Synthesis of ultrasmall CsPbBr3 nanoclusters and their · S8 Fig. S7. (a) FTIR spectrum of CsPbBr3...

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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: agdong@fudan.edu.cn (A.D.)

Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2017

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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.

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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.

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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

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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.

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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.

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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.

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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.

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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.

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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.

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Fig. S10. (a) Absorption spectra and (b) small-angle XRD pattern of CsPbBr3 cluster

assemblies synthesized with the ligands of n-octanoic acid/OAm.

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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.

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Fig. S12. (a, b) Low-magnification TEM images of CsPbBr3 nanoribbon bundles.

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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.