Upload
others
View
0
Download
0
Embed Size (px)
Citation preview
S1
Electronic Supplementary Information (ESI) for
Synthesis of ultrasmall CsPbBr3 nanoclusters and their
transformation to highly deep-blue-emitting nanoribbons at room
temperature
Yibing Xu,a Qiang Zhang,a Longfei Lv,b Wenqian Han,a Guanhong Wu,a Dong Yang,b
and Angang Dong *a
aCollaborative Innovation Center of Chemistry for Energy Materials, Shanghai
Key Laboratory of Molecular Catalysis and Innovative Materials, and Department of
Chemistry, Fudan University, Shanghai 200433, China.
bState Key Laboratory of Molecular Engineering of Polymers, Collaborative
Innovation Center of Polymers and Polymer Composite Materials, and Department
of Macromolecular Science, Fudan University, Shanghai 200433, China.
*To whom correspondence should be addressed: [email protected] (A.D.)
Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2017
S2
380 385 390 395 400 405 410
Self-assembly
CsPbBr3 clusters
CsPbBr3 cluster assemblies
Ab
so
rba
nc
e (
a.u
.)
Wavelength (nm)
Fig. S1. The first absorption peak of CsPbBr3 nanoclusters and their assemblies,
respectively, showing a ~7 nm red-shift along with the cluster assembly.
S3
300 350 400 450 500 550 600 650 700
CsPbBr3 cluster assmblies
CsPbBr3 cluster assmblies after 3 days
Ab
so
rba
nc
e (
a.u
.)
Wavelength (nm)
Fig. S2. Absorption spectra of the as-formed CsPbBr3 cluster assemblies and those after
3 days of storage in air. The essentially unchanged absorption spectrum upon prolonged
exposure to air indicated the high chemical stability of CsPbBr3 cluster ensembles.
S4
Fig. S3. (a) PL spectrum of CsPbBr3 cluster assemblies, showing a broad PL peak near
410 nm. (b) PL spectra of OA and OAm ligands
S5
Fig. S4. (a) Photograph of a CsPbBr3 nanocluster solution after centrifugation, showing
the white cluster precipitates. (b) Low-magnification TEM image of CsPbBr3 cluster
assemblies. (c) Magnified TEM image of the cluster assemblies, showing the parallel
fringe patterns. The black dots in (c) are expected to be Pb nanoparticles formed upon
prolonged electron-beam exposure. Similar dark dots, originating from the reduction of
Pb2+ by the electron beam, have been commonly observed in TEM on CsPbBr3
nanosheets or nanocrystals.
S6
Fig. S5. (a) Dark-field STEM image of CsPbBr3 cluster assemblies and (b-d) the
corresponding elemental mapping images, showing the existence of Cs, Pb, and Br
within the cluster assemblies.
S7
Fig. S6. (a) XPS spectrum and the Pb 4f (b), Cs 3d (c), and Br 3d (d) spectral profiles
of CsPbBr3 cluster assemblies. The solid lines are the experimental data and the dotted
lines are the fits. The atomic ratio of Cs/Pb/Br was determined to be 0.9:0.9:3.0.
S8
Fig. S7. (a) FTIR spectrum of CsPbBr3 cluster assemblies, showing the presence of a
large amount of OA/OAm ligands as indicated by the strong C-H stretching bands near
2900 cm-1. (b) TGA curves of CsPbBr3 cluster assemblies (black curve) and CsPbBr3
bulk materials (red curve) conducted in air. The weight loss of CsPbBr3 cluster
assemblies before 500 oC was attributed to the thermally decomposed organic ligands,
whereas the weight loss after 500 oC was probably caused by the decomposition of
CsPbBr3, as indicated by the bulk curve.
S9
Fig. S8. 1H NMR spectroscopic analysis of the isolated CsPbBr3 cluster assemblies.
The reference spectra of OA and OAm as well as OA/OAm in ODE were also provided
for comparison. The organic residues derived from CsPbBr3 cluster assemblies
exhibited the characteristic resonances of 1 and α, corresponding to OA and OAm,
respectively, in the 1H NMR spectra, corroborating the presence of both OA and OAm
ligands. Note that both characteristic resonances of 1 and α were slightly shifted
compared with those of OA and OAm reference spectra, which was presumably caused
by the reaction between OA and OAm. This was further confirmed by collecting the
NMR spectrum of an OA and OAm mixture in ODE, where the characteristic
resonances of 1 and α matched well with those of CsPbBr3 cluster assemblies.
S10
300 400 500 600
25 oC
45 oC
55 oC
Ab
so
rba
nc
e (
a.u
.)
Wavelength (nm)
Fig. S9. Absorption spectra of CsPbBr3 cluster assemblies synthesized under different
reaction temperatures. The characteristic absorption peak at ~398 nm suggested the
formation of the same sized clusters irrespective of the reaction temperature.
S11
Fig. S10. (a) Absorption spectra and (b) small-angle XRD pattern of CsPbBr3 cluster
assemblies synthesized with the ligands of n-octanoic acid/OAm.
S12
0.5 1.0 1.5 2.0 2.5 3.0
0
10
20
30
40
50
60
70
Fre
qu
en
cy
Width (nm)
Fig. S11. Width distribution histogram of CsPbBr3 quantum nanoribbons, showing that
the average width was 2.2 nm.
S13
Fig. S12. (a, b) Low-magnification TEM images of CsPbBr3 nanoribbon bundles.
S14
100 200 300 400 500 600 700 800
0
20
40
60
80
100
34 wt%
Clusters
Nanoribbons
We
igh
t (%
)
T (oC)
67 wt%
Fig. S13. TGA curves of CsPbBr3 cluster assemblies (black curve) and nanoribbons
(red curve), showing the significant loss of organic ligands along with the
transformation of CsPbBr3 nanoclusters.