Evolution of ordered nanoporous phases during h-BN growth: Controlling the route from gas-phase precursor to 2D material by $\textit{in-situ}$ monitoring
Adrian Ruckhofer, Marco Sacchi, Anthony Payne, Andrew P. Jardine, Wolfgang E. Ernst, Nadav Avidor, Anton Tamtögl
Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene and hexagonal boron nitride (h-BN) can be grown by chemical vapour deposition (CVD). However, the high temperatures and fast timescales at which the conversion from a gas-phase precursor to the 2D material appear, make it extremely challenging to simultaneously follow the atomic arrangements. We utilise helium atom scattering to discover and control the growth of novel 2D h-BN nanoporous phases during the CVD process. We find that prior to the formation of h-BN from the gas-phase precursor, a metastable $(3\times3)$ structure is formed, and that excess deposition on the resulting 2D h-BN leads to the emergence of a $(3\times4)$ structure. We illustrate that these nanoporous structures are produced by partial dehydrogenation and polymerisation of the borazine precursor upon adsorption. These steps are largely unexplored during the synthesis of 2D materials and we unveil the rich phases during CVD growth. Our results provide significant foundations for 2D materials engineering in CVD, by adjusting or carefully controlling the growth conditions and thus exploiting these intermediate structures for the synthesis of covalent self-assembled 2D networks.
Few layer graphene/carbon (FLG/C) composites are prepared directly via the rapid and simple exfoliation of expanded graphite in the presence of carbon based natural precursors (i.e. protein, polysaccharide) in water, followed by carbonization process. Several parameters such as nature of C-precursor, FLG/C ratio and carbonization conditions (gas, temperature) are modified in order to optimize the morphology, composition and porosity of FLG/C and thereby investigate their impact on gravimetric and volumetric capacitance, their stability and contribution of pseudocapacitance (Ps) vs. double-laye…
CaxCoO2 thin films can be promising for widespread flexible thermoelectric applications in a wide temperature range from room-temperature self-powered wearable applications (by harvesting power from body heat) to energy harvesting from hot surfaces (e.g., hot pipes) if a cost-effective and facile growth technique is developed. Here, we demonstrate a time resolved, facile and ligand-free soft chemical method for the growth of nanoporous Ca0.35CoO2 thin films on sapphire and mica substrates from a water-based precursor ink, composed of in-situ prepared Ca2+-DMF and Co2+-DMF complexes. Mica serve…
The evolution of the nanoporous structure of cylindrical sintered silver samples during high temperature aging, ranging from 200 {\textdegree}C to 350 {\textdegree}C for 350 min, is studied through in-situ Computed X-Ray Tomography. Investigations were performed for two types of specimens: pure sintered silver and 2 specimens containing a silver-copper interface. It is shown that the overall pore evolution is driven by the evolution of very few large ones. The smaller pores, although being more numerous, do not really evolve before being absorbed by the few bigger ones. In pure silver, pore ev…
Sequential infiltration synthesis (SIS) provides a successful route to grow inorganic materials into polymeric films by penetrating of gaseous precursors into the polymer, both in order to enhance the functional properties of the polymer creating an organic-inorganic hybrid material, and to fabricate inorganic nanostructures when infiltrating in patterned polymer films or in selfassembled block copolymers. A SIS process consists in a controlled sequence of metal organic precursor and co-reactant vapor exposure cycles of the polymer films in an atomic layer deposition (ALD) reactor. In this wor…
Solid-state synthesis from powder precursors is the primary processing route to advanced multicomponent ceramic materials. Designing ceramic synthesis routes is usually a laborious, trial-and-error process, as heterogeneous mixtures of powder precursors often evolve through a complicated series of reaction intermediates. Here, we show that phase evolution from multiple precursors can be modeled as a sequence of pairwise interfacial reactions, with thermodynamic driving forces that can be efficiently calculated using ab initio methods. Using the synthesis of the classic high-temperature superco…
Selective laser reaction sintering techniques (SLRS) techniques were investigated for the production of near net-shape non-oxide ceramics including SiC, Si$_3$N$_4$, and HfC/SiC composites that might be compatible with prevailing powder bed fusion additive manufacturing processes. Reaction bonded layers of covalent ceramics were produced using in-situ reactions that occur during selective laser processing and layer formation. During SLRS, precursor materials composed of metal and/or metal oxide powders were fashioned into powder beds for conversion to non-oxide ceramic layers. Laser-processing…
Monolayer transition metal dichalcogenides (TMDCs) are two-dimensional (2D) materials with many potential applications. Chemical vapour deposition (CVD) is a promising method to synthesize these materials. However, CVD-grown materials generally have poorer quality than mechanically exfoliated ones and contain more defects due to the difficulties in controlling precursors' distribution and concentration during growth where solid precursors are used. Here, we propose to use thiol as a liquid precursor for CVD growth of high quality and uniform 2D MoS2. Atomic-resolved structure characterizations…
Understanding the gypsum (CaSO4.2H2O) formation pathway from aqueous solution has been the subject of intensive research in the past years. This interest stems from the fact that gypsum appears to fall into a broader category of crystalline materials whose formation does not follow classical nucleation and growth theories. The pathways involve transitory precursor cluster species, yet the actual structural properties of such clusters are not very well understood. Here, we show how in situ high-energy X-ray diffraction experiments and molecular dynamics (MD) simulations can be combined to deriv…
This paper investigates by in situ high-resolution X-ray radiography and tomography the behaviour of colloidal suspensions of alumina particles during directional solidification by freezing. The combination of these techniques provided both qualitative and quantitative information about the propagation kinetic of the solid/liquid interface, the particles redistribution between the crystals and a particle enriched phase and the 3D organisation of the ice crystals. In this first part of two companion papers, the precursor phenomena leading to directional crystallisation during the first instants…
Visualizing Crystallization Dynamics and Transformation Pathways of Disordered Rocksalt Oxides During Thermally Activated Sol-Gel Synthesis
Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）；Brazilian Synchrotron Light Laboratory (LNLS), Brazilian Center for Research in Energy and Materials (CNPEM)（巴西同步辐射光源实验室（LNLS），巴西能源与材料研究中心（CNPEM））；University of California, Berkeley（加州大学伯克利分校）
Glassy carbon is a graphene-rich form of elemental carbon obtained from pyrolysis of polymers, which is composed of three-dimensionally arranged, curved graphene fragments alongside fractions of disordered carbon and voids. Pyrolysis encompasses gradual heating of polymers above 900 degree C under inert atmosphere, followed by cooling to room temperature. Here we report on an experimental method to perform in situ high-resolution transmission electron microscopy (HR-TEM) for the direct visualization of microstructural evolution in a pyrolyzing polymer in the 500-1200 degree C temperature range…
Sequential infiltration synthesis (SIS) consists in a controlled sequence of metal organic precursors and co-reactant vapor exposure cycles of polymer films. Two aspects characterize a SIS process: precursor molecule diffusion within the polymer matrix and precursor molecule entrapment into polymer films via chemical reaction. In this paper, we investigated SIS process for the alumina synthesis using trimethylaluminum (TMA) and H2O in thin films of poly(styrene-random-methyl methacrylate) (P(S-r-MMA)) with variable MMA content. The amount of alumina grown in the P(S-r-MMA) films linearly depen…
AlV$_2$O$_4$ thin films via in-situ interfacial topotaxy
California Institute of Technology（加州理工学院）；Institute for Quantum Information and Matter, California Institute of Technology（加州理工学院量子信息研究所）；Center for High Technology Materials, University of New Mexico（新墨西哥大学高等技术材料中心）
Contemporary powder-based polycrystalline nickel-base superalloys inherit microstructures and properties that are heavily determined by the thermo-mechanical treatments during processing. Here, the influence of a thermal exposure alone to an alloy powder is studied to elucidate the controlling formation mechanisms of the strengthening precipitates using a combination of atom probe tomography and in-situ neutron diffraction. The initial powder comprised a single-phase supersaturated gamma only; from this, the evolution of gamma-prime volume fraction and lattice misfit was assessed. The initial …
High-quality dielectric-semiconductor interfaces are critical for reliable high-performance transistors. We report the in-situ metalorganic chemical vapor deposition (MOCVD) of Al$_2$O$_3$ on $β$-Ga$_2$O$_3$ as a potentially better alternative to the most commonly used atomic layer deposition (ALD). The growth of Al$_2$O$_3$ is performed in the same reactor as Ga$_2$O$_3$ using trimethylaluminum and O$_2$ as precursors without breaking the vacuum at a growth temperature of 600 $^0$C. The fast and slow near interface traps at the Al$_2$O$_3$/ $β$-Ga$_2$O$_3$ interface are identified and quantif…
This work presents the synthesis of SiC nanowires floating in a gas stream through the vapour-liquid-solid (VLS) mechanism using an aerosol of catalyst nanoparticles. These conditions lead to ultrafast growth at 8.5 μm/s (maximum of 50 μm/s), which is up to 3 orders of magnitude above conventional substrate-based chemical vapour deposition. The high aspect ratio of the nanowires (up to 2200) favours their entanglement and the formation of freestanding network materials consisting entirely of SiCNWs. The floating catalyst chemical vapour deposition growth process is rationalised through in-situ…
Decoding Thermal Stability: In situ Insights into Phase Controlled Phosphine-free Colloidal Bi-Te Nanosheets
University of Rostock（罗斯托克大学）；Pidstryhach Institute for applied problems of mechanics and mathematics of NAS of Ukraine（乌克兰国家科学院普季里哈赫应用力学与数学研究所）；Center for Interdisciplinary Electron Microscopy (ELMI-MV), Department “Life, Light & Matter”, University of Rostock（罗斯托克大学生·光·物质学院跨学科电子显微镜中心）
An HVPE reactor for the growth of bulk GaN crystals with a diameter of 50 mm was developed. Growth rate non-uniformity of 1% was achieved using an axisymmetric vertical gas injector with stagnation point flow. Chemically-resistant refractory materials were used instead of quartz in the reactor hot zone. High-capacity external gallium precursor sources were developed for the non-stop growth of the bulk GaN layers. A load-lock vacuum chamber and a dry in-situ growth chamber cleaning were implemented to improve the growth process reproducibility. Freestanding GaN crystals with a diameter of 50 mm…
Achieving superconductivity in infinite-layer nickelate thin films by aluminum sputtering deposition
Laboratoire Albert Fert, CNRS, Thales, Université Paris-Saclay（阿尔伯特·费尔特实验室，法国国家科学研究中心，泰雷兹集团，巴黎萨克雷大学）；Laboratoire de Physique des Solides, CNRS, Université Paris-Saclay（固体物理实验室，法国国家科学研究中心，巴黎萨克雷大学）；Synchrotron SOLEIL（索莱尔同步辐射中心）
