High-Performance Li-CO2 Battery Based on Carbon-Free Porous Ru@QNFs Cathode.

Lithium-carbon dioxide (Li-CO2 ) batteries have attracted much attention due to their high theoretical energy density. However, due to the existance of lithium carbonate and amorphous carbon in the discharge products that are difficult to decompose, the battery shows low coulombic efficiency and poor cycle performance. Here, by adjusting the adsorption of carbon dioxide (CO2 ) on ruthenium (Ru) catalysts surface, this work reports an ultralow charge overpotential and long cycle life Li-CO2 battery that consists of typical lithium metal, ternary molten salt electrolyte (TMSE), and Ru-based cathode. Experimental results show that the Ru catalysts deposited on quartz nanofiber (QF) can suppress the four-electron conversion of CO2 to lithium carbonate (Li2 CO3 ). As a result, the battery shows a long-cycle-life of over 457 cycles at 1.0 A g-1 with a limited capacity of 500 mAh g-1 Ru . Remarkably, a recorded low discharge potential of ≈3.0 V has been achieved after 35 cycles at 0.5 A g-1 , with a charge potential retention of over 99%. Moreover, the battery can operate over 25 A g-1 and recover 96% potential. This battery technology paves the way for designing high-performance rechargeable Li-CO2 batteries with carbon neutrality.

Highly efficient electroluminescence from SnO2 nanocrystals and Er3+ co-doped silica thin film via introducing Ca2.

Efficient and stable near-infrared silicon-based light source is a challenge for future optoelectronic integration and interconnection. In this paper, alkaline earth metal Ca2+ doped SiO2-SnO2: Er3+ films were prepared by sol-gel method. The oxygen vacancies introduced by the doped Ca2+ significantly increase the near-infrared luminescence intensity of Er3+ ions. It was found that the doping concentration of Sn precursors not only modulate the crystallinity of SnO2 nanocrystals but also enhance the luminescence performance of Er3+ ions. The stable electroluminescent devices based on SiO2-SnO2: Er3+/Ca2+ films exhibit the power efficiency as high as 1.04×10-2 with the external quantum efficiency exceeding 10%.

Experimental observations on metal-like carrier transport and Mott hopping conduction behaviours in boron-doped Si nanocrystal multilayers.

Studies on the carrier transport characteristics of semiconductor nanomaterials are the important and interesting issues which are helpful for developing the next generation of optoelectronic devices. In this work, we fabricate B-doped Si nanocrystals/SiO2multilayers by plasma enhanced chemical vapor deposition with subsequent high temperature annealing. The electronic transport behaviors are studied via Hall measurements within a wide temperature range (30-660 K). It is found that when the temperature is above 300 K, all the B-doped Si nanocrystals with the size near 4.0 nm exhibit the semiconductor-like conduction characteristics, while the conduction of Si nanocrystals with large size near 7.0 nm transforms from semiconductor-like to metal-like at high B-doping ratios. The critical carrier concentration of conduction transition can reach as high as 2.2 × 1020cm-3, which is significantly higher than that of bulk counterpart and may be even higher for the smaller Si nanocrystals. Meanwhile, the Mott variable-range hopping dominates the carrier transport when the temperature is below 100 K. The localization radius of carriers can be regulated by the B-doping ratios and Si NCs size, which is contributed to the metallic insulator transition.

A stable solid-state lithium-oxygen battery enabled by heterogeneous silicon-based interface.

Solid-state lithium-metal batteries using inorganic solid-state electrolyte (SSE) instead of liquid-electrolyte, especially lithium-oxygen (Li-O2) battery, have attracted much more attention due to their high-energy density and safety. However, the poor interface contact between electrodes and SSEs makes these batteries lose most of their capacity and power during cycling. Here we report that by coating a heterogeneous silicon carbide on lithium metal anode and Li1.5Al0.5Ge1.5P3O12(LAGP)-SSE, a good interface contact is created between the electrode and electrolyte that can effectively reduce the interface impedance and improve the cycle performance of the assembled battery. As a result, the solid-sate Li-O2battery demonstrates a cycle lifespan of ∼78 cycles being at least 3-times higher than the solid-state Li-O2battery without silicon carbide with a capacity limitation of 1000 mAh g-1at 250 mA g-1. The characterization of discharge products indicates a typical two-electron convention of oxygen-to-lithium oxide for the solid-state Li-O2battery system. This work paves a way for developing high-energy long-cycle solid-state lithium-metal battery. The work provides insights into the interface between the Li-metal and SSE to develop high-energy long-cycle all solid-state Li-metal batteries.

Alkaline earth metal ion doping to enhance the light emission from Er3+:SnO2 nanocrystal Co-doped silica films.

Alkaline earth metal ions (Mg2+, Ca2+, Sr2+) have been introduced into Er3+:SnO2 nanocrystal co-doped silica thin films fabricated by a sol-gel method combined with a spin-coating technique. It is found that the incorporation of alkaline earth metal ions can enhance the light emission from Er3+ at the wavelength around 1540 nm and the strongest enhancement is observed in samples doped with 5 mol% Sr2+ ions. Based on X-ray diffraction, X-ray photoelectron spectroscopy and other spectroscopic measurements, the improved light emission can be attributed to more oxygen vacancies, better crystallinity and a stronger cross-relaxation process with the introduction of alkaline earth metal ions.

Designable Integration of Silicide Nanowire Springs as Ultra-Compact and Stretchable Electronic Interconnections.

Stretchable electronics are finding widespread applications in bio-sensing, skin-mimetic electronics, and flexible displays, where high-density integration of elastic and durable interconnections is a key capability. Instead of forming a randomly crossed nanowire (NW) network, here, a large-scale and precise integration of highly conductive nickel silicide nanospring (SiNix -NS) arrays are demonstrated, which are fabricated out of an in-plane solid-liquid-solid guided growth of planar Si nanowires (SiNWs), and subsequent alloy-forming process that boosts the channel conductivity over 4 orders of magnitude (to 2 × 104 S cm-1 ). Thanks to the narrow diameter of the serpentine SiNix -NS channels, the elastic geometry engineering can be accomplished within a very short interconnection distance (down to ≈3 µm), which is crucial for integrating high-density displays or logic units in a rigid-island and elastic-interconnection configuration. Deployed over soft polydimethylsiloxane thin film substrate, the SiNix -NS array demonstrates an excellent stretchability that can sustain up to 50% stretching and for 10 000 cycles (at 15%). This approach paves the way to integrate high-density inorganic electronics and interconnections for high-performance health monitoring, displays, and on-skin electronic applications, based on the mature and rather reliable Si thin film technology.

Ultra-Confined Catalytic Growth Integration of Sub-10 nm 3D Stacked Silicon Nanowires Via a Self-Delimited Droplet Formation Strategy.

Fabricating ultrathin silicon (Si) channels down to critical dimension (CD) <10 nm, a key capability to implementing cutting-edge microelectronics and quantum charge-qubits, has never been accomplished via an extremely low-cost catalytic growth. In this work, 3D stacked ultrathin Si nanowires (SiNWs) are demonstrated, with width and height of Wnw  = 9.9 ± 1.2 nm (down to 8 nm) and Hnw  = 18.8 ± 1.8 nm, that can be reliably grown into the ultrafine sidewall grooves, approaching to the CD of 10 nm technology node, thanks to a new self-delimited droplet control strategy. Interestingly, the cross-sections of the as-grown SiNW channels can also be easily tailored from fin-like to sheet-like geometries by tuning the groove profile, while a sharply folding guided growth indicates a unique capability to produce closely-packed multiple rows of stacked SiNWs, out of a single run growth, with the minimal use of catalyst metal. Prototype field effect transistors are also successfully fabricated, achieving Ion/off ratio and sub-threshold swing of >106 and 125 mV dec-1 , respectively. These results highlight the unexplored potential of versatile catalytic growth to compete with, or complement, the advanced top-down etching technology in the exploitation of monolithic 3D integration of logic-in-memory, neuromorphic and charge-qubit applications.

Enhanced subband light emission from Si quantum dots/SiO2 multilayers via phosphorus and boron co-doping.

Seeking light sources from Si-based materials with an emission wavelength meeting the requirements of optical telecommunication is a challenge nowadays. It was found that the subband emission centered near 1200 nm can be achieved in phosphorus-doped Si quantum dots/SiO2 multilayers. In this work, we propose the phosphorus/boron co-doping in Si quantum dots/SiO2 multilayers to enhance the subband light emission. By increasing the B co-doping ratio, the emission intensity is first increased and then decreased, while the strongest integrated emission intensity is almost two orders of magnitude stronger than that of P solely-doped sample. The enhanced subband light emission in co-doped samples can be attributed to the passivation of surface dangling bonds by B dopants. At high B co-doping ratios, the samples transfer to p-type and the subband light emission from phosphorus-related deep level is suppressed but the emission centered around 1400 nm is appeared.

Superfast Growth Dynamics of High-Quality Silicon Nanowires on Polymer Films via Self-Selected Laser-Droplet-Heating.

Growing high quality silicon nanowires (SiNWs) at elevated temperature on cooler polymer films seems to be contradictive but highly desirable for building high performance flexible and wearable electronics. In this work, we demonstrate a superfast (vnw > 3.5 µm·s-1) growth of high quality SiNWs on polymer/glass substrates, powered by self-selected laser at 808 nm heating of indium catalyst droplets that absorb amorphous Si layer to produce SiNWs. Because of the tiny heat capacity of the nanodroplets, the SiNW growth can be quickly heated up and frozen via rapid laser ON/OFF switching, enabling a deterministic diameter modulation in the ultralong SiNWs. Finally, prototype field effect transistors are also fabricated upon the laser-droplet-heating grown SiNWs with a high Ion/Ioff ratio of >104 and reasonable subthreshold swing of 386 mV·dec-1, opening a generic new route to integrate high-quality NW channels directly upon large area and lightweight polymer substrates for developing high-performance flexible electronics.

Ab Initio Design, Shaping, and Assembly of Free-Standing Silicon Nanoprobes.

Free-standing silicon nanoprobes (SiNPs) are critical tools for intracellular bioelectrical signal recording, while a scalable fabrication of these tiny SiNPs with ab initio geometry designs has not been possible. In this work, we demonstrate a novel growth shaping of slim Si nanowires (SiNWs) into SiNPs with sharp tips (curvature radii <300 nm), tunable angles of 30°, 60°, to 120° and even programmable triangle/circular shapes. A precise growth integration of orderly single, double, and quadruple SiNPs at prescribed locations enables convenient electrode connection, transferring and mounting these tiny tips onto movable arms to serve as long-protruding (over 4-20 µm) nanoprobes. Mechanical flexibility, resilience, and field-effect sensing functionality of the SiNPs were systematically testified in liquid nanodroplet and cell environments. This highly reliable and economic manufacturing of advanced SiNPs holds a strong potential to boost and open up the market implementations of a wide range of intracellular sensing, monitoring, and editing applications.

Terrace-confined guided growth of high-density ultrathin silicon nanowire array for large area electronics.

Ultrathin silicon nanowires (SiNWs) are ideal 1D channels to construct high performance nanoelectronics and sensors. We here report on a high-density catalytic growth of orderly ultrathin SiNWs, with diameter down toDnw=27±2nmand narrow NW-to-NW spacing of onlySnw âˆ¼80 nm, without the use of high-resolution lithography. This has been accomplished via a terrace-confined strategy, where tiny indium (In) droplets move on sidewall terraces to absorb precoated amorphous Si layer as precursor and produce self-aligned SiNW array. It is found that, under proper parameter control, a tighter terrace-step confinement can help to scale the dimensions of the SiNW array down to the extremes that have not been reported before, while maintaining still a stable guiding growth over complex contours. Prototype SiNW field effect transistors demonstrate a highIon/Ioffcurrent ratio ∼107, low leakage current of ∼0.3 pA and steep subthreshold swing of 220 mV dec-1. These results highlight the unexplored potential of catalytic growth in advanced nanostructure fabrication that is highly relevant for scalable SiNW logic and sensor applications.

Multiple channels to enhance near-infrared emission from SiO2-SnO2:Er3+ films by Ba2+ ion doping.

Ba2+ ions co-doped SiO2-SnO2:Er3+ thin films are prepared using a sol-gel method combined with a spin-coating technique and post-annealing treatment. The influence of Ba2+ ion doping on the photoluminescence properties of thin films is carefully investigated. The enhancement of near-infrared (NIR) emission of Er3+ ions by as much as 12 times is obtained via co-doping with Ba2+ ions. To illustrate the relevant mechanisms, X-ray diffraction, X-ray photoelectron spectroscopy and comprehensive spectroscopic measurements are carried out. The enhanced NIR emission induced by Ba2+ co-doping can be explained by more oxygen vacancies, improved crystallinity and strong cross-relaxation processes between Er3+ ions. The incorporation of Ba2+ ions into SiO2-SnO2:Er3+ thin films results in a considerable enhancement in the NIR emission, making the thin films more suitable for Si-based optical lasers and amplifiers.

Unprecedented Uniform 3D Growth Integration of 10-Layer Stacked Si Nanowires on Tightly Confined Sidewall Grooves.

Bottom-up catalytic growth offers a high-yield, versatile, and powerful tool for the construction of versatile 3D nanocomplexes, while the major challenge is to achieve a precise location and uniformity control, as guaranteed by top-down lithography. Here, an unprecedented uniform and reliable growth integration of 10-layer stacked Si nanowires (SiNWs) has been accomplished, for the very first time, via a new groove-confined and tailored catalyst formation and guided growth upon the truncated sidewall of SiO2/SiNx multilayers. The SiNW array accomplishes a narrow diameter of Dnw = 28 ± 2.4 nm, NW-to-NW spacing of tsp = 40 nm, and extremely stable growth over Lnw > 50 µm and bending locations, which can compete with or even outperform the state-of-the-art top-down lithography and etching approaches, in terms of stacking number, channel uniformity at different levels, fabrication cost, and efficiency. These results provide a solid basis to establish a new 3D integration approach to batch-manufacture various advanced electronic and sensor applications.

Cylindrical Line-Feeding Growth of Free-Standing Silicon Nanohelices as Elastic Springs and Resonators.

Three-dimensional (3D) construction of free-standing silicon (Si) nanohelices has been a formidable challenge for planar lithography and etching technology. We here demonstrate a convenient 3D growth and integration of Si nanohelices (SiNHs) upon bamboolike cylinders with corrugated sidewall grooves, where the indium catalyst droplets grow around the cylinders in a helical fashion, while consuming precoated amorphous Si (a-Si) thin film to produce crystalline Si nanowires on the sidewalls. At the end of each groove cycle, the droplets are enforced to linefeed/switch into the neighbor groove to continue a spiral growth of SiNHs with readily tunable diameter, pitch, aspect-ratio, and chiral/achiral symmetries. In addition, the SiNHs can be reliably released as free-standing units to serve as elastic links, supports and vibrational resonators. These results highlight the unexplored potential of high precision 3D self-assembly growth in constructing a wide range of sophisticated electromechanical, sensor, and optoelectronic functionalities.

Low power consumption light emitting device containing TiO2:Er3+ thin film prepared by sol-gel method.

Er3+ ions doped titanium dioxide (TiO2) thin films have been prepared by sol-gel method. The photoluminescence both in visible light range (510-580 nm and 640-690 nm) and near infrared light range (1400-1700nm) have been observed. The photoluminescence excitation spectra demonstrate that energy transfer from wide band-gap TiO2 to Er3+ ions causes the infrared light emission. It is also found that the post annealing temperature can influence the luminescence intensity significantly. Based on sol-gel prepared TiO2:Er3+ thin films, we fabricate light emitting device containing ITO/TiO2:Er3+/SiO2/n+-Si/Al structure. Both the visible and near infrared electroluminescence (EL) can be detected under the operation voltage as low as 5.6 V and the working current of 0.66 mA, which shows the lower power consumption compared with the conventional EL devices.

Germanium quantum dot infrared photodetectors addressed by self-aligned silicon nanowire electrodes.

Germanium quantum dots (GeQDs), addressed by self-aligned and epitaxial silicon nanowires (SiNWs) as electrodes, represent the most fundamental and the smallest units that can be integrated into Si optoelectronics for 1550 nm wavelength detection. In this work, individual GeQD photodetectors have been fabricated based on a low temperature self-condensation of uniform amorphous Si (a-Si)/a-Ge bilayers at 300 °C, led by rolling indium (In) droplets. Remarkably, the diameter of the GeQD nodes can be independently controlled to achieve wider GeQDs for maximizing infrared absorption with narrower SiNW electrodes to ensure a high quality Ge/Si hetero-epitaxial connection. Importantly, these hetero GeQD/SiNW photodetectors can be deployed into predesigned locations for scalable device fabrication. The photodetectors demonstrate a responsivity of 1.5 mA W-1 and a photoconductive gain exceeding 102 to the communication wavelength signals, which are related to the beneficial type-II Ge/Si alignment, gradient Ge/Si epitaxial transition and a larger QD/NW diameter ratio. These results indicate a new approach to batch-fabricate and integrate GeQDs for ultra-compact Si-compatible photodetection and imaging applications.

Monolithic Integration of Silicon Nanowire Networks as a Soft Wafer for Highly Stretchable and Transparent Electronics.

Assembling nanoscale building blocks into an orderly network with a programmable layout and channel designs represents a critical capability to enable a wide range of stretchable electronics. Here, we demonstrate the growth-in-place integration of silicon nanowire (SiNW) springs into highly stretchable, transparent, and quasicontinuous functional networks with a close to unity interconnection among the discrete electrode joints because of a unique double-lane/double-step guiding edge design. The SiNW networks can be reliably transferred to a soft elastomer substrate, conformally attached to highly curved surfaces, or deployed as self-supporting/movable membranes suspended over voids. A high stretchability of >40% is achieved for the SiNW network on an elastomer, which can be employed as a transparent and semiconducting thin-film material endowed with a high carrier mobility of >50 cm2/(V s), Ion/Ioff ratio >104, and a tunable transmission of >80% over a wide spectrum range. Reversibly stretchable and bendable sensors based on the SiNW network have been successfully demonstrated, where the local strain distribution within the spring network can be directly observed and analyzed by finite element simulations. This SiNW network has a unique potential to eventually establish a new generically purposed waferlike platform for constructing soft electronics with Si-based hard performances.

Coupled boron-doping and geometry control of tin-catalyzed silicon nanowires for high performance radial junction photovoltaics.

Geometry and doping control in silicon nanowires (SiNWs) are both crucial aspects in fabricating three-dimensional (3D) radial junction thin film solar cells, while the coupling between them remains a peculiar aspect to be better understood. In this work, we focus on the geometry evolution and the doping effects realized in tin-catalyzed SiNWs grown via a plasma-enhanced vapor-liquid-solid procedure by using different diborane (B2H6) dopant flows. It is shown that with the increase of B2H6 flow rate from 0.3 to 2.1 SCCM, the radial growth of SiNWs is greatly accelerated by more than 30%, while the length is shortened to 50%. This can be related to the enhanced chemisorption probability of SiHx radicals, with the addition of B2H6, on the SiNW sidewall during silane (SiH4) plasma deposition in PECVD system, which leads to easier nucleation directly on the sidewalls and faster radial expansion of the SiNWs. A trade-off has to be sought between seeking a strong light trapping and ensuring a sufficient doping for high-quality PIN junction with the increase of B2H6 doping flow. These new understandings lay a critical basis for understanding and searching for an optimal growth control for constructing high-performance 3D radial junction thin-film solar cells.

Plasmon-enhanced upconversion luminescence in pyrochlore phase Yb x Er2-x Ti2O7 thin film.

Pyrochlore phase Yb x Er2-x Ti2O7 (YETO) thin films have been prepared by employing a facile sol-gel method combining with spin-coating technique and post-annealing treatment at 700 °C. High concentration of Yb3+ ions can promote the transformation from Yb3+/Er3+ co-doped anatase phase TiO2 to pyrochlore phase YETO at 700 °C temperature. We find that the YETO thin film with 30 mol% Yb3+ ions exhibits the brightest upconversion (UC) emission. Moreover, the introduction of Au nanorods (Au NRs) in the YETO thin film can further enhance the UC fluorescence. By adjusting the density of Au NRs, the UC emission intensity is increased by about 2.8-fold due to the excitation field enhancement caused by the localized surface plasmon resonance effect.

Hybrid channel induced forming-free performance in nanocrystalline-Si:H/a-SiNx:H resistive switching memory.

The unique forming-free feature of Si-based resistive switching memory plays a key role in the industrialization of next generation memory in the nanoscale. Here we report on a new forming-free nanocrystalline-Si:H (nc-Si:H)/SiNx:H resistive switching memory that can be obtained by deposition of hydrogen diluted nc-Si on hydrogen plasma treated a-SiNx:H layer. It is found that nc-Si dots with areal density of 5.6 × 1012/cm2 exist in nc-Si:H sublayer. Si dangling bonds (DBs) of volume density of 4.13 × 1023 cm-3 are produced in the a-SiNx:H sublayer. Temperature dependent current characteristic and theoretical calculations further reveal that hybrid channel of nc-Si and Si dangling bonds are the origin of the forming-free performance of nc-Si:H/SiNx:H resistive switching memory, which obey the trap assisted tunneling model at the low resistance state and P-F model at the high resistance state. Our discovery of hybrid channel supplies a new way to make Si-based RRAM be used in high density memory in the future.