Ordered arrays of plasmonic nanoparticles, supercrystals can lead to the formation of plasmon-polaritons. Coupling light emitters with plasmon polaritons might allow the formation of exciton–plasmon polaritons with properties tuneable by the supercrystal design. To construct such optically active materials, the inclusion of emitters is imperative. The addition of organic dyes without affecting the periodic order of the nanocrystals is difficult, as post-formation protocols might dissolve the supercrystals, and pre-formation addition might affect the self-assembly process. Here, we present an exemplary strategy to functionalize gold nanoparticles prior to self-assembly with a cyanine isothiocyanate dye that was obtained by a straightforward reaction of the amine functionalized dye with carbon disulfide. In the second step, the nanoparticles are functionalized with a thiol-terminated polystyrene, which stabilizes the nanoparticles and governs the self-assembly process. The dye can be integrated in a quantitative fashion, and the nanoparticles can be self-assembled into supercrystals. The strategy should be applicable in general for amine functionalized dyes, which is a common modification.

1.
E. B.
Barros
,
B. G.
Vieira
,
N. S.
Mueller
, and
S.
Reich
, “
Plasmon polaritons in nanoparticle supercrystals: Microscopic quantum theory beyond the dipole approximation
,”
Phys. Rev. B
104
,
035403
(
2021
).
2.
J.
Kang
,
Z. M.
Sherman
,
D. L.
Conrad
,
H. S.
Crory
,
M. N.
Dominguez
,
S. A.
Valenzuela
,
E. V.
Anslyn
,
T. M.
Truskett
, and
D. J.
Milliron
, “
Structural control of plasmon resonance in molecularly linked metal oxide nanocrystal gel assemblies
,”
ACS Nano
17
(
23
),
24218
24226
(
2023
).
3.
A. M.
Green
,
W. J.
Chang
,
Z. M.
Sherman
,
Z.
Sakotic
,
K.
Kim
,
D.
Wasserman
,
D. J.
Milliron
, and
T. M.
Truskett
, “
Structural order and plasmonic response of nanoparticle monolayers
,”
ACS Photonics
11
,
1280
(
2024
).
4.
N. J.
Greybush
,
I.
Liberal
,
L.
Malassis
,
J. M.
Kikkawa
,
N.
Engheta
,
C. B.
Murray
, and
C. R.
Kagan
, “
Plasmon resonances in self-assembled two-dimensional Au nanocrystal metamolecules
,”
ACS Nano
11
(
3
),
2917
2927
(
2017
).
5.
M.
Brust
,
D.
Bethell
,
C. J.
Kiely
, and
D. J.
Schiffrin
, “
Self-assembled gold nanoparticle thin films with nonmetallic optical and electronic properties
,”
Langmuir
14
(
19
),
5425
5429
(
1998
).
6.
N. S.
Mueller
,
Y.
Okamura
,
B. G. M.
Vieira
,
S.
Juergensen
,
H.
Lange
,
E. B.
Barros
,
F.
Schulz
, and
S.
Reich
, “
Deep strong light–matter coupling in plasmonic nanoparticle crystals
,”
Nature
583
,
780
784
(
2020
).
7.
J.-H.
Song
,
T.
Atay
,
S.
Shi
,
H.
Urabe
, and
A. V.
Nurmikko
, “
Large enhancement of fluorescence efficiency from CdSe/ZnS quantum dots induced by resonant coupling to spatially controlled surface plasmons
,”
Nano Lett.
5
,
1557
1561
(
2005
).
8.
B. S.
Kim
,
L.
Avila
,
L. E.
Brus
, and
I. P.
Herman
, “
Organic ligand and solvent kinetics during the assembly of CdSe nanocrystal arrays using infrared attenuated total reflection
,”
Appl. Phys. Lett.
76
,
3715
3717
(
2000
).
9.
A. J.
Hallock
,
P. L.
Redmond
, and
L. E.
Brus
, “
Optical forces between metallic particles
,”
Proc. Natl. Acad. Sci. U. S. A.
102
,
1280
1284
(
2005
).
10.
Q.
Li
,
U.
Jonas
,
X.
Zhao
, and
M.
Kappl
, “
The forces at work in colloidal self-assembly: A review on fundamental interactions between colloidal particles
,”
Asia-Pac. J. Chem. Eng.
3
(
3
),
255
268
(
2008
).
11.
N.
Vogel
,
M.
Retsch
,
C.-A.
Fustin
,
A.
Del Campo
, and
U.
Jonas
, “
Advances in colloidal assembly: The design of structure and hierarchy in two and three dimensions
,”
Chem. Rev.
115
(
13
),
6265
6311
(
2015
).
12.
F.
Schulz
,
O.
Pavelka
,
F.
Lehmkühler
,
F.
Westermeier
,
Y.
Okamura
,
N. S.
Mueller
,
S.
Reich
, and
H.
Lange
, “
Structural order in plasmonic superlattices
,”
Nat. Commun.
11
(
1
),
3821
(
2020
).
13.
Y.
Zheng
,
X.
Zhong
,
Z.
Li
, and
Y.
Xia
, “
Successive, seed-mediated growth for the synthesis of single-crystal gold nanospheres with uniform diameters controlled in the range of 5–150 nm
,”
Part. Part. Syst. Charact.
31
(
2
),
266
273
(
2014
).
14.
A.
Dong
,
J.
Chen
,
P. M.
Vora
,
J. M.
Kikkawa
, and
C. B.
Murray
, “
Binary nanocrystal superlattice membranes self-assembled at the liquid–air interface
,”
Nature
466
,
474
477
(
2010
).
15.
X.
Qian
,
S. R.
Emory
, and
S.
Nie
, “
Anchoring molecular chromophores to colloidal gold nanocrystals: Surface-enhanced Raman evidence for strong electronic coupling and irreversible structural locking
,”
J. Am. Chem. Soc.
134
(
4
),
2000
2003
(
2012
).
16.
C.-Y.
Lin
,
C.-H.
Liu
, and
W.-L.
Tseng
, “
Fluorescein isothiocyanate-capped gold nanoparticles for fluorescent detection of reactive oxygen species based on thiol oxidation and their application for sensing glucose in serum
,”
Anal. Methods
2
(
11
),
1810
1815
(
2010
).
17.
I.
Fratoddi
,
A.
Cartoni
,
I.
Venditti
,
D.
Catone
,
P.
O’Keeffe
,
A.
Paladini
,
F.
Toschi
,
S.
Turchini
,
F.
Sciubba
,
G.
Testa
et al, “
Gold nanoparticles functionalized by rhodamine B isothiocyanate: A new tool to control plasmonic effects
,”
J. Colloid Interface Sci.
513
,
10
19
(
2018
).
18.
F.
Schulz
,
W.
Friedrich
,
K.
Hoppe
,
T.
Vossmeyer
,
H.
Weller
, and
H.
Lange
, “
Effective pegylation of gold nanorods
,”
Nanoscale
8
(
13
),
7296
7308
(
2016
).
19.
C.
Kinnear
,
H.
Dietsch
,
M. J.
Clift
,
C.
Endes
,
B.
Rothen-Rutishauser
, and
A.
Petri-Fink
, “
Gold nanorods: Controlling their surface chemistry and complete detoxification by a two-step place exchange
,”
Angew. Chem.
125
,
1988
(
2013
).
20.
M. J.
Hore
,
X.
Ye
,
J.
Ford
,
Y.
Gao
,
J.
Fei
,
Q.
Wu
,
S. J.
Rowan
,
R. J.
Composto
,
C. B.
Murray
, and
B.
Hammouda
, “
Probing the structure, composition, and spatial distribution of ligands on gold nanorods
,”
Nano Lett.
15
(
9
),
5730
5738
(
2015
).
21.
S.
Gomez-Grana
,
F.
Hubert
,
F.
Testard
,
A.
Guerrero-Martínez
,
I.
Grillo
,
L. M.
Liz-Marzán
, and
O.
Spalla
, “
Surfactant (bi)layers on gold nanorods
,”
Langmuir
28
(
2
),
1453
1459
(
2012
).
22.
F.
Schulz
,
S.
Tober
, and
H.
Lange
, “
Size-dependent phase transfer functionalization of gold nanoparticles to promote well-ordered self-assembly
,”
Langmuir
33
(
50
),
14437
14444
(
2017
).
23.
F.
Stete
,
W.
Koopman
, and
M.
Bargheer
, “
Signatures of strong coupling on nanoparticles: Revealing absorption anticrossing by tuning the dielectric environment
,”
ACS Photonics
4
,
1669
1676
(
2017
).
24.
K. G.
Thomas
and
P. V.
Kamat
, “
Chromophore-functionalized gold nanoparticles
,”
Acc. Chem. Res.
36
,
888
898
(
2003
).
25.
A.
Vujacic
,
V.
Vasic
,
M.
Dramicanin
,
S. P.
Sovilj
,
N.
Bibic
,
S.
Milonjic
, and
V.
Vodnik
, “
Fluorescence quenching of 5,5′-Disulfopropyl-3,3′-dichlorothiacyanine dye adsorbed on gold nanoparticles
,”
J. Phys. Chem. C
117
,
6567
6577
(
2013
).
26.
F.
Schulz
and
H.
Lange
, “
Optimizing interparticle gaps in large-scale gold nanoparticle supercrystals for flexible light-matter coupling
,”
Adv. Opt. Mater.
10
,
2202064
(
2022
).
27.
B.
Jasse
,
R.
Chao
, and
J.
Koenig
, “
Laser Raman scattering in uniaxially oriented atactic polystyrene
,”
J. Polym. Sci., Polym. Phys. Ed.
16
(
12
),
2157
2169
(
1978
).
28.
C.
Liang
and
S.
Krimm
, “
Infrared spectra of high polymers. VI. Polystyrene
,”
J. Polym. Sci.
27
(
115
),
241
254
(
1958
).
29.
N. S.
Mueller
,
E.
Pfitzner
,
Y.
Okamura
,
G.
Gordeev
,
P.
Kusch
,
H.
Lange
,
J.
Heberle
,
F.
Schulz
, and
S.
Reich
, “
Surface-enhanced Raman scattering and surface-enhanced infrared absorption by plasmon polaritons in three-dimensional nanoparticle supercrystals
,”
ACS Nano
15
(
3
),
5523
5533
(
2021
).
30.
Y. U.
Staechelin
,
D.
Hoeing
,
F.
Schulz
, and
H.
Lange
, “
Size-dependent electron–phonon coupling in monocrystalline gold nanoparticles
,”
ACS Photonics
8
,
752
757
(
2021
).
31.
G. V.
Hartland
, “
Optical studies of dynamics in noble metal nanostructures
,”
Chem. Rev.
111
,
3858
3887
(
2011
).
32.
F.
Stete
,
M.
Bargheer
, and
W.
Koopman
, “
Ultrafast dynamics in plasmon–exciton core–shell systems: The role of heat
,”
Nanoscale
15
(
40
),
16307
16313
(
2023
).
33.
S.
Rodriguez
and
J. G.
Rivas
, “
Surface lattice resonances strongly coupled to rhodamine 6G excitons: Tuning the plasmon–exciton–polariton mass and composition
,”
Opt. Express
21
(
22
),
27411
27421
(
2013
).
34.
A. D.
Sample
,
J.
Guan
,
J.
Hu
,
T.
Reese
,
C. R.
Cherqui
,
J.-E.
Park
,
F.
Freire-Fernández
,
R. D.
Schaller
,
G. C.
Schatz
, and
T. W.
Odom
, “
Strong coupling between plasmons and molecular excitons in metal–organic frameworks
,”
Nano Lett.
21
(
18
),
7775
7780
(
2021
).
35.
A. K.
Boddeti
,
Y.
Wang
,
X. G.
Juarez
,
A.
Boltasseva
,
T. W.
Odom
,
V.
Shalaev
,
H.
Alaeian
, and
Z.
Jacob
, “
Reducing effective system dimensionality with long-range collective dipole–dipole interactions
,”
Phys. Rev. Lett.
132
(
17
),
173803
(
2024
).
You do not currently have access to this content.