping of GaAs nanowires, which is a typical picture in molecular beam epitaxy. The oscillations become weaker and may finally disappear in vapor deposition techniques such as hydride vapor phase epitaxy, where the n-type Si doping of GaAs nanowires is more easily achievable.

Si-doping increases the adjuvant activity of hydroxyapatite nanorods.

Recombinant protein-based vaccines generally show limited immunogenicity and need adjuvants to achieve robust immune responses. Herein, to combine the excellent biocompatibility of hydroxyapatite (HA) and exciting adjuvant activity of silica, Si-doped HA nanorods with Si/P molar ratio from 0 to 0.65 were hydrothermally synthesized and evaluated as immunoadjuvants. Si-doping decreases the size and increases the BET surface area of the nanorods. Si-doping in HA nanorods increases the in vitro adjuvant activity, including CD11c+CD86+ expression and cytokine secretion of bone marrow derived dendritic cells (BMDCs). Moreover, Si-doping in HA increases the ex vivo adjuvant activity as shown by the increase in both Th1 and Th2 cytokines secretion. Si-doped HA nanorods are promising as a new immunoadjuvant.

Sol-Gel Synthesis of Silicon-Doped Lithium Manganese Oxide with Enhanced Reversible Capacity and Cycling Stability.

A series of silicon-doped lithium manganese oxides were obtained via a sol-gel process. XRD characterization results indicate that the silicon-doped samples retain the spinel structure of LiMn2O4. Electrochemical tests show that introducing silicon ions into the spinel structure can have a great effect on reversible capacity and cycling stability. When cycled at 0.5 C, the optimal Si-doped LiMn2O4 can exhibit a pretty high initial capacity of 140.8 mAh g-1 with excellent retention of 91.1% after 100 cycles, which is higher than that of the LiMn2O4, LiMn1.975Si0.025O4, and LiMn1.925Si0.075O4 samples. Moreover, the optimal Si-doped LiMn2O4 can exhibit 88.3 mAh g-1 with satisfactory cycling performance at 10 C. These satisfactory results are mainly contributed by the more regular and increased MnO6 octahedra and even size distribution in the silicon-doped samples obtained by sol-gel technology.

Si-Doping Effects in Cu(In,Ga)Se2 Thin Films and Applications for Simplified Structure High-Efficiency Solar Cells.

We found that elemental Si-doped Cu(In,Ga)Se2 (CIGS) polycrystalline thin films exhibit a distinctive morphology due to the formation of grain boundary layers several tens of nanometers thick. The use of Si-doped CIGS films as the photoabsorber layer in simplified structure buffer-free solar cell devices is found to be effective in enhancing energy conversion efficiency. The grain boundary layers formed in Si-doped CIGS films are expected to play an important role in passivating CIGS grain interfaces and improving carrier transport. The simplified structure solar cells, which nominally consist of only a CIGS photoabsorber layer and a front transparent and a back metal electrode layer, demonstrate practical application level solar cell efficiencies exceeding 15%. To date, the cell efficiencies demonstrated from this type of device have remained relatively low, with values of about 10%. Also, Si-doped CIGS solar cell devices exhibit similar properties to those of CIGS devices fabricated with post deposition alkali halide treatments such as KF or RbF, techniques known to boost CIGS device performance. The results obtained offer a new approach based on a new concept to control grain boundaries in polycrystalline CIGS and other polycrystalline chalcogenide materials for better device performance.

Effects of Silicon on Osteoclast Cell Mediated Degradation, In Vivo Osteogenesis and Vasculogenesis of Brushite Cement.

Calcium phosphate cements (CPCs) are being widely used for treating small scale bone defects. Among the various CPCs, brushite (dicalcium phosphate dihydrate, DCPD) cement is widely used due to its superior solubility and ability to form new bone. In the present study, we have studied the physical, mechanical, osteoclast-like-cells differentiation and in vivo osteogenic and vasculogenic properties of silicon (Si) doped brushite cements. Addition of Si did not alter the phase composition of final product and regardless of Si level, all samples included ß-tricalcium phosphate (ß-TCP) and DCPD. 1.1 wt. % Si addition increased the compressive strength of undoped brushite cement from 4.78±0.21 MPa to 5.53±0.53 MPa, significantly. Cellular activity was studied using receptor activator of nuclear factor κß ligand (RANKL) supplemented osteoclast-like-cells precursor RAW 264.7 cell. Phenotypic expressions of the cells confirmed successful differentiation of RAW264.7 monocytes to osteoclast-like-cells on undoped and doped brushite cements. An increased activity of osteoclast-like cells was noticed due to Si doping in the brushite cement. An excellent new bone formation was found in all cement compositions, with significant increase in Si doped brushite samples as early as 4 weeks post implantation in rat femoral model. After 4 weeks of implantation, no significant difference was found in blood vessel formation between the undoped and doped cements, however, a significant increase in vasculgenesis was found in 0.8 and 1.1 wt. % Si doped brushite cements after 8 weeks. These results show the influence of Si dopant on physical, mechanical, in vitro osteoclastogenesis and in vivo osteogenic and vasculogenic properties of brushite cements.

Enhanced current transport and injection in thin-film gallium-nitride light-emitting diodes by laser-based doping.

This paper reports improvements in the electrical and optical properties of blue-emission gallium nitride (GaN)-based thin-film light-emitting diodes (TFLEDs) after laser-based Si doping (LBSD) of a nitrogen-face n-GaN (denoted as hereafter n-GaN) layer. Experimental results show that the light-output powers of the flat- and rough-surface TFLEDs after LBSD are 52.1 and 11.35% higher than those before LBSD, respectively, at a current of 350 mA, while the corresponding operating voltages are decreased by 0.22 and 0.28 V for the flat- and rough-surface TFLEDs after LBSD, respectively. The reduced operating voltage after LBSD of the top n-GaN layer may result from the remarkably decreased specific contact resistance at the metal/n-GaN interface and the low series resistance of the TFLED device. The LBSD of n-GaN increases the number of nitrogen vacancies, and Si substitutes for Ga (SiGa) at the metal/n-GaN interface to produce highly Si-doped regions in n-GaN, leading to a decrease in the Schottky barrier height and width. As a result, the specific contact resistances are significantly decreased to 1.56 × 10(-5) and 2.86 × 10(-5) Ω cm(2) for the flat- and rough-surface samples after LBSD, respectively. On the other hand, the increased light-output power after LBSD can be explained by the uniform current spreading, efficient current injection, and enhanced light scattering resulting from the low contact resistivity, low lateral current resistance, and additional textured surface, respectively. Furthermore, LBSD did not degrade the electrical properties of the TFLEDs owing to low reverse leakage currents. The results indicate that our approach could potentially enable high-efficiency and high-power capabilities for optoelectronic devices.

Ferroelectricity in Si-doped HfO2 revealed: a binary lead-free ferroelectric.

Static domain structures and polarization dynamics of silicon doped HfO2 are explored. The evolution of ferroelectricity as a function of Si-doping level driving the transition from paraelectricity via ferroelectricity to antiferroelectricity is investigated. Ferroelectric and antiferroelectric properties can be observed locally on the pristine, poled and electroded surfaces, providing conclusive evidence to intrinsic ferroic behavior.