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DOI: 10.1002/asia.

201800573 Communication

Lead-free Perovskites

Synthesis of Lead-free CsGeI3 Perovskite Colloidal Nanocrystals


and Electron Beam-induced Transformations
Xiaotong Wu+,[a, b] Weidong Song+,[a] Qian Li,[a] Xixia Zhao,[a] Dongsheng He,[c] and
Zewei Quan*[a]

tention recently, especially after reliable synthetic procedures


Abstract: Colloidal nanocrystals (NCs) of metal halide per-
were developed two years ago.[6]
ovskite have recently aroused great research interest, due
Metal halide perovskites usually have a general formula of
to their remarkable optical and electronic properties. We
ABX3, where corner-sharing BX6 octahedra create a 3D frame-
report a solution synthesis of a new member in this cate-
work with an A component coordinated by 12X anions. The
gory, that is, all-inorganic lead-free cesium germanium
perovskite structure naturally lends itself to combinatorial
iodine (CsGeI3) perovskite NCs. These CsGeI3 colloidal NCs
chemistry, enabling the broad chemical tunability of metal
are confirmed to adopt a rhombohedral structure. More-
halide perovskite NCs. Both small organic amines (e.g.,
over, the electron beam-induced transformations of these
CH3NH3 + , NH2CHNH2 + ) and Cs + cation can occupy A sites to
lead-free perovskite NCs have been investigated for the
construct hybrid and all-inorganic perovskite NCs, and the
first time. The fracture of single-crystalline CsGeI3 nano-
latter one that exhibits an improved stability under ambient
cubes occurs first, followed by the emergence and growth
conditions, is now the subject of intensive research.[6d, 7] As for
of cesium iodine (CsI) single crystals and the final frag-
B sites, the current choice is limited to Pb divalent cation (Pb2 + )
mentation into small debris with random orientations. No-
in most perovskite NCs, and all-inorganic cesium lead halide
tably, the electron-reduced Ge species in CsGeI3 nano-
(CsPbX3) NCs with tunable composition, size and morphologies
cubes exhibit a distinctive transformation path, compared
have been successfully synthesized.[6d, 8] However, the serious
to heavier Pb atoms in lead halide perovskite NCs.
environmental complications of Pb make it necessary to search
for nontoxic lead-free alternatives. The most straightforward
option for Pb replacement is to use another group 14 metal,
The recent emergence of metal halide perovskites has been such as Sn or Ge, as these divalent cations possess similar elec-
demonstrated to be a novel class of promising semiconductor tron configurations (ns2np0).[9] Very recently, the implementa-
materials in various applications, including photovoltaic cells,[1] tion of cesium tin halide (CsSnX3) colloidal NCs with tailored
light-emitting diodes,[2] lasers[3] and photodetectors.[4] This composition and size was successfully demonstrated.[10]
progress is built on their remarkable physical characteristics Cesium germanium halide (CsGeX3) perovskites, possessing
such as high luminescence efficiency, sharp absorption edge, smaller band gap compared with heavier Pb and Sn atoms
and excellent carrier mobility.[5] Consequentially, colloidal NCs that is advantageous for its photovoltaic applications, have
of semiconducting metal halide perovskites that represent the been prepared in bulk solids, and they also exhibit intriguing
latest entries in this field have been attracting considerable at- nonlinear optical properties.[11] However, analogous CsGeX3
NCs still remain unexplored, possibly due to the increased diffi-
culty in colloidal synthesis. Furthermore, a reduction in stability
of the divalent oxidation state are expected to occur as a
[a] X. Wu,+ W. Song,+ Dr. Q. Li, X. Zhao, Prof. Dr. Z. Quan
Department of Chemistry result of reduced inert electron pair effects upon proceeding
Southern University of Science and Technology, SUSTech up group 14 (Pb2 + !Sn2 + !Ge2 + ), which may hinder its practi-
Shenzhen, Guangdong 518055 (P. R. China) cal applications. It is therefore of great significance to perform
E-mail: quanzw@sustc.edu.cn
in situ transformation investigations on these Ge-based perov-
[b] X. Wu+
skite NCs, aiming to provide insights to the origins of this in-
School of Chemical Biology and Biotechnology
Shenzhen Graduate School of Peking University stability.
Shenzhen, Guangdong 518055 (P. R. China) Herein, we report the first synthesis of all-inorganic lead-free
[c] Dr. D. He CsGeI3 colloidal NCs. By using a series of characterization
Materials Characterization and Preparation Center probes including X-ray and electron, these CsGeI3 NCs are con-
Southern University of Science and Technology, SUSTech
firmed to crystallize in the rhombohedral structure (R3m space
Shenzhen, Guangdong 518055 (P. R. China)
group). Moreover, the degradation process of CsGeI3 NCs
[+] These authors contributed equally to this work.
under electron beam irradiation is investigated in detail to
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under: reveal its in situ morphology evolution and structure variation,
https://doi.org/10.1002/asia.201800573.

Chem. Asian J. 2018, 13, 1654 – 1659 1654 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication

providing more insights into the instability origins of CsGeI3 these CsGeI3 nanocubes, from which almost all peaks can be
perovskite NCs. assigned to the reference card (#01-085-1274) for rhombohe-
Colloidal synthesis of CsGeI3 NCs follows a recipe modified dral phase. The presence of one diffraction peak at 2q = 27.598
from the literature.[6a] The preparation of CsGeI3 NCs is per- (#06-0311) originates from the incomplete removal of CsI NCs
formed under air-free conditions using standard Schlenk tech- during the purification process. The presence of a few CsI NCs
niques. The controlled precipitation reaction of Cs + , Ge2 + , I@ together with CsGeI3 NCs in the final product can also be clear-
ions into CsGeI3 nanocrystal is triggered by the rapid injection ly seen from the TEM image at a different location (Figure S3).
of Cs-oleate precursor solution into GeII iodide solution at Further investigations are therefore necessary to improve the
180 8C that is solubilized and stabilized by the mixture of oleyl- purification process, although we have been making great ef-
amine, oleic acid, and 1-octadecene solvents. The ionic nature forts in this regard. Considering that the standard XRD peaks
of this reaction determines the rapid nucleation and growth ki- of orthorhombic phase mostly overlap with those of rhombo-
netics of the resulting CsGeI3 NCs, and therefore the reaction hedral phase, the possibility that those CsGeI3 nanocubes crys-
conditions have to be rigidly controlled to obtain high-quality tallize in the orthorhombic phase cannot be ruled out. High
CsGeI3 NCs instead of CsI NCs, as provided in Supporting Infor- resolution TEM (HRTEM) analysis of one representative CsGeI3
mation. nanocube (Figure 1 d) reveals its single-crystalline nature, in
Figure 1 present transmission electron microscopy (TEM) re- which three well-resolved interplanar spacings in different di-
sults of the CsGeI3 NCs. Uniform CsGeI3 colloidal nanocubes rections are determined to be 5.99, 4.19 and 3.42 a, respective-
with an average edge length of 45 nm are shown in Figure 1 a ly. These d-spacings together with the measured angles be-
and b. It is known that CsGeI3 perovskite crystal exhibits two tween crystal planes (as marked in Figure 1 d), are consistent
different phases (orthorhombic Pmmm and rhombohedral with the values from the rhombohedral phase of CsGeI3 perov-
R3m) with varied temperatures.[12] The higher-temperature skite crystal in the [-1-10] zone axis. Additionally, fast Fourier
phase is found to be Pmmm, while the lower-temperature transform (FFT) pattern (Figure 1 e) obtained from this HRTEM
phase is found to have the R3m symmetry. For intuitive com- image matches well with the simulated corresponding electron
parison, schematic representations of CsGeI3 perovskite crystal diffraction pattern from the rhombohedral phase (inset). No-
structure in Pmmm and R3m phases are illustrated in Figure S1. ticeably, crystal faces with interplanar spacing 5.98 and 1.99 a
In Pmmm structure, Ge atom sits exactly in the body center of are parallel with each other, so they represent (001) and (003)
this CsGeI3 unit cell. As for R3m structure, both Ge and I atoms crystal faces in R3m phase, rather than (010) and (220) faces in
slightly deviate from the body center and face centers of the Pmmm phase of CsGeI3 perovskite. All these results suggest
unit cell (Figure 1 c), respectively. The crystal structure of these that CsGeI3 perovskite nanocubes are unequivocally deter-
nanocubes is determined to adopt this rhombohedral R3m mined to adopt the rhombohedral R3m phase instead of or-
phase. Figure S2 shows the X-ray diffraction (XRD) pattern of thorhombic Pmmm phase.
To understand the optical properties of as-synthesized
CsGeI3 perovskite NCs, we recorded UV/Vis absorption and
photoluminescence (PL) emission spectra, and also measured
PL quantum yield (PLQY) and PL lifetime of the CsGeI3 nano-
cubes, as shown in Figure S4. Based on the absorption spec-
trum of these CsGeI3 nanocube colloidal solution (Figure S4 a),
the direct band gap of CsGeI3 nanocubes is determined to be
1.6 eV close to the value for bulk CsGeI3,[13] by plotting (ahn)2
vs. hn obtained from the corresponding Tauc equation (Fig-
ure S4 b).[14] These CsGeI3 colloidal nanocubes exhibit a narrow
PL emission peak centered at 804 nm (Figure S4 a), and its
PLQY is measured to be 3.7 %. The emission lifetime is calculat-
ed to be 51 ns (Figure S4 c), which has the same order of mag-
nitude as in CsPbI3 and CsSnI3 nanocrystals.
It has been widely accepted that the electron beam irradia-
tion can significantly degrade the performances of several lead
halide perovskite devices, including hybrid[6e, 15] and all-inorgan-
ic perovskites.[8] As for nanoparticles of lead halide perovskites
with high surface-to-volume ratio, they are more susceptible
to electron irradiation than bulk crystals, and their electron
Figure 1. (a,b) TEM images of CsGeI3 perovskite nanocubes. (c) Schematic
representation of CsGeI3 perovskite crystal structure in the trigonal crystal beam-induced transformations under TEM have been recently
system (R3m space group). (d) HRTEM image showing the [-1-10] projection investigated.[7, 16] Compared with lead halide perovskite NCs,
of one CsGeI3 perovskite nanocube, with corresponding crystal planes the effect of high energy electron irradiation on lead-free per-
shown in the inset. (e) FFT pattern obtained from the HRTEM image in (d),
ovskite NCs has not been explored. The ability to synthesize
with blue, orange, green and yellow dotted circles indicating (001), (1-10),
(1-11) and (003) spots, respectively. The inset shows the corresponding simu- uniform CsGeI3 colloidal NCs allows us to perform the detailed
lated electron diffraction pattern. explorations of the degradation of lead-free CsGeI3 perovskite

Chem. Asian J. 2018, 13, 1654 – 1659 www.chemasianj.org 1655 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication

NCs under electron beam irradiation, which exhibit distinctive HRTEM image in Figure 2 a, together with the corresponding
transformation behaviors. selected area electron diffraction (SAED) pattern in Figure 2 g.
Figure 2 illustrates the in situ TEM observation of CsGeI3 per- Upon further irradiation, electron stimulated oxidation of I@
ovskite nanocubes under electron beam with incident electron anions and reduction of Ge2 + cations occur simultaneously, as
energy of 300 kV. Upon electron irradiation, electron stimulated mentioned above. Similar to other halogens in lead halide per-
oxidation of I@ anions into I0 atoms and subsequent desorption ovskite nanoparticles, the oxidized neutral I0 atoms diffuse and
of I atoms occur on CsGeI3 nanocubes. Similar processes have are subsequently desorbed from parent CsGeI3 nanocubes, due
been extensively reported in other systems, such as the oxida- to their low reactivity. The appearance of low-contrast portion
tion and desorption of Br@ ions in lead bromide perovskites, F@ in the center of this CsGeI3 nanocube (Figure 2 b) confirms
ions in fluorides and O2@ ions in oxides under electron irradia- such component loss, although the surface is still exclusively
tion.[16, 17] Considering the analogous electronic structure be- composed of R3m (100) planes. When the electron dose is ac-
tween Pb2 + and Ge2 + cations (ns2np0), the concomitant reduc- cumulated to be around 2.8 V 104 e@/A2, some lattice fluctua-
tion of Ge2 + ions into Ge0 atoms is also expected to occur on tions and atomic stacking faults at the juncture areas start to
CsGeI3 nanocubes. appear in Figure 2 c, as marked with orange dotted lines.
The electron beam-induced transformation experiments Through the magnified HRTEM image (inset), the newly emerg-
have been conducted on a series of CsGeI3 nanocubes in dif- ing R3m (1–11) planes with d-spacing of 3.42 a is clearly seen,
ferent spots, and all of them exhibit similar degradation pro- and the angle between these (1–11) planes and (100) planes in
cess. As shown in Figure 2 a–f, HRTEM images of one represen- parent CsGeI3 nanocube is measured to be 858, which holds a
tative CsGeI3 nanocube under continuous electron beam irradi- deviation of 308 compared to the calculated angle of 558 be-
ation clearly reveal its in situ morphology and structural evolu- tween two planes in R3m phase (Figure 1 d). This deviation in-
tions. In the initial stage with low electron dose, the single- dicates the partial fracture of single-crystalline CsGeI3 nano-
crystalline nature of CsGeI3 nanocubes is clearly seen from the cube into tiny debris losing original epitaxial bounds to the

Figure 2. (a–f) HRTEM images of one CsGeI3 nanocube under high energy (300 kV) electron beam irradiation with increasing electron dose. The green,
orange, blue and yellow colors in these images represent the crystal lattice faces of CsGeI3 (100), CsGeI3 (1–11), CsGeI3 (200) and CsI (110), respectively. Insets
of (c–e) show the magnified crystal lattices from the sections marked with dotted circles, and the relative angle between different lattice faces is shown in (c).
For a clearer view, magnified HRTEM images of Figure 2 (c-e) is shown in Figure S5–7. (g–i) Representative SAED patterns captured at three critical transforma-
tion stages under continuous electron beam irradiation, with insets in (g) and (h) showing the corresponding simulated electron diffraction patterns. (j) Sche-
matic illustration of the electron beam irradiation induced transformations in colloidal CsGeI3 nanocubes. The scalebars in (a–f) represent 20 nm.

Chem. Asian J. 2018, 13, 1654 – 1659 www.chemasianj.org 1656 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication

parent lattice. It should be pointed out that the formation of electron dose is around 7.5 V 104 e@/A2. The appearance of mul-
high-contrast Pb nanoparticles via the diffusion and aggrega- tiple sets of diffraction spots in the corresponding SAED pat-
tion of reduced Pb0 atoms is usually observed in lead halide tern (Figure 2 i) is consistent with this TEM observation. The
perovskite nanoparticles at this stage. However, the analogous evolution of a series of CsGeI3 nanocubes under electron beam
formation of Ge nanoparticles does not occur in CsGeI3 nano- is also shown in Figure S9, which shows similar degradation
cubes, possibly due to the high formation energy of Ge nano- process as mentioned above. The schematic illustration of this
particles. Germanium is a semi-metal element with a strong electron beam-induced transformations of CsGeI3 nanocubes is
lone pair effect,[18] it is more difficult for Ge atoms to crystalize shown in Figure 2 j: the lattice fluctuations appear first with
compared with Pb. Instead of aggregating into nanoparticles, continuous loss of I@ and Ge2 + species from parent CsGeI3 per-
Ge prefers to exist in the atomic and amorphous state.[19] In ovskite structure, CsI spot starts to develop and evolves into
this case, the reduced Ge0 atoms in these CsGeI3 nanocubes single-crystalline CsI, and the final decomposition of CsI crystal
should take a distinctive transformation path, in which they into small fragments. The stability of CsGeI3 nanocubes at am-
prefer to diffuse randomly across the nanocube without pro- bient conditions was also investigated. The degradation pro-
ducing Ge nanoparticles and some of them may spread out on cess can be accordingly identified: single crystalline CsGeI3 per-
the supporting carbon film with further irradiation. This hy- ovskite nanocubes are stable for few hours (Figure S10 a) and
pothesis is supported by the energy dispersive X-ray spectros- then some parts gradually change into CsI crystals (Fig-
copy (EDS) mapping results of CsGeI3 nanocubes in Figure 3, ure S10 b), followed by the complete transformation into CsI
as will be discussed below. As the electron dose reaches above NCs after one day (Figure S10 c). The fast degradation of CsGeI3
4 V 104 e@/A2, the electron irradiation induced loss of I and Ge NCs in air should be caused by the presence of moisture to
species in the perovskite nanocube accumulated to an appreci- dissociate CsGeI3 nanocubes and the invasion of oxygen to
able amount, and then crystalline CsI with Pm3m cubic sym- Ge2 + cations.
metry started to develop with a little spot as the initial seed, An accurate characterization of the elemental composition
as revealed by a set of characteristic CsI (110) planes with d- (Cs, Ge, and I) after degradation of particles would provide
spacing of 3.21 a in Figure 2 d (marked with yellow dotted complementary evidence to support the transformation mech-
lines). At this stage, most of the nanocube surface is still en- anism, as proposed above. The average atomic ratio of Cs/Ge/I
closed by the (200) planes of R3m phase CsGeI3 (as highlighted in these CsGeI3 nanocubes after electron beam-induced degra-
with blue dotted lines), and the variation of surface planes dation is determined to be 1:1.14:1.33 according to scanning
from (100) plane in Figure 2 b to (200) plane in Figure 2 d is TEM (STEM)-EDS characterizations. Compared to the theoretical
due to electron irradiation-induced lattice vibrations on CsGeI3 atomic ratio (1:1:3) in starting CsGeI3 nanocubes, the signifi-
nanocubes. As the total electron dose is around 6 V 104 e@/A2, cantly reduced I percentage confirms the electron stimulated
this CsI phase rapidly extend to the whole particle to evolve desorption of I. Meanwhile, the ratio of Cs:Ge only deviates
into single-crystalline CsI nanocube (Figure 2 e), which is also from 1 with small errors, implying that Ge element is still pre-
confirmed by the corresponding SAED pattern in Figure 2 h served within the sample acquisition area, although Ge2 + cat-
(CsGeI3 and CsI unit cells are shown in Figure S8). Since CsI is ions are reduced into Ge0 atoms under electron irradiation.
also sensitive to high-energy sources (X-ray, gamma-ray, laser, High-angular annular dark field (HAADF)-STEM image and cor-
electron),[20] high energy electron irradiation (300 kV) in TEM responding elemental mapping images of CsGeI3 nanocubes
can further decompose single-crystalline CsI nanocubes into after irradiation are shown in Figure 3. From these images, it is
small fragments with different orientations (Figure 2 f) as the clear that Cs and residual I elements are still constrained within
the original CsGeI3 nanocube framework, while Ge atoms are
distributed throughout the whole area, including the gap re-
gions between nanocubes. This observation suggests that the
reduced Ge0 atoms in CsGeI3 nanocubes exhibit distinctive
electron beam-induced transformation behaviors compared to
heavier Pb0 atoms in lead halide perovskite nanoparticles.
Without forming nanoparticles, all Ge0 atoms are believed to
diffuse across the CsGeI3 nanocubes, and some of them spread
out to the gap regions while some of them are left on the
nanocubes.
In summary, lead-free CsGeI3 perovskite colloidal NCs have
been successively synthesized, and they are confirmed to crys-
tallize in a rhombohedral perovskite structure with R3m phase.
Additionally, electron beam-induced degradation of CsGeI3 per-
ovskite nanocubes under high-energy electron beam irradia-
tion was systematically studied by TEM, revealing the in situ
morphology evolution and structure variation of CsGeI3 nano-
Figure 3. (a) HAADF-STEM image, and (b–d) STEM-EDS mapping images of
CsGeI3 perovskite nanocubes after irradiation. The scale bars represent cubes. Along with the desorption of oxidized I species from
100 nm. the parent CsGeI3 nanocubes, reduced Ge atoms diffuse across

Chem. Asian J. 2018, 13, 1654 – 1659 www.chemasianj.org 1657 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication

the nanocube and spread out on the supporting carbon film, NIR Spectrophotometer, respectively. To measure PL quantum
which is different from the electron-stimulated formation of Pb yield, HAMAMATSU ABSOLUTE PL QUANTUM YIEDL SPECTROME-
nanoparticles in lead halide perovskite NCs. The gradual trans- TER C11347 was used. PL lifetime measurements were performed
by using the Edinburgh Instruments LP920-Laser Flash Photolysis
formation of nanocubes from single-crystalline CsGeI3 (rhom-
Spectrometer and the excitation source used was a 355 nm
bohedral R3m) to single-crystalline CsI (cubic Pm3m) and then
output.
to polycrystalline CsI fragments under continuous electron irra-
diation is also observed. This work could provide novel insights
to understand the electron-induced instability of lead-free per- Acknowledgements
ovskites and accelerate the development of such nanomateri-
als for potential optical and electronic applications. This work is supported by the National Natural Science Foun-
dation of China (NSFC) (Nos. 11604141, 51772142), Shenzhen
Science and Technology Innovation Committee (Nos.
Experimental Section JCYJ20170412152528921, JCYJ20160530190842589), Develop-
Chemicals. Germanium(II) iodide (GeI2, + 99.8 % trace metals basis), ment and Reform Commission of Shenzhen Municipality
cesium carbonate (Cs2CO3, 99.95 % trace metals basis), 1-octade- (Novel Nanomaterial Discipline Construction Plan), and start-up
cene (ODE, technical grade, 90 %), oleylamine (OAm, technical fund and Presidential fund from SUSTech.
grade, 70 %), oleic acid (OA, technical grade, 90 %) were bought
from Sigma–Aldrich. n-Hexane (C6H14, AR, + 97.0 %) was purchased
from Shanghai Lingfeng Chemical Reagent Co., Ltd. All chemicals Conflict of interest
were used without any further purification, except for OAm, OA,
and ODE that were degassed at 120 8C for 2 h under vacuum. The authors declare no conflict of interest.
Preparation of Cs-oleate precursor. Cs-oleate precursor was pre-
pared according to the previously reported procedure.[6a] 0.407 g
of Cs2CO3 was mixed with 1.25 mL of OA and 20 mL of ODE in a Keywords: electron beam irradiation · germanium · lead-free
100 mL three-neck flask. The solution was degassed for 1 h under perovskites · nanocrystals · stability
vacuum at 120 8C, and then heated to 150 8C under Ar flow until
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