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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

Front. Chem. Sci. Eng.    2021, Vol. 15 Issue (6) : 1360-1379    https://doi.org/10.1007/s11705-021-2101-7
REVIEW ARTICLE
Scaling up of cluster beam deposition technology for catalysis application
Giuseppe Sanzone1,2, Jinlong Yin1(), Hailin Sun1
1. Teer Coatings Ltd., Droitwich, Worcestershire WR9 9AS, UK
2. Quantum Solid-State Physics, Department of Physics and Astronomy, B-3001 Leuven, Belgium
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Abstract

Many research works have demonstrated that the combination of atomically precise cluster deposition and theoretical calculations is able to address fundamental aspects of size-effects, cluster-support interactions, and reaction mechanisms of cluster materials. Although the wet chemistry method has been widely used to synthesize nanoparticles, the gas-phase synthesis and size-selected strategy was the only method to prepare supported metal clusters with precise numbers of atoms for a long time. However, the low throughput of the physical synthesis method has severely constrained its wider adoption for catalysis applications. In this review, we introduce the latest progress on three types of cluster source which have the most promising potential for scale-up, including sputtering gas aggregation source, pulsed microplasma cluster source, and matrix assembly cluster source. While the sputtering gas aggregation source is leading ahead with a production rate of ~20 mg·h–1, the pulsed microplasma source has the smallest physical dimensions which makes it possible to compact multiple such devices into a small volume for multiplied production rate. The matrix assembly source has the shortest development history, but already show an impressive deposition rate of ~10 mg·h–1. At the end of the review, the possible routes for further throughput scale-up are envisaged.

Keywords nanoparticle      cluster      cluster beam deposition      magnetron sputtering      heterogeneous catalysis     
Corresponding Author(s): Jinlong Yin   
Online First Date: 15 October 2021    Issue Date: 09 November 2021
 Cite this article:   
Giuseppe Sanzone,Jinlong Yin,Hailin Sun. Scaling up of cluster beam deposition technology for catalysis application[J]. Front. Chem. Sci. Eng., 2021, 15(6): 1360-1379.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-021-2101-7
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I6/1360
Type of source Reported flux/(nm·s–1) Materials usable Typical cluster size Typical vacuum regime Proportion of ionized particles
SSNS ~20 Low-boiling point metals ~100–103 atoms UHV 0
TGAS ~0.05 Any material that attains 1 mbar vapor pressure at 2000 K ~103 atoms UHV 0
SGAS ~100
(~1)
Virtually any solid (using RF or HiPIMS for insulators) 1–60 nm HV Up to 50%
LAS ~0.1 Virtually any solid ~100–102 atoms UHV ≈10%
PACIS ~1 Virtually any solid 1–10 nm HV ≈10%
PMCS 1–30 Conductive solids ~101–104 atoms UHV ≈10%
MACS 10 mg·h–1 Any metal can be vaporised ~100–103 atoms HV 0
Tab.1  Comparison of different types of cluster sources a)
Fig.1  (a) Cross section schematics of a planar magnetron. Reprinted with permission from ref. [27], copyright 2020, Elsevier. (b) A racetrack developed on a 2-inch circular aluminum target, showing the target erosion in a magnetron sputtering process.
Fig.2  Schematic drawing of the cross section of a magnetron sputtering cluster source. Reprinted with permission from ref. [33], copyright 2020, Elsevier.
Fig.3  (a) High resolution transmission electron microscope image of a Ag-Au alloy nanoparticle (NP) and energy dispersive spectrometer (EDS) line scan performed at the Ag and Au along the line depicted. Reprinted with permission from ref. [48], copyright 2012, American Chemical Society. (b), (c) and (d) Cs-corrected scanning transmission electron microscope (STEM) representative image of, respectively, a Ag-Au core-shell NP, Co-Au core-shell NP and a Co-Ag-Au core-shell-shell NP and EDS line scan performed at the Co, Ag, and Au, along the lines depicted. Reprinted with permission from ref. [49], copyright 2014, the Royal Society of Chemistry.
Fig.4  TiOx cluster deposition rate generated by continuous DC (solid fill) and pulsed DC (textured fill) under two different power applied (50 and 100 W). Reprinted with permission from ref. [54], copyright 2013, AIP Publishing.
Fig.5  Time-resolved ion current measurements for different pulse frequencies: (a) 7, (b) 10, (c) 20, and (d) 100 Hz (The dashed lines in (d) show the deconvolution in five traces as shown in (a)). Reprinted with permission from ref. [55], copyright 2013, American Chemical Society.
Fig.6  (a) Sketch of the early-stage cluster growth, occurring in Zone I in (c); (b) sketch of the OML collection of ions process, showing a much larger cross section compared to the neutral case; (c) schematic drawing of the regions corresponding to different stages of cluster growth. A movable anode ring is installed to tune the size of the second cluster growth region; (d) cluster growth rate for OML collection of ions as a function of the electron temperature Te. The neutral collection rate (blue dashed line) is 2.8 nm·s–1, while for the experimental observed growth rate by OML collection of 470 nm·s–1, Te needs to be 1.7 eV. Reprinted with permission from ref. [58], copyright 2013, AIP Publishing.
Fig.7  Scanning electron microscopy images and calculated size distribution for anode ring position at 30, 45, and 60 mm from the hollow cathode. Reprinted with permission from ref. [58], copyright 2013, AIP Publishing.
Fig.8  (a) Au single atom number density profile inside the condensation chamber in the case where the gas is provided from the rear of the chamber (top) and from within the magnetron source (bottom). A logarithmic scale is used to show the number density distribution. (b) Au single atom number density profile in a region close to the target surface, in the case where the gas is provided from the rear of the chamber (top) and from within the magnetron source (bottom). A linear scale is used to show the number density distribution. (c) The probability of Au atom–atom collision in front of the sputtering target, if the gas inlet is within the magnetron source (red cross symbol) and at the rear of the chamber (gray dash symbol). Reprinted with permission from ref. [35], copyright 2021, AIP Publishing.
Fig.9  Fraction of clusters departing from lines perpendicular to the chamber axis and successfully going out through the nozzle vs. the distance of such lines from the nozzle. The results for clusters of different sizes are shown here: (a) 10 atoms per cluster, (b) 100 atoms per cluster, and (c) 1000 atoms per cluster. Reprinted with permission from ref. [35], copyright 2021, AIP Publishing.
Fig.10  (a) Cross section of a PMCS, featuring the main constituents. Reprinted with permission from ref. [71], copyright 1999, IOP Publishing. (b) 3-D sketch of a PMCS with a system of aerodynamic lenses mounted on the nozzle exit. The rod (cathode) in specifically designed for the experiment in ref. [75]. Here a MoS2 target needed to be eroded but, because of its mechanical fragility and electrical resistivity, a system of Mo ring and holder rods hosting two MoS2 pellet cylinders has been designed, so to overcome such problems. (c) Schematics of a PMCS (left) mounted on a typical supersonic cluster beam deposition system, showing the different sections in the sequential pumping. Reprinted with permission from ref. [75], copyright 2015, IOP Publishing.
Fig.11  (a) Photographs of a cluster film deposited at 300 mm from the source with (left) and without (right) the use of a focuser; (b) histogram of the high magnification AFM results showing the two size distributions for the focused and unfocused cluster deposition, respectively in black and gray color. Reprinted with permission from ref. [76], copyright 2001 AIP, Publishing.
Fig.12  Critical diameter as a function of the gap distance for different values of the Reynolds number Re0. Reprinted with permission from ref. [61], copyright 2002, Taylor & Francis.
Fig.13  (a) Radial displacement at the end of the nozzle as a function of the particle diameter for different particle injection radial position without the focuser; (b) same as in (a) but with the use of a focuser. Reprinted with permission from ref. [61], copyright 2002, Taylor & Francis. (c) Histogram of the radial displacement of the particles exiting the nozzle without the use of a focuser. Brownian motion is considered in the calculation; (d) same as in (c) but with the use of a focuser. Reprinted with permission from ref. [78], copyright 2002, Springer Nature.
Fig.14  (a) Gas carrier streamlines from simulation results for a pressure of 345 Pa and 20% of H2 in Ar; (b) cluster trajectories for a particle diameter of 15 nm; (c) schematics of the cluster trajectories for different particle size, showing the principles of aerodynamic focusing and size-selection. Reprinted with permission from ref. [74], copyright 2006, IOP Publishing.
Fig.15  (a) Schematics of a MACS in the “transmission mode”; (b) graphic representation of the Ar+ ion beam impacting on the metal and gas condensed matrix and eroded in the “transmission mode”. Reprinted with permission from ref. [82], copyright 2016, AIP Publishing. (c) Schematics of a MACS in the “reflection mode”; (d) graphic representation of the Ar+ ion beam impacting on the metal and gas condensed matrix and eroded in the “reflection mode”. Reprinted with permission from ref. [9], copyright 2016, the Royal Society of Chemistry.
Fig.16  (a) HAADF-STEM images for Au clusters for different concentration of Au atoms embedded in the condensed gas matrix different concentration: 0.5%, 1%, 2.1% and 2.8%. The scale bar corresponds to 10 nm; (b) plot of the cluster mean size and of the cluster beam intensity vs. the metal concentration in the matrix as extrapolated by the HAADF-STEM images. Reprinted with permission from ref. [83], copyright 2020, Springer.
Fig.17  MD simulation results on the average size of Ag clusters varying the number of Ar+ ions impacting the condensed matrix for three different concentration of Ag: 5%, 10% and 20%. Reprinted with permission from ref. [84], copyright 2017, American Physical Society.
Fig.18  (a) Experimental data of the measured cluster intensity as a function of the collection angle in the case of four different incident angle of the Ar+ ion beam: 10°, 15°, 35° and 45° (It can be noted how a lower incident angle results in a higher overall cluster intensity, which is the integral of each curve); (b) optimal collection angle, which is the peak value of each curve in (a)), as a function of the incident angle of the Ar+ ion beam. Reprinted with permission from ref. [86], copyright 2019, Springer.
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