The adsorption and self-assembly structures of melamine molecules on an Ag(111) surface are studied by low temperature scanning tunneling microscopy (STM) combined with tip-enhanced Raman spectroscopy (TERS). Two ordered self-assembly phases of melamine molecules on Ag(111) were studied by STM and TERS, combining with first-principles simulations. The α-phase consists of flat-lying melamine molecules, while the β-phase consists of mixed up-standing/tilted melamine molecules. Moreover, dehydrogenation of melamine can be controlled by annealing the sample as well as by a tip-enhanced photo-catalytic effect. Our work demonstrates TERS as a powerful tool not only for investigating the configuration and vibration properties of molecules on a metal surface with high spatial resolution but also for manipulating the chemical reactions with tip and photo-induced effects.
REFERENCES
1.
N. E.
Mircescu
, M.
Oltean
, V.
Chiş
, and N.
Leopold
, “FTIR, FT-Raman, SERS and DFT study on melamine
,” Vib. Spectrosc.
62
, 165
–171
(2012
).2.
H.
Horacek
and R.
Grabner
, “Advantages of flame retardants based on nitrogen compounds
,” Polym. Degrad. Stab.
54
(2
), 205
–215
(1996
).3.
P. O.
Powers
, “Phenol-, urea-, and melamine-formaldehyde plastics
,” Ind. Eng. Chem.
45
(5
), 1063
–1066
(1953
).4.
M.
Dunky
, “Urea–formaldehyde (UF) adhesive resins for wood
,” Int. J. Adhes. Adhes.
18
(2
), 95
–107
(1998
).5.
Q.
Liang
, B.
Shao
, S.
Tong
, Z.
Liu
, L.
Tang
, Y.
Liu
, M.
Cheng
, Q.
He
, T.
Wu
, Y.
Pan
, J.
Huang
, and Z.
Peng
, “Recent advances of melamine self-assembled graphitic carbon nitride-based materials: Design, synthesis and application in energy and environment
,” Chem. Eng. J.
405
, 126951
(2021
).6.
F.
Silly
, A. Q.
Shaw
, M. R.
Castell
, G. A. D.
Briggs
, M.
Mura
, N.
Martsinovich
, and L.
Kantorovich
, “Melamine structures on the Au(111) surface
,” J. Phys. Chem. C
112
(30
), 11476
–11480
(2008
).7.
C. H.
Schmitz
, J.
Ikonomov
, and M.
Sokolowski
, “Two commensurate hydrogen-bonded monolayer structures of melamine on Ag(111)
,” Surf. Sci.
605
(1-2
), 1
–6
(2011
).8.
J.
Greenwood
, H. A.
Früchtl
, and C. J.
Baddeley
, “Self-assembly of upright, partially dehydrogenated melamine on Pd(111)
,” J. Phys. Chem. C
117
(44
), 22874
–22879
(2013
).9.
J.
Greenwood
, H. A.
Früchtl
, and C. J.
Baddeley
, “Ordered growth of upright melamine species on Ni(111): A study with scanning tunnelling microscopy and reflection absorption infrared spectroscopy
,” J. Phys. Chem. C
116
(11
), 6685
–6690
(2012
).10.
Y.-P.
Lin
, O.
Ourdjini
, L.
Giovanelli
, S.
Clair
, T.
Faury
, Y.
Ksari
, J.-M.
Themlin
, L.
Porte
, and M.
Abel
, “Self-assembled melamine monolayer on Cu(111)
,” J. Phys. Chem. C
117
(19
), 9895
–9902
(2013
).11.
L.
Wang
, P.
Li
, H.
Shi
, Z.
Li
, K.
Wu
, and X.
Shao
, “Thickness-dependent adsorption of melamine on Cu/Au(111) films
,” J. Phys. Chem. C
121
(14
), 7977
–7984
(2017
).12.
S.
Pan
, Q.
Fu
, T.
Huang
, A.
Zhao
, B.
Wang
, Y.
Luo
, J.
Yang
, and J.
Hou
, “Design and control of electron transport properties of single molecules
,” Proc. Natl. Acad. Sci. U. S. A.
106
(36
), 15259
–15263
(2009
).13.
R.-P.
Wang
, B.
Yang
, Q.
Fu
, Y.
Zhang
, R.
Zhu
, X.-R.
Dong
, Y.
Zhang
, B.
Wang
, J.-L.
Yang
, Y.
Luo
, Z.-C.
Dong
, and J. G.
Hou
, “Raman detection of bond breaking and making of a chemisorbed up-standing single molecule at single-bond level
,” J. Phys. Chem. Lett.
12
(7
), 1961
–1968
(2021
).14.
R. B.
Jaculbia
, H.
Imada
, K.
Miwa
, T.
Iwasa
, M.
Takenaka
, B.
Yang
, E.
Kazuma
, N.
Hayazawa
, T.
Taketsugu
, and Y.
Kim
, “Single-molecule resonance Raman effect in a plasmonic nanocavity
,” Nat. Nanotechnol.
15
(2
), 105
–110
(2020
).15.
L.
Li
, J. F.
Schultz
, S.
Mahapatra
, X.
Liu
, C.
Shaw
, X.
Zhang
, M. C.
Hersam
, and N.
Jiang
, “Angstrom-scale spectroscopic visualization of interfacial interactions in an organic/borophene vertical heterostructure
,” J. Am. Chem. Soc.
143
(38
), 15624
–15634
(2021
).16.
F.
Shao
, W.
Wang
, W.
Yang
, Z.
Yang
, Y.
Zhang
, J.
Lan
, A.
Dieter Schlüter
, and R.
Zenobi
, “In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)
,” Nat. Commun.
12
(1
), 4557
(2021
).17.
H.
Li
, Y.-F.
Zhang
, X.-B.
Zhang
, A.
Farrukh
, Y.
Zhang
, Y.
Zhang
, and Z.-C.
Dong
, “Probing the deformation of [12]cycloparaphenylene molecular nanohoops adsorbed on metal surfaces by tip-enhanced Raman spectroscopy
,” J. Chem. Phys.
153
(24
), 244201
(2020
).18.
J.
Lee
, K. T.
Crampton
, N.
Tallarida
, and V. A.
Apkarian
, “Visualizing vibrational normal modes of a single molecule with atomically confined light
,” Nature
568
(7750
), 78
–82
(2019
).19.
S.
Mahapatra
, L.
Li
, J. F.
Schultz
, and N.
Jiang
, “Tip-enhanced Raman spectroscopy: Chemical analysis with nanoscale to angstrom scale resolution
,” J. Chem. Phys.
153
(1
), 010902
(2020
).20.
J.
Xu
, X.
Zhu
, S.
Tan
, Y.
Zhang
, B.
Li
, Y.
Tian
, H.
Shan
, X.
Cui
, A.
Zhao
, Z.
Dong
, J.
Yang
, Y.
Luo
, B.
Wang
, and J. G.
Hou
, “Determining structural and chemical heterogeneities of surface species at the single-bond limit
,” Science
371
(6531
), 818
–822
(2021
).21.
Z.-F.
Cai
, L.-Q.
Zheng
, Y.
Zhang
, and R.
Zenobi
, “Molecular-scale chemical imaging of the orientation of an on-surface coordination complex by tip-enhanced Raman spectroscopy
,” J. Am. Chem. Soc.
143
(31
), 12380
–12386
(2021
).22.
C.
Zhang
, R. B.
Jaculbia
, Y.
Tanaka
, E.
Kazuma
, H.
Imada
, N.
Hayazawa
, A.
Muranaka
, M.
Uchiyama
, and Y.
Kim
, “Chemical identification and bond control of π-skeletons in a coupling reaction
,” J. Am. Chem. Soc.
143
(25
), 9461
–9467
(2021
).23.
S.
Sheng
, J.-b.
Wu
, X.
Cong
, W.
Li
, J.
Gou
, Q.
Zhong
, P.
Cheng
, P.-h.
Tan
, L.
Chen
, and K.
Wu
, “Vibrational properties of a monolayer silicene sheet studied by tip-enhanced Raman spectroscopy
,” Phys. Rev. Lett.
119
(19
), 196803
(2017
).24.
S.
Sheng
, W.
Li
, J.
Gou
, P.
Cheng
, L.
Chen
, and K.
Wu
, “Low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy combined with molecular beam epitaxy for in situ two-dimensional materials’ studies
,” Rev. Sci. Instrum.
89
(5
), 053107
(2018
).25.
P. E.
Blöchl
, “Projector augmented-wave method
,” Phys. Rev. B
50
(24
), 17953
–17979
(1994
).26.
G.
Kresse
and J.
Hafner
, “Ab initio molecular dynamics for open-shell transition metals
,” Phys. Rev. B
48
(17
), 13115
–13118
(1993
).27.
G.
Kresse
and J.
Furthmüller
, “Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
,” Comput. Mater. Sci.
6
(1
), 15
–50
(1996
).28.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, “Generalized gradient approximation made simple
,” Phys. Rev. Lett.
77
(18
), 3865
–3868
(1996
).29.
S.
Grimme
, J.
Antony
, S.
Ehrlich
, and H.
Krieg
, “A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
,” J. Chem. Phys.
132
(15
), 154104
(2010
).30.
31.
K.
Momma
and F.
Izumi
, “VESTA: A three-dimensional visualization system for electronic and structural analysis
,” J. Appl. Crystallogr.
41
(3
), 653
–658
(2008
).32.
M.
Simenas
and E. E.
Tornau
, “A model of melamine molecules ordering on metal surfaces
,” J. Chem. Phys.
141
(5
), 054701
(2014
).33.
M.
Sassi
, V.
Oison
, and J.-M.
Debierre
, “First principle study of a bimolecular thin film on Ag(111) surface
,” Surf. Sci.
602
(17
), 2856
–2862
(2008
).34.
S.
Liu
, M.
Müller
, Y.
Sun
, I.
Hamada
, A.
Hammud
, M.
Wolf
, and T.
Kumagai
, “Resolving the correlation between tip-enhanced resonance Raman scattering and local electronic states with 1 nm resolution
,” Nano Lett.
19
(8
), 5725
–5731
(2019
).35.
R.
Zhang
, Y.
Zhang
, Z. C.
Dong
, S.
Jiang
, C.
Zhang
, L. G.
Chen
, L.
Zhang
, Y.
Liao
, J.
Aizpurua
, Y.
Luo
, J. L.
Yang
, and J. G.
Hou
, “Chemical mapping of a single molecule by plasmon-enhanced Raman scattering
,” Nature
498
(7452
), 82
–86
(2013
).36.
B.
Pettinger
, K. F.
Domke
, D.
Zhang
, G.
Picardi
, and R.
Schuster
, “Tip-enhanced Raman scattering: Influence of the tip-surface geometry on optical resonance and enhancement
,” Surf. Sci.
603
(10
), 1335
–1341
(2009
).37.
T.
Deckert-Gaudig
, A.
Taguchi
, S.
Kawata
, and V.
Deckert
, “Tip-enhanced Raman spectroscopy - from early developments to recent advances
,” Chem. Soc. Rev.
46
(13
), 4077
–4110
(2017
).38.
L.
Olesen
, M.
Brandbyge
, M. R.
Sørensen
, K. W.
Jacobsen
, E.
Lægsgaard
, I.
Stensgaard
, and F.
Besenbacher
, “Apparent barrier height in scanning tunneling microscopy revisited
,” Phys. Rev. Lett.
76
(9
), 1485
–1488
(1996
).39.
L.-B.
Zhao
, M.
Zhang
, Y.-F.
Huang
, C. T.
Williams
, D.-Y.
Wu
, B.
Ren
, and Z.-Q.
Tian
, “Theoretical study of plasmon-enhanced surface catalytic coupling reactions of aromatic amines and nitro compounds
,” J. Phys. Chem. Lett.
5
(7
), 1259
–1266
(2014
).40.
M.
Sun
, Z.
Zhang
, L.
Chen
, Q.
Li
, S.
Sheng
, H.
Xu
, and P.
Song
, “Plasmon-driven selective reductions revealed by tip-enhanced Raman spectroscopy
,” Adv. Mater. Interfaces
1
(5
), 1300125
(2014
).41.
A. O.
Govorov
and H. H.
Richardson
, “Generating heat with metal nanoparticles
,” Nano Today
2
(1
), 30
–38
(2007
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
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