We report on the electron beam-induced segregation of alloyed Ni-Au clusters into a Ni and Au rich phase at temperatures above the miscibility gap of a binary system. The nanoparticles, with diameters less than 10 nm, are grown fully inert in superfluid helium droplets with a Ni-Au core-shell morphology. Upon heating, the clusters are alloyed and subsequently transformed to a Janus-type morphology under irradiation with swift electrons. The underlying mechanisms are studied experimentally via in situ scanning transmission electron microscopy and theoretically via atomistic simulation techniques under consideration of elastic electron interactions. We find that the segregation kinetics is highly temperature-dependent and attribute this behavior to diffusive relaxation processes. The presented results shed light on radiation induced phenomena using clusters as a model system and suggest new routes for the synthesis of structures in nonequilibrium configurations.
References
1.
E. A.
Little
, “Development of radiation resistant materials for advanced nuclear power plant
,” Mater. Sci. Technol.
22
, 491
–518
(2013
).2.
F.
Faccio
and G.
Cervelli
, “Radiation-induced edge effects in deep submicron CMOS transistors
,” IEEE Trans. Nucl. Sci.
52
, 2413
–2420
(2005
).3.
M.
Baumann
, M.
Krause
, J.
Overgaard
, J.
Debus
, S. M.
Bentzen
, J.
Daartz
, C.
Richter
, D.
Zips
, and T.
Bortfeld
, “Radiation oncology in the era of precision medicine
,” Nat. Rev. Cancer
16
, 234 EP
(2016
).4.
B. L.
Gregory
and C. W.
Gwyn
, “Radiation effects on semiconductor devices
,” Proc. IEEE
62
, 1264
–1273
(1974
).5.
R. F.
Egerton
, P.
Li
, and M.
Malac
, “Radiation damage in the TEM and SEM
,” Micron
35
, 399
–409
(2004
).6.
A. V.
Krasheninnikov
and K.
Nordlund
, “Ion and electron irradiation-induced effects in nanostructured materials
,” J. Appl. Phys.
107
, 71301
(2010
).7.
F.
Tamisier
, C.
Jaouen
, P.
Guérin
, and G.
Gladyszewski
, “Effect of ion irradiation on the structure of multilayers
,” Thin Solid Films
275
, 247
–250
(1996
).8.
K.
Niwase
, F.
Phillipp
, and A.
Seeger
, “Self-organized nanostructures generated on Au, Ag, and Cu surfaces by low-temperature electron irradiation
,” Jpn. J. Appl. Phys., Part 1
39
, 4624
–4628
(2000
).9.
X-w
Du
, M.
Takeguchi
, M.
Tanaka
, and K.
Furuya
, “Formation of crystalline Si nanodots in Sio2 films by electron irradiation
,” Appl. Phys. Lett.
82
, 1108
–1110
(2003
).10.
D.
Knez
, P.
Thaler
, A.
Volk
, G.
Kothleitner
, W. E.
Ernst
, and F.
Hofer
, “Transformation dynamics of Ni clusters into NiO rings under electron beam irradiation
,” Ultramicroscopy
176
, 105
–111
(2017
).11.
J.
Kotakoski
, C.
Mangler
, and J. C.
Meyer
, “Imaging atomic-level random walk of a point defect in graphene
,” Nat. Commun.
5
, 3991
(2014
).12.
T.
Susi
, J. C.
Meyer
, and J.
Kotakoski
, “Manipulating low-dimensional materials down to the level of single atoms with electron irradiation
,” Ultramicroscopy
180
, 163
–172
(2017
).13.
O.
Dyck
, S.
Kim
, S. V.
Kalinin
, and S.
Jesse
, “Placing single atoms in graphene with a scanning transmission electron microscope
,” Appl. Phys. Lett.
111
, 113104
(2017
).14.
P. E.
Batson
, “Motion of gold atoms on carbon in the aberration-corrected STEM
,” Microsc. Microanal.
14
, 89
–97
(2008
).15.
T.
Furnival
, D.
Knez
, E.
Schmidt
, R. K.
Leary
, G.
Kothleitner
, F.
Hofer
, P. D.
Bristowe
, and P. A.
Midgley
, “Adatom dynamics and the surface reconstruction of Si(110) revealed using time-resolved electron microscopy
,” Appl. Phys. Lett.
113
, 183104
(2018
).16.
Y.
Niu
, P.
Schlexer
, B.
Sebok
, I.
Chorkendorff
, G.
Pacchioni
, and R. E.
Palmer
, “Reduced sintering of mass-selected Au clusters on Sio2 by alloying with Ti: An aberration-corrected stem and computational study
,” Nanoscale
10
, 2363
–2370
(2018
).17.
F.
Hofer
and P.
Warbichler
, “Spinodal decomposition in the gold-nickel system
,” Z. Metallkd.
76
, 11
–15
(1985
).18.
M.
Bienzle
, T.
Oishi
, and F.
Sommer
, “Thermodynamics and local atomic arrangements of gold-nickel alloys
,” J. Alloys Compd.
220
, 182
–188
(1995
).19.
J.
Marian
and A.
Caro
, “Moving dislocations in disordered alloys: Connecting continuum and discrete models with atomistic simulations
,” Phys. Rev. B
74
, 024113
(2006
).20.
A.
Perovic
, J.
Garrett
, and J.
Kirkaldy
, “A unique state of solid matter: Stochastic spinodal modulations in the Au–50Ni transition above 600K
,” Scr. Mater.
60
, 1020
–1022
(2009
).21.
W. M.
Haynes
, CRC Handbook of Chemistry and Physics
, 95th ed. (CRC Press
, Hoboken
, 2014
).22.
F.
Hofer
and K.
Torkar
, “Thermodynamik properties of solid gold-nickel alloys
,” Z. Phys. Chem.
130
, 229
–239
(1982
).23.
K.
Nakai
and C.
Kinoshita
, “Irradiation-induced spinodal decomposition in alloys
,” J. Nucl. Mater.
169
, 116
–125
(1989
).24.
P.
Thaler
, A.
Volk
, D.
Knez
, F.
Lackner
, G.
Haberfehlner
, J.
Steurer
, M.
Schnedlitz
, and W. E.
Ernst
, “Synthesis of nanoparticles in helium droplets-A characterization comparing mass-spectra and electron microscopy data
,” J. Chem. Phys.
143
, 134201
(2015
).25.
J. P.
Toennies
and A. F.
Vilesov
, “Superfluid helium droplets: A uniquely cold nanomatrix for molecules and molecular complexes
,” Angew. Chem. Int. Ed.
43
, 2622
–2648
(2004
).26.
A.
Volk
, P.
Thaler
, M.
Koch
, E.
Fisslthaler
, W.
Grogger
, and W. E.
Ernst
, “High resolution electron microscopy of Ag-clusters in crystalline and non-crystalline morphologies grown inside superfluid helium nanodroplets
,” J. Chem. Phys.
138
, 214312
(2013
).27.
G. J.
McLachlan
and D.
Peel
, Finite Mixture Models
, Wiley series in Probability and Statistics Applied Probability and Statistics Section (Wiley
, New York
, 2005
).28.
L. F.
Gomez
, E.
Loginov
, and A. F.
Vilesov
, “Traces of vortices in superfluid helium droplets
,” Phys. Rev. Lett.
108
, 155302
(2012
).29.
P.
Thaler
, A.
Volk
, F.
Lackner
, J.
Steurer
, D.
Knez
, W.
Grogger
, F.
Hofer
, and W. E.
Ernst
, “Formation of bimetallic core-shell nanowires along vortices in superfluid He nanodroplets
,” Phys. Rev. B
90
, 155442
(2014
).30.
M.
Schnedlitz
, M.
Lasserus
, R.
Meyer
, D.
Knez
, F.
Hofer
, W. E.
Ernst
, and A. W.
Hauser
, “Stability of core–shell nanoparticles for catalysis at elevated temperatures: Structural inversion in the Ni–Au system observed at atomic resolution
,” Chem. Mater.
30
, 1113
–1120
(2018
).31.
J.-P.
Palomares-Baez
, E.
Panizon
, and R.
Ferrando
, “Nanoscale effects on phase separation
,” Nano Lett.
17
, 5394
–5401
(2017
).32.
N. L.
Pleth
, F.
Besenbacher
, I. I.
Stensgaard
, E.
Laegsgaard
, C.
Engdahl
, P.
Stoltze
, K. W.
Jacobsen
, and J. K.
Norskov
, “Initial growth of Au on Ni(110): Surface alloying of immiscible metals
,” Phys. Rev. Lett.
71
, 754
–757
(1993
).33.
D.
Knez
, M.
Schnedlitz
, M.
Lasserus
, A.
Schiffmann
, W. E.
Ernst
, and F.
Hofer
, “Modelling electron beam induced dynamics in metallic nanoclusters
,” Ultramicroscopy
192
, 69
–79
(2018
).34.
J. C.
Meyer
, F.
Eder
, S.
Kurasch
, V.
Skakalova
, J.
Kotakoski
, H. J.
Park
, S.
Roth
, A.
Chuvilin
, S.
Eyhusen
, G.
Benner
, A. V.
Krasheninnikov
, and U.
Kaiser
, “Accurate measurement of electron beam induced displacement cross sections for single-layer graphene
,” Phys. Rev. Lett.
108
, 196102
(2012
).35.
R.
Egerton
, “Mechanisms of radiation damage in beam-sensitive specimens, for TEM accelerating voltages between 10 and 300 kV
,” Microsc. Res. Tech.
75
, 1550
–1556
(2012
).36.
F.
Niekiel
, S. M.
Kraschewski
, J.
Müller
, B.
Butz
, and E.
Spiecker
, “Local temperature measurement in TEM by parallel beam electron diffraction
,” Ultramicroscopy
176
, 161
–169
(2017
).37.
R. F.
Egerton
, F.
Wang
, and P. A.
Crozier
, “Beam-induced damage to thin specimens in an intense electron probe
,” Microsc. Microanal.
12
, 65
(2006
).38.
R.
Egerton
, R.
McLeod
, F.
Wang
, and M.
Malac
, “Basic questions related to electron-induced sputtering in the TEM
,” Ultramicroscopy
110
, 991
–997
(2010
).39.
N.
Jiang
, “Electron beam damage in oxides: A review
,” Rep. Prog. Phys. Phys. Soc.
79
, 016501
(2016
).40.
S.
Plimpton
, “Fast parallel algorithms for short-range molecular dynamics
,” J. Comput. Phys.
117
, 1
–19
(1995
).41.
A.
Jablonski
, F.
Salvat
, and C. J.
Powell
, NIST Electron Elastic-Scattering Cross-Section Database: Version 3.2
(National Institute of Standards and Technology
, Gaithersburg, MD
, 2010
).42.
A. J.
Ardell
and P.
Bellon
, “Radiation-induced solute segregation in metallic alloys
,” Curr. Opin. Solid State Mater. Sci.
20
, 115
–139
(2016
).43.
G. S.
Was
, Fundamentals of Radiation Materials Science: Metals and Alloys
, 2nd ed. (Springer
New York, New York
, 2017
).© 2019 Author(s).
2019
Author(s)
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