基于抛光基材的热蒸镀铜箔生长高平整单层石墨烯薄膜

在石墨烯的化学气相沉积工艺中,铜箔是决定石墨烯薄膜质量的重要因素。传统铜箔由于制备工艺的限制,存在大量的缺陷,导致石墨烯薄膜的成核密度较高。本工作选用抛光铝板、抛光不锈钢板、微晶玻璃和SiO₂/Si作为基材,用热蒸镀法制备了不同粗糙度的铜箔,并详细讨论了以该系列铜箔生长高平整度石墨烯薄膜的条件及铜箔对石墨烯薄膜品质的影响。实验结果表明,铜箔以(111)取向为主,与基材分离后,表面具有纳米级平整度。在生长石墨烯后,从SiO₂/Si剥离的铜箔成核密度是4种基材中最小的。同时,从SiO₂/Si剥离的铜箔晶体结构变化最不明显,具有良好的结晶性,表面几乎不存在铜晶界缺陷。当压强为3 000 Pa,氢气和甲烷流速分别为300 mL/min和0.5 mL/min时,可以获得约1 mm横向尺寸的石墨烯单晶晶畴。     

Comprehensive performance of a ball-milled La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al magnetocaloric composite

Due to the hydrogen embrittlement effect, La(Fe,Si)₁₃-based hydrides can only exist in powder form, which limits their practical application. In this work, ductile and thermally conductive Al metal was homogeneously mixed with La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2 using the ball milling method. Then hydrogenation and compactness shaping of the magnetocaloric composites were performed in one step via a sintering process under high hydrogen pressure. As the Al content reached 9 wt.%, the La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2H_y/Al composite showed the mechanical behavior of a ductile material with a yield strength of ~44 MPa and an ultimate strength of 269 MPa accompanied by a pronounced improvement in thermal conductivity. Due to the ease of formation of Fe-Al-Si phases and the several micron and submicron sizes of the composite particles caused by ball milling process, the magnetic entropy change of the composites was substantially reduced to ~1.2 J/kg· K-1.5 J/kg· K at 0 T-1.5 T.     

Multifunctional Sulfur-Hyperdoped Silicon Nanoparticles with Engineered Mid-Infrared Sulfur-Impurity and Free-Carrier Absorption

Si nanoparticles (NPs), which are innovative promising light-harvesting components of thin-film solar cells and key-enabling biocompatible theranostic elements of infrared-laser and radiofrequency hyperthermia-based therapies of cancer cells in tumors and metastases, are significantly advanced in their near/mid-infrared band-to-band and free-carrier absorption via donor sulfur-hyperdoping during high-throughput facile femtosecond-laser ablative production in liquid carbon disulfide. High-resolution transmission electron microscopy and Raman microscopy reveal their mixed nanocrystalline/amorphous structure, enabling the extraordinary sulfur content of a few atomic percents and very minor surface oxidation/carbonization characterized by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. A 200-nm thick layer of the nanoparticles exhibits near−mid-infrared absorbance, comparable to that of the initial 380-micron thick n-doped Si wafer (phosphor-dopant concentration ≈10¹⁵ cm⁻³), with the corresponding extinction coefficient for the hyperdoped NPs being 4–7 orders higher over the broadband spectral range of 1–25 micrometers. Such ultimate, but potentially tunable mid-IR structured, multi-band absorption of various sulfur-impurity clusters and smooth free-carrier absorption are break through advances in mid-infrared (mid-IR) laser and radiofrequency (RF) hyperthermia-based therapies, as envisioned in the RF-heating tests, and in fabrication of higher-efficiency thin-film and bulk photovoltaic devices with ultra-broad (UV−mid-IR) spectral response.     

Engineering Carbon Distribution in Silicon-Based Anodes at Multiple Scales

The successful commercialization of promising silicon-based anode materials has been hampered by their poor cycling stability caused by the huge volume change. Integration of the carbon matrix with silicon-based (C/Si-based) anode materials has been demonstrated to be a powerful solution to achieve satisfactory electrochemical performance. This minireview aims to outline recent developments on C/Si-based composites, with the emphasis on the importance of carbon distribution at multiple scales. In addition, the forms of the carbon framework (carbon sources and doping of heteroatoms) have been summarized. Particularly, a novel C/Si-based hybrid with carbon distributed at the atomic scale has been highlighted.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Measurement of the surface excitation parameter of Kapton,polyethylene (PE), polymethyl methacrylate (PMMA), polystyrene (PS) and polytetrafluoroethylene (PTFE)

Reflection electron energy loss spectra (REELS) were measured for five insulating organic compounds: Kapton, polyethylene (PE), poly(methyl methacrylate) (PMMA), polystyrene (PS) and polytetrafluoroethylene (PTFE), as well as for Ni and Si, in the energy range between 200 and 1600 eV. The average number of surface excitations for a single surface crossing were determined from the experimental data and were found to be considerably smaller than for earlier studied materials, which mainly consisted of elemental metals [Surf. Sci. 486(2001)L461]. The surface excitation parameter, a material parameter used to quantify the relative intensity of surface losses in (photo)electron spectroscopy, was extracted from the data and compared with values found in the literature. The results indicate that surface excitations only have a minor influence on quantification of XPS spectra of polymers. On the other hand, a correction for surface excitations turns out to be essential for measurements of the electron inelastic mean free path of polymers when a metal is used as reference material.     

Micro-Mesoporous Carbons from Cyclodextrin Nanosponges Enabling High-Capacity Silicon Anodes and Sulfur Cathodes for Lithiated Si-S Batteries

Manufactured globally on industrial scale, cyclodextrins (CD) are cyclic oligosaccharides produced by enzymatic conversion of starch. Their typical structure of truncated cone can host a wide variety of guest molecules to create inclusion complexes; indeed, we daily use CD as unseen components of food, cosmetics, textiles and pharmaceutical excipients. The synthesis of active material composites from CD resources can enable or enlarge the effective utilization of these products in the battery industry with some economical as well as environmental benefits. New and simple strategies are here presented for the synthesis of nanostructured silicon and sulfur composite materials with carbonized hyper cross-linked CD (nanosponges) that show satisfactory performance as high-capacity electrodes. For the sulfur cathode, the mesoporous carbon host limits polysulfide dissolution and shuttle effects and guarantees stable cycling performance. The embedding of silicon nanoparticles into the carbonized nanosponge allows to achieve high capacity and excellent cycling performance. Moreover, due to the high surface area of the silicon composite, the characteristics at the electrode/electrolyte interface dominate the overall electrochemical reversibility, opening a detailed analysis on the behavior of the material in different electrolytes. We show that the use of commercial LP30 electrolyte causes a larger capacity fade, and this is associated with different solid electrolyte interface layer formation and it is also demonstrated that fluoroethylene carbonate addition can significantly increase the capacity retention and the overall performance of our nanostructured Si/C composite in both ether-based and LP30 electrolytes. As a result, an integration of the Si/C and S/C composites is proposed to achieve a complete lithiated Si−S cell.     

GaN单晶衬底上同质外延界面杂质的研究

氮化镓单晶衬底上的同质外延具有显著的优势,但是二次生长界面上的杂质聚集一直是困扰同质外延广泛应用的难题,特别是对电子器件会带来沟道效应,对激光器应用会影响谐振腔中的光场分布。本文通过金属有机化合物化学气相沉积(MOCVD)生长的原位处理,实现了界面杂质聚集的有效抑制。研究发现,界面上的主要杂质是C、H、O和Si,其中C、H、O可以通过原位热清洗去除;界面Si聚集的问题主要是由衬底外延片保存过程中暴露空气带来的,其次是氮化镓衬底中Si背底浓度,在外延过程中,生长载气对氮化镓单晶衬底不稳定的N面造成刻蚀,释放的杂质元素会对二次生长界面产生影响,本文较系统地阐明了界面杂质的形成机制,并提出了解决方案。     

An NHC–Silyl–NHC Pincer Ligand for the Oxidative Addition of C−H,N−H,and O−H Bonds to Cobalt(I) Complexes

N‐Heterocyclic carbene based pincer ligands bearing a central silyl donor, [CSiC]⁻, have been envisioned as a class of strongly σ‐donating ligands that can be used for synthesizing electron‐rich transition‐metal complexes for the activation of inert bonds. However, this type of pincer ligand and complexes thereof have remained elusive owing to their challenging synthesis. We herein describe the first synthesis of a CSiC pincer ligand scaffold through the coupling of a silyl–NHC chelate with a benzyl–NHC chelate induced by one‐electron oxidation in the coordination sphere of a cobalt complex. The monoanionic CSiC ligand stabilizes the Co^I dinitrogen complex [(CSiC)Co(N₂)] with an unusual coordination geometry and enables the challenging oxidative addition of E−H bonds (E=C, N, O) to Co^I to form Co^III complexes. The structure and reactivity of the cobalt(I) complex are ascribed to the unique electronic properties of the CSiC pincer ligand, which provides a strong trans effect and pronounced σ‐donation.