Water-Stable 1D Hybrid Tin(II) Iodide Emits Broad Light with 36% Photoluminescence Quantum Efficiency

Article abstract of DOI:10.1021/jacs.0c03004

The optical and light emission properties of tin and lead halide perovskites are remarkable because of the robust room-temperature (RT) performance, broad wavelength tunability, high efficiency, and good quenching resistance to defects. These highly desirable attributes promise to transform current light-emitting devices, phosphors, and lasers. One disadvantage in most of these materials is the sensitivity to moisture. Here, we report a new air-stable one-dimensional (1D) hybrid lead-free halide material (DAO)Sn2I6 (DAO, 1,8-octyldiammonium) that is resistant to water for more than 15 h. The material exhibits a sharp optical absorption edge at 2.70 eV and a strong broad orange light emission centered at 634 nm, with a full width at half-maximum (fwhm) of 142 nm (0.44 eV). The emission has a long photoluminescence (PL) lifetime of 582 ns, while the intensity is constant over a very broad temperature range (145-415 K) with a photoluminescence quantum yield (PLQY) of at least 20.3% at RT. Above 415 K the material undergoes a structural phase transition from monoclinic (C2/c) to orthorhombic (Ibam) accompanied by a red shift in the band gap and a quench in the photoluminescence emission. Density functional theory calculations support the trend in the optical properties and the 1D electronic nature of the structure, where the calculated carrier effective masses along the inorganic chain are significantly lower than those perpendicular to the chain. Thin films of the compound readily fabricated from solutions exhibit the same optical properties, but with improved PLQY of 36%, for a 60 nm thick film, among the highest reported for lead-free low-dimensional 2D and 1D perovskites and metal halides.

Full text of DOI:10.1021/jacs.0c03004

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Article
Water Stable 1D Hybrid Tin(II) Iodide Emits Broad Light
with 36% Photoluminescence Quantum Efficiency
Ioannis Spanopoulos, Ido Hadar, Weijun Ke, Peijun Guo, Siraj Sidhik, Mikaël Kepenekian,
Jacky Even, Aditya D. Mohite, Richard D. Schaller, and Mercouri G. Kanatzidis
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c03004 • Publication Date (Web): 13 Apr 2020
Downloaded from pubs.acs.org on April 13, 2020
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Water Stable 1D Hybrid Tin(II) Iodide Emits Broad
Light with 36% Photoluminescence Quantum
Efficiency
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Ioannis Spanopoulos1, Ido Hadar1, Weijun Ke1, Peijun Guo2#, Siraj Sidhik5, Mikaël
Kepenekian3, Jacky Even4, Aditya D. Mohite5, Richard D. Schaller1, and Mercouri G.
Kanatzidis*,1
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1Department of Chemistry, Northwestern University, Evanston, IL 60208, United States
2Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue,
Lemont, Illinois 60439, United States
3Univ Rennes, ENSCR, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes),
UMR 6226, Rennes F-35000, France
4Univ Rennes, INSA Rennes, CNRS, Institut FOTON, UMR 6082, Rennes F-35000, France
5Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX 77005,
United States
ABSTRACT
The optical and light emission properties of tin and lead halide perovskites are
remarkable because of the robust room temperature performance, broad wavelength
tunability, high efficiency and good quenching-resistance to defects. These highly
desirable attributes promise to transform current light emitting devices, phosphors and
lasers. One disadvantage in most of these materials is the sensitivity to moisture. Here
we report a new air-stable one-dimensional (1D) hybrid lead-free halide material
(DAO)Sn2I6 (DAO: 1,8-octyldiammonium) that is resistant to water for more than 15h.
The material exhibits a sharp optical absorption edge at 2.70 eV and a strong broad
orange light emission centered at 634 nm, with a full width at half maximum (FWHM)
of 142 nm (0.44 eV). The emission has a long photoluminescence (PL) lifetime of 582
ns, while the intensity is constant over a very broad temperature range (145-415 K) with
a photoluminescence quantum yield (PLQY) of at least 20.3% at RT. Above 415 K the
material undergoes a structural phase transition from monoclinic (C2/c) to
orthorhombic (Ibam) accompanied by a red shift in the bandgap and a quench in the
photoluminescence emission. Density functional theory calculations support the trend
in the optical properties and the 1D electronic nature of the structure, where the
calculated carrier effective masses along the inorganic chain are significantly lower
than those perpendicular to the chain. Thin films of the compound readily fabricated
from solutions exhibit the same optical properties, but with improved PLQY of 36%,
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for a 60 nm thick film, among the highest reported for lead-free low-dimensional 2D
and 1D perovskites and metal halides.
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INTRODUCTION
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Halide perovskites are a unique family of semiconductors1-2 that can be
efficiently exploited in a wide range of applications spanning from solid state solar
cells,3-4 γ-ray detectors,5 lasing,6 thermography7 and photocatalysis8 to LEDs.9-10 The
vast majority of these materials have the perovskite structure which is defined as one
featuring octahedral metal MX6 centers where the octahedra connect to each other by
sharing only corners to form 3D, 2D, and 1D structures. The 3D halide perovskites are
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formulated as AMX3 (A = CH3NH3 (MA), HC(NH2)2 (FA), Cs+; M = Ge2+, Sn2+, Pb2+;
X = Cl-, Br-, I-).11,12 A′2An-1MnX3n+1 formula describes 2D perovskites, where A′ is a
monovalent or divalent (A′An-1MnX3n+1) organic cation acting as a spacer between the
perovskite layers and A is monovalent cation,13-14 while 1D materials (e.g.
+
+
A′MnX2n+1)
15-16 and often 0D nanostructures are referred to as perovskites (e.g. AMX3
quantum dots). If the MX6 octahedra, however, are not connected by sharing corners,
the structures are not proper perovskites and can be referred to as perovskitoids.17
A relatively recent and most prominent property of this class of materials is their
ability to chemically engineer and shape the light emission spectra (e.g. strong broad
light and white light emission),18-20 color stability, and color rendering capability, either
as stand-alone semiconductor compounds in light emitting diodes (LEDs)21 or in
combination with a phosphor.22 Hybrid halide perovskites also offer the advantage of
solution processability,23 fine tuning of optical properties,24 high photoluminescence
quantum yield (PLQY) and composition of earth abundant chemical elements,25 thus
lowering the cost and expanding the color gamut application range of the existing
technologies.26
A plethora of hybrid perovskite and metal halide candidate materials with
notable PLQY values have been reported towards this end: 2D compounds such as
(EDBE)-[PbBr4] (EDBE: 2,2′-(ethylenedioxy)bis(ethylammonium) with 9% PLQY,27
(2,6- dmpz)3Pb2Br10 (2,6-dmpz: 2,6-dimethylpiper-azine) with 12% PLQY,28 1D
compounds such as (AD)Pb2Cl5 (AD: acridine) with 7.45% PLQY,29 (AQ)PbCl4 (AQ:
3-aminoquinoline)
with
9%
PLQY,30
(TMEDA)Pb2Br6
(TMEDA:
N,N,N’-trimethylethylene-diammonium) with 10% PLQY,31 (C4N2H14)PbBr4 and
(C4N2H14)Pb0.987Mn0.013Br4 (C4N2H14: N, N-dimethylethylenediamine) with 20% and
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28% PLQY respectively,32-33 (TDMP)PbBr4 (TDMP: trans-2,5-dimethylpiperazine)
with 45% PLQY,34 and 0D materials in single crystal form such as
(C4N2H14Br)4SnBr3I3 with 85% PLQY,35 and (C9NH20)2SbCl5 with 95% PLQY.36 In
the latter two cases the achieved PLQY values are comparable to those recorded for
CsPbX3 (X: Br, I) perovskite quantum dots (QD),37 which exhibit near-unity PLQY.38-
39 However perovskite QDs suffer from poor long-term stability that could limit their
implementation in real life applications.40-41
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Two fundamental prerequisites for the commercial utilization of a new material
are their composition of non-toxic elements (e.g. Sn2+) and their long-term
environmental stability.42 Most of the reported hybrid materials with highly efficient
light emission are based on Pb2+, and only few are stable under extreme conditions,
-
such as [Pb2Cl2]2+[-O2C(CH2)4CO2 ] which is water stable for 24h43 and [N-
methyldabconium]PbI3 which is water stable for one month.44
Nonetheless, there is significant interest in developing less toxic lead-free
compounds. Progress in this regard includes (C8NH12)4Bi0.57Sb0.43Br7·H2O (4.5%
PLQY),45 (PEA)2SnI4 (PEA: phenylethylamine, 6.4% PLQY as nanodisks),46
(TEA)2SnI4 (TEA: thienylethylamine, 18.8% PLQY as nanodisks),47
(C18H35NH3)2SnBr4 (88% PLQY as colloidal suspension),48 (C5H7N2)2ZnBr4 (19%
PLQY)49, (Bmpip)2SnI4 (Bmpip: 1-butyl-1-methyl-piperidinium, 35% PLQY),50
(C4N2H14I)4SnI6 (75% PLQY),36 Cs3Cu2I5 (90% PLQY)51 and (C9NH20)2SbCl5 (95%
PLQY).36 In the majority of cases these materials have molecular 0D structures. Even
though they can be efficient light emitters, generally there is limited information on
their environmental stability, or how they perform well above room temperature.
Addressing the above concerns, we report here the synthesis of 1D (DAO)Sn2I6
(DAO: 1,8-octyldiammonium) compound with a new structure, which is water stable
for more than 15h, and exhibits strong broad orange light emission at room temperature
(RT) with 20.3% PLQY. To our knowledge, this PLQY value is among the highest for
low dimensional (1D, 2D) metal halide broad light emitters in single crystal form (Table
S1). The PL is characterized by a constant PL linewidth in the 175-415 K temperature
range and a stable PL intensity in the 145-415 K range. Power dependent PL studies
suggest that the origin of the broad light emission is ascribed to trap states. Films of
(DAO)Sn2I6 can be made using a one-step (OS) solution deposition method based on
this material’s precursor components. The films maintained the crystal’s excellent
optical properties, and achieve an enhanced bright broad light emission with at least 36%
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PLQY.
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RESULTS AND DISCCUSSION
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Synthetic Aspects and Water Stability
High quality single crystals of (DAO)Sn2I6 were obtained by the reaction of an
off-stoichiometric amount of SnCl2×2H2O and 1,8-diamino octane (2:0.5) in hydrogen
iodide (HI) and hypophosphorous acid (H3PO2) solution (volume ratio 5:8). This
specific reagent ratio was used for the acquisition of large yellow single crystals (~0.2
cm). When equimolar reactants ratio (1:1) for Sn and DAO was tested instead, powder
size crystals were formed. The resulting (DAO)Sn2I6 crystals were filtered in air and
dried under vacuum. The presence of high amount of H3PO2 in the solution helps to
suppress Sn2+ oxidation and formation of orange SnI4 crystals that can contaminate the
final product. Notably, (DAO)Sn2I6 can remain in its mother liquor for months without
formation of SnI4.
Powder X-ray diffraction (PXRD) measurements verified the phase purity of
the as made single crystals, as the calculated PXRD pattern from the single crystal
structure refinement matched exactly the experimentally recorded one (Figure 1a, b).
SEM studies revealed the uniform well faceted rectangular shape of the single crystals,
see Figure 1c. Remarkably, the resulting (DAO)Sn2I6 crystals are stable not only after
washing with water, but can also remain in liquid water for more than 15h without
structural decomposition as determined by PXRD, Figure 1a, b. Given the well-known
extreme moisture sensitivity of Sn2+ based perovskite materials, the water stability of
(DAO)Sn2I6 is surprising. To illustrate this performance, we compared the stabilities of
the most air stable Pb based perovskites, such as the highly “hollow” 3D
(MA)0.56(en)0.44(Pb)0.692(I)2.824 (en: ethylenediammonium),52 the 2D (HA)2(MA)3Pb4I13
(HA: hexylammonium) and also the pristine 3D MAPbI3.53 All these crystals
decomposed immediately upon contact with water to yellow PbI2, whereas the
(DAO)Sn2I6 crystals remained intact for at least 15h (Figure 2). This exceptional water
stability is accompanied by a diminished crystal solubility (at least three times lower)
in common polar solvents such as dimethylformamide (DMF), dimethylacetamide
(DMA), N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO) as compared
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to higher dimensional hybrid halide perovskite analogues, such as 3D MAPbI3 and
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2D (NH3CmH2mNH3)(CH3NH3)n−1PbnI3n+1
.
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X-Ray Photoelectron Spectroscopy (XPS) measurements performed on the
samples before and after the water treatment indicated no valence changes (using SnI2
and SnI4 crystals as standards), (Figure S1). Furthermore, the UV-VIS optical
absorption and Raman spectra of fresh crystals and crystals after water immersion were
unchanged (Figure 3, S2a). After 2 weeks of air exposure XPS measurements detected
surface oxidation of the Sn2+ into Sn4+ (Figure S1b) and crystal color change from
yellow to brown and black. However, this is limited to the surface of the crystals and
there is no underlying decomposition even after 90 days exposure in air, as concluded
by PXRD measurements (Figure S3). Thermogravimetric analysis (TGA)
measurements revealed that (DAO)Sn2I6 is thermally stable up to 558K, which is the
same temperature range as the 2D Pb based Ruddlesden-Popper perovskites53 and about
25 K lower than the 3D MASnI3 perovskites (Figure S4b).52 Differential scanning
calorimetry (DSC) measurements followed by PXRD indicate the presence of a phase
transition, expressed as an endothermic peak at 425K (Figure S4a). We therefore,
investigated the crystal structure over a wide range of temperature to elucidate the
distinguishing features of the phase changes and look for other phase transitions, as
described below.
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Structural properties
Single crystal XRD analysis revealed that the material crystallizes in the
monoclinic centrosymmetric C2/c space group at room temperature. There is one
crystallographically independent Sn2+ cation and four I- ions which through the
presence of an inversion centre and a glide plane generate a 1D inorganic chain along
the crystallographic c-axis. The chain consists of corner sharing [SnI5]3- moieties
(Figure 4a). The Sn2+ cations are coordinated by five I- ions and exhibit a distorted
square pyramidal geometry. The structure consists of an unprecedented 1D double
inorganic chain based on corner sharing square pyramidal [SnI5]3- moieties, which are
separated and charge balanced by 1,8-octyldiammonium cations. Each square
pyramidal moiety is connected by the equatorial iodide atoms to four other [SnI5]3- units
at an angle (Sn-I(4)-Sn) of 114.638(11)° creating in this way a 1D double inorganic
ladder-like chain of opposite facing pyramids (Figure 4b). This geometry indicates that
the 5s2 lone pair in the Sn2+ ions is stereochemically active with its expected location
being on the opposite side of the axial Sn-I bonds. In the square pyramidal [SnI5]3-
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moiety the axial Sn-I(3) distance is 2.8948(3) Å while the equatorial distances range
from 3.0890(3) Å to 3.3116(3) Å, for Sn-I(4) and Sn-I(2) respectively.
Among the inorganic chains, propagating along the crystallographic c-axis
reside two opposite phasing, double protonated organic (DAO) molecules charge
balancing the structure. The linkers are staggered along the axis direction, while the
terminal ammonium groups on the alternating organic molecules are pointing along the
b-axis towards opposite chains. The planes of the linkers are separated by 2.5 Å, while
the distance among the N-H hydrogens and the bridging equatorial I(2) anions of the
[SnI5]3- pyramids is 2.87 Å, signalling moderate hydrogen bond interactions (Figure
S6).56
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Phase transition. The (DAO)Sn2I6 exhibits a temperature dependent phase transition
from monoclinic to orthorhombic as determined by PXRD and single crystal XRD
studies. Scanning the range of 80K to 500K we observed one clear phase transition
between 410K-440K and verified the compound is stable up to at least 500K. From 80K
to 410K there is a shift of the PXRD pattern to lower 2θ values, indicative of lattice
thermal expansion. The solved and refined single crystal structure at 100K was found
to be the same as the RT one (Table 1). From 410K to 500K, however, a structural
phase transformation is evidenced by the disappearance of the (111) diffraction peak of
the monoclinic phase and the appearance of the (121) peak of the orthorhombic phase
(Figure S5). When the temperature reaches 440K the structure increases in symmetry,
adopting the orthorhombic centrosymmetric Ibam space group, based on single crystal
XRD measurements (Figure 5, Table 1). This phase transition is accompanied by a
change in color from yellow to dark red and a gradual increase in the unit cell volume
from 2369.30(15) Å3 to 2476.9(2) Å3 representing a ~4.5% expansion (Table 1). This
large expansion is coupled to the relaxation of the structure, as the inorganic chain
becomes less distorted at high temperature (HT), as evidenced by the opposite
equatorial Sn-I(1)-Sn and Sn-I(4)-Sn angles changing from 101.108(8)° and
114.638(11)° at room temperature (RT), to 98.94(3)° and 139.38(5)° at HT
respectively. The asymmetry of the distorted [SnI5]3- pyramid at RT as compared to the
less distorted HT phase, is also clear by the change in the equatorial Sn-I bond lengths.
In the RT phase they reside at distances of Sn-I(4), Sn-I(1) and Sn-I(2) 3.0890(3) Å,
3.2896(3) Å and 3.3116(3) Å respectively, while at HT, the corresponding values are
3.1783(7) Å and 3.2050(8) Å, for Sn-I(2) and Sn-I(3) respectively. These parameters
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clearly depict the higher distortion of the pyramids of the RT phase, which have a direct
effect on the optical properties, as there is crystal colour change from yellow to red.
The organic cations at HT are also relaxed, shifting from the bent RT
configuration, to an almost linear one, stretching across two neighboring inorganic
chains. The corresponding distance among the N-H hydrogens and the axial I(1) anions
of the [SnI5]3- pyramids is 2.93 Å. This is a significant difference between the HT and
RT structures, as in the first case the two ammonium groups are facing the same
inorganic chain, whereas at HT, the two ammonium groups charge balance opposite
inorganic chains across the a-axis (Figure S7). In this case the ammonium groups lay
closer to the axial iodide ions and not to the equatorial as it observed in the RT phase.
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Electronic structure calculations
Density functional theory (DFT) calculations provide insight about the
electronic structure and the semiconductor properties of (DAO)Sn2I6 at room
temperature (298 K, C2/c) and high temperature (440 K, Ibam). The electronic band
structure at RT, exhibits bands with strong energy dispersion in the [Sn2I6] chain
direction and low dispersions in perpendicular directions, reflecting the 1D character of
the crystals (Figure 6). The conduction band minimum (CBM) is located at the Γ point
of the Brillouin zone (BZ), while the valence band maximum (VBM) is found, at the
edge of BZ (M point) giving rise to an indirect bandgap of 2.215 eV. The computed
band gap is a little bit lower than the experimental determined one at 2.70 eV, which is
expected from the chosen level of theory (see Supporting Information). The valence
band maximum (VBM) consists mostly of I(5p) orbitals with a contribution from Sn(5s)
lone pair states, while CBM consists mostly of Sn(5p) orbitals (Figure S8a, S10a). For
the less distorted HT phase, the band gap remains indirect in nature, the CBM being
located at the X point of the BZ, and the VBM at the G0 point, exhibiting again an
indirect bandgap of 2.149 eV at this level of computation. The calculations therefore
do predict a red shift of the band gap consistently with crystal color change from yellow
to red for the HT phase (Figure 6b). Partial densities of states do not exhibit strong
difference between the two phases (Figure S8). The main contrast is found in the
contributions of the outer (Iout, axial) and inner (Iin, equatorial) iodide atoms of the
inorganic chain to the VBM and CBM at both temperatures (Figure S9). At RT the Iout
peak is shifted in comparison to the Iin peak, indicating more localized states, while at
HT the contributions of Iin and Iout exhibit a better overlap. This could be ascribed to the
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stronger interaction of the axial iodide atoms with the ammonium groups at RT, through
moderate hydrogen bonding. The distance among the N-H hydrogens and the bridging
equatorial I(2) anions of the [SnI5]3- pyramids is 2.87 Å at RT (see above) while at HT
it shifts to 3.50 Å, signalling weaker interaction.
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An important parameter for the evaluation of the charge transport properties in
a semiconductor material, is the carrier effective masses.57 In (DAO)Sn2I6 due to the
reduced dimensionality of the framework, we calculated these parameters along the
inorganic chain and perpendicular to the chain. For the RT phase, the values are me,//*
= 0.32m0 and mh,//*= 0.72m0 for electrons and holes respectively along the 1D inorganic
chain, while these values exhibit a strong anisotropy perpendicular to the chain, me,*
= 2.72m0 and mh,* = 2.86m0. These results clearly suggest that there is negligible
electronic coupling between neighbouring inorganic chains.The effective masses of 1D
(DAO)Sn2I6 me*and mh* along the inorganic chain are slightly larger than those
reported for the 3D MASnI3 and 2D (BA)SnI4 (BA: butylammonium) compounds, me*
= 0.13m0 , mh* = 0.28m058 and me* = 0.13m0, mh* = 0.15m059 respectively.
For the HT phase, DFT calculations yield lower masses me,//* = 0.09m0, mh,//* =
0.33m0 and me,* = 1.18m0, mh,* = 6.23m0 along the 1D inorganic chain and
perpendicular to the chain respectively. This significant difference between the two
phases is clearly connected to the much less distorted nature of the HT phase, where
the increased Sn-I orbital overlap leads to broader bands and better charge transport
properties. This trend was also observed for the 3D MAPbI3 analogs, where lowering
of the crystal symmetry from the cubic undistorted phase to the distorted tetragonal
phase, lead to a reduction of the Pb-I orbital overlap and higher carrier effective
masses.60
Optical absorption and photoluminescence
UV-VIS absorption spectra of (DAO)Sn2I6 reveal a sharp absorption edge at
2.70 eV for both the pristine and the water treated sample (Figure 3, S2a). The RT
Raman spectra of the fresh and water treated sample were also identical (Figure S2b).
The spectra are dominated by sharp vibrational peaks, which are characteristic of low-
dimensional non-perovskite metal halide materials,28 in contrast to the broad spectral
features that are observed for 3D perovskites.61 Comparing the spectra for (DAO)Sn2I6
to those of the 1D compound (CH3)3SSnI3, we can ascribe the peaks at lower
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wavenumbers (15-100 cm-1) to the bending of the I−Sn−I bonds, whereas the peaks at
higher wavenumbers (100-200 cm-1) derive from the stretching of the Sn−I bonds.62-63
Notably the vibration peaks of (DAO)Sn2I6 at RT, are much sharper than those of
(CH3)3SSnI3, depicting the higher rigidity of the (DAO)Sn2I6 structure.
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Upon excitation of the as made crystals with a 400 nm beam (DAO)Sn2I6
exhibits a broad strong emission centered at 634 nm with a large full width at half
maximum (FWHM) of 142 nm (0.44 eV). The PL maximum has a large energy shift of
174 nm (0.75 eV) (Figure 7a). This behavior is typical for broad light emitter
materials,64 however, its origin depends on a number of structural parameters
(dimensionality,65 composition,66 presence of defects67), and is unique for each
compound.68-69 The strong broad light emission of (DAO)Sn2I6 gave a PLQY of 20.3%
(Figure S11), while the PL peak position and FWHM is the same regardless of
excitation power (Figure S12). This PLQY value is the among the highest recorded for
1D metal halides, and a record value for lead free 1D broad light emitter materials in
single crystal form.70
The corresponding CIE (International Commission on Illumination)
chromaticity coordinates are (0.55, 0.42), with a much larger contribution from the red
region of the spectrum as compared to pure white light, which has chromaticity
coordinates of (0.33, 0.33). This gives the emission from (DAO)Sn2I6 a correlated color
temperature (CCT) of 1822 K (warm orange light), and a color-rendering index (CRI)
value of 75, meaning that this material is suitable for outdoor lighting (Figure 8b). CIE
coordinates and CCT values were calculated using the ColorCalculator by OSRAM
Sylvania, Inc. CRI index quantifies how accurately illuminated colors are reproduced;
for indoor lighting values above 80 are required.71
Photoemission yield spectroscopy in air (PYSA) measurements provided
insight into the electronic band alignment of the synthesized perovskite materials.72 The
position of the valence band maxima (VBM) was determined through PYSA
measurements, while the conduction band minima (CBM) was determined by
subtracting the corresponding optical band gap values from the measured VBM
energies. The recorded values for the pristine crystals, the water treated ones as well as
the 3D MASnI3 are presented in Figure S13. The VBM of the pristine material lays a
little deeper in energy than the water treated one, which could be an indication of the
surface degradation of the water treated sample. Furthermore, the fact that the pristine
material has higher ionization energy than MASnI3, is consistent with the higher air
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stability of (DAO)Sn2I6, considering that MASnI3 is stable in air for a few minutes
only.73
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Origin of PL emission
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In order to verify whether the emission is a bulk property and does not originate
from surface defects, the large single crystals were grounded and the PL spectra were
recorded, showing no difference in PL intensity (Figure S14), suggesting that the PL is
indeed a bulk property. To gain insight into the mechanism of the broad emission,
variable-temperature PL measurements were performed from 5 to 295K. With
decreasing temperature there is a small gradual red shift of the PL peak from 631 nm
(295K) position to 655 nm (145K), while at 115K a big red shift to 745 nm is observed
(Figure 7b). This could be ascribed to an unidentified phase transition close/below
100K (Figure 5). The FWHM of the peaks gradually shrinks, from 142 nm to 135 nm
from 295K to 175K (Figure S15b). Below this temperature the PL emission becomes
significantly broader, exhibiting FWHM values ranging from 198 to180 nm, for 145K
to 5K respectively (Figure S15b).
The measured average decay lifetime at RT is 582 ns using multi-exponential
fitting of the emission decay curve (Figure 7c), showing three components with decay
constants of 0.7, 187 and 935 ns. At 77 K the lifetime shows a single exponential decay
with decay constant of 968 ns, comparable with the long decay component at RT (Table
S14). The magnitude of the PL lifetime in (DAO)Sn2I6 may be ascribed to a trap
assisted emission mechanism (see below).74 Notably, at RT the recorded lifetime is
much longer than those in QDs (Quantum dots) materials, with values of few ns,38 1D
strong light emitting metal halide materials, such as C4N2H14PbBr4 with recorded
values of few tens of ns,32 C5H16N2Pb2Br6 with a lifetime of about one hundred ns,31
and 1D fully inorganic white light emitters such as CsCu2I3, with values below one
hundred ns.75
We also measured the dependence of PL intensity as a function of excitation
power density and found that it does not follow a linear trend (for various temperatures),
as it saturates at high power flux. This suggests that the source of emission stems from
permanent defects and not self-trapped excitons (STEs) (Figure 7d).76-77 Correcting the
PL spectra by the excitation intensity, we observe that the PL quenches at higher
excitation power (Figure S16), which is a typical behavior for radiative trap-assisted
recombination.74, 78-79 In the latter case, emission is observed when a photogenerated
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charge is trapped in a midgap state and combines with a counter charge before it relaxes
back to the ground state via a nonradiative pathway.80
To evaluate the robustness of the PL emission at higher temperatures, variable
temperature measurements were carried out up to 575 K (high temperature range)
(Figure S17). Remarkably, the (DAO)Sn2I6 emission exhibits not only a constant PL
linewidth in the temperature range of 175-415 K but a sustainable PL intensity over the
broad range of 145-415 K (Figure S15a). Interestingly, above 415K the PL quenches
(Figure S17). This is in accordance with the recorded phase transition (Figure S5) from
the distorted monoclinic phase (C2/c) at 410 K, to the less distorted orthorhombic phase
(Ibam) at 440 K (Figure 5). It is possible that under this structural configuration, and
heat treatment of the material, any emitting defect is suppressed or changed in character.
Similarly, although the structural and electronic properties are unaffected by the water
treatment (based on PXRD, UV-VIS and Raman measurements), the PL emission is
quenched. This is in alignment with the assignment of PL to permanent defects that can
be modified without perturbing the bulk material’s properties.
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The PL emission spectra are intact, both in terms of emission wavelength and
shape until the temperature of the phase transition is reached (Figure S18). The PL
stability within the RT phase limit is further supported by the determined CIE
chromaticity coordinates of (0.53, 0.45) at 415 K, and the color-rendering index (CRI)
value of 73, which are very close to the RT recorded values of (0.55, 0.42) and 75
respectively, verifying the excellent high temperature emission performance of the
material. This finding is important because an LED operating temperature can be as
high as 425K.81-82
Film deposition
A highly attractive feature of (DAO)Sn2I6 is its ability to deposit uniform high-
quality thin films. Because of the moderate solubility (see above) of the crystals in a
variety of polar solvents, we used precursor salts instead. Freshly prepared
octylenediammonium diodide (DAO-I2) (see S.I.) and SnI2 were dissolved in DMF, in
an off stoichiometric ratio (DAO-I2: SnI2 = 1:1), and spin coated, using a one-step (OS)
deposition method (see S.I.) giving rise to a colorless film which upon UV illumination
exhibited strong orange light emission (Figure 8c). If a stoichiometric ratio (DAO-I2:
SnI2 = 1:2) is used instead, a red film is formed, which can be ascribed to the formation
of the 2D Ruddlesden-Popper (DAO)SnI4 compound. This can be verified by
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comparing the PXRD patterns of the reported Pb analogue (DAO)PbI4 and the
corresponding film (Figure S19).
Atomic force microscopy (AFM) measurements revealed that a uniform, 60 nm
thin film was formed, with a surface roughness RMS value of 9.8 nm (Figure S20).
PXRD measurements shed light on the film composition, which consists of an (110)
oriented (DAO)Sn2I6 major crystalline phase (Figure S21). There is also a small
diffraction peak present at 6.6° 2θ, which is not predicted from the calculated pattern,
nor from unreacted precursor species (Figure S22) and may be an indication of the
formation of a different minor phase. Nonetheless, the film’s optical absorption,
emission and the PLE spectra (Figures 9, S23-24) are very similar to those of the single
crystals. This verifies that the origin of the PL emission is the same in both the film and
the crystals. The thin films, however, exhibited a much improved PLQY of 36% (Table
2). The enhanced PLQY value is further supported by the significantly longer PL decay
average lifetime at RT which was determined to be 1114 ns by multi-exponential fitting
(Figure S25). The decay components are similar to those of the crystals but with much
larger portion of the photons emitted from the longer decay route (see table S14),
similar to the dynamics at 77K. The slower decay seems to indicate a more efficient
transfer of the excitons to the lower energy states. Furthermore, the corresponding CIE
chromaticity coordinates of (0.59, 0.40) (Figure 8d), are very close to the bulk crystals
recorded ones of (0.55, 0.42), while the calculated color-rendering index (CRI) value
is 74, rendering this film a competent light emitter as the single crystals (CRI value 75).
PYSA measurements demonstrated the corresponding CBM and VBM energy levels
with values of 2.73(5) eV and 5.43(5) eV respectively. These results lay the path for
the further optimization of film assembly and PL performance for future device
explorations.
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CONCLUSIONS
The new 1D Sn based metal halide compound (DAO)Sn2I6 is stable in contact
with water for 15h, posing as a record stability for a Sn(II) based metal halide material,
while exhibiting highly efficient broad light emission with PLQY of 20.3%, in single
crystal form. Equally important is that the material maintains this emission performance
over a wide temperature range, and up to 415 K, surpassing the operating temperature
of an LED. Furthermore, at RT the PL lifetime is very long (582 ns) thus allowing for
efficient carrier recombination. Thin films can be fabricated exhibiting the same
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emission properties (CRI values and CIE coordinates) as the bulk crystals but with an
improved PLQY value of 36%, for a 60 nm thick film. The origin of the strong emission
is ascribed to the existence of permanent defects. The (DAO)Sn2I6 stands out not only
as an auspicious environmentally friendly and stable potential LED semiconductor
candidate, but also as a photocatalyst, based on its high PL lifetime values and water
stability. These results demonstrate the versatile nature of perovskitoid hybrid halide
materials, laying the path for the design of next generation of water stable lead-free
semiconductors.
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ASSOCIATED CONTENT
Supporting Information
Materials and methods, synthetic details, additional supplementary figures and tables
about material characterization, X-ray diffraction measurements, photoluminescence
measurements, XPS measurements, AFM measurements, thermogravimetric analysis
and PYSA measurements.
This material is available free of charge via the Internet at http://pubs.acs.org.
X-ray crystallographic data for (DAO)Sn2I6-100K
X-ray crystallographic data for (DAO)Sn2I6-293K
X-ray crystallographic data for (DAO)Sn2I6-440K
AUTHOR INFORMATION
Corresponding Authors
m-kanatzidis@northwestern.edu
Present address
#Department of Chemical and Environmental Engineering, Yale University, 9
Hillhouse Avenue, New Haven, CT 06520, USA
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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This work is primarily supported by the Department of Energy, Office of Science, Basic
Energy Sciences, under Grant No. SC0012541 (sample synthesis, structure and
property characterization). This work made use of the SPID, and EPIC facilities of
Northwestern University’s NUANCE Center, as well as the IMSERC facilities, which
have received support from the Soft and Hybrid Nanotechnology Experimental
(SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-
1720139) at the Materials Research Center, from the State of Illinois, and the
International Institute for Nanotechnology (IIN). J.E. acknowledges Institut
Universitaire de France for funding. This project has received funding from the
European Union’s Horizon 2020 research and innovation Program under the grant
agreement No 862656. This work was granted access to the HPC resources of
[TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI.
This work was performed, in part, at the Center for Nanoscale Materials, a U.S.
Department of Energy Office of Science User Facility, and supported by the U.S.
Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357.
Work on the thin film fabrication and evaluation at Rice was supported by start-up
funds under the molecular nanotechnology initiative and also the DOE-EERE 2022-
1652 program.
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Figure 1. A) Comparison of the PXRD patterns for the as made (DAO)Sn2I6 crystals
and the water treated ones, to the calculated pattern based from the solved single crystal
structure and B) zoom into the highlighted area of the PXRD patterns from 20° to 34°
2θ verifying the high crystallinity and phase purity of the water treated sample. C)
Representative SEM images of the as made (DAO)Sn2I6 single crystals.
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Figure 2. Water stability test. Top: Single crystals of (DAO)Sn2I6 (1) along with some
of the most stable in air Pb based perovskites, such as the 2D (HA)2(MA)3Pb4I13 (2) the
highly “hollow” 3D (MA)0.56(en)0.44(Pb)0.692(I)2.824 (3), and the pristine 3D MAPbI3 (4)
for comparison. Bottom: The corresponding crystals immersed in water. Compounds
(2), (3) and (4) decomposed immediately, while (1) is structurally intact even after 15
hours.
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Figure 3. Tauc plot and determined band gap for (A) the fresh crystals and (B) the
water treated ones.
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Figure 4. A) Part of the 1D structure of (DAO)Sn2I6 at RT, looking down the c-axis.
B) Representation of the 1D double inorganic chain based on [SnI5]3- moieties. C) The
distorted square pyramidal geometry of the Sn2+ cations of the inorganic chain, along
with the corresponding Sn-I bond lengths and atom numbers.
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Figure 5. The recorded temperature dependent phase transition of (DAO)Sn2I6. A) The
yellow crystals crystallize at the monoclinic C2/c space group at 293K, B) while at
440K the structure exhibits a profound phase transition to the orthorhombic phase
(Ibam space group) accompanied by less distorted, highly oriented organic and
inorganic parts and a crystal color change from yellow to dark red. C) Part of the RT
and D) HT structures viewing along c-axis.
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Figure 6. Electronic band structures for A) RT yellow crystals of (DAO)Sn2I6 and as
well as for B) the high temperature red crystals.
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Figure 7. A) The recorded absorption and emission spectra of compound (DAO)Sn2I6,
B) temperature dependent PL measurements from 295K to 5K, C) Time-resolved
photoluminescence decay at 77K and 295K, D) Emission intensity versus excitation
power at various temperatures, revealing the saturation of PL intensity with increasing
power.
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Figure 8. A) Photographs of (1) as made single crystals in the mother liquor of
hydrogen iodide and hypophosphorous acid, (2) dried crystals under ambient light, and
(3) and under UV light. B) CIE chromaticity coordinates for (DAO)Sn2I6. C)
Photographs of fabricated thin film under ambient light and under UV light. D) CIE
chromaticity coordinates for the thin film emission.
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Figure 9. Comparison of (A) PL emission spectra and (B) PLE spectra for (DAO)Sn2I6
single crystals and thin film.
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Table 1. Crystal and Structure Refinement Data for (DAO)Sn2I6 at 100K, 293K and
440K.
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Temperature
Crystal system
Space group
100K
monoclinic
293K
monoclinic
440K
orthorhombic
Ibam
C2/c
C2/c
a = 21.0227(12) Å, α = 90°
b = 13.4267(8) Å, β =
108.8167(19)°
c = 8.6803(5) Å, γ = 90°
2319.2(2) Å3
a = 21.1574(8) Å, α = 90°
b = 13.5267(5) Å, β =
108.8895(17)°
c = 8.7500(3) Å, γ = 90°
2369.30(15) Å3
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a = 13.7210(3) Å, α = 90°
b = 20.3857(6) Å, β = 90°
c = 8.8553(8) Å, γ = 90°
Unit cell dimensions
Volume
Z
Density (calculated)
Independent reflections
Completeness to θ =
29.33°
2476.9(2) Å3
4
4
3.2796 g/cm3
3.2103 g/cm3
3.0708 g/cm3
1304 [Rint = 0.0294]
4230 [Rint = 0.0395]
5392 [Rint = 0.0378]
98%
98%
5392 / 0 / 58
1.35
99%
1304 / 3 / 38
2.82
Data / restraints /
parameters
4230 / 0 / 58
1.42
Goodness-of-fit
Robs = 0.0171, wRobs = 0.0516
Robs = 0.0472, wRobs
0.1194
=
Final R indices [I>2σ(I)]
Robs = 0.0287, wRobs = 0.0718
Rall = 0.0380, wRall = 0.0764
0.99 and -0.64 e·Å-3
R indices [all data]
Largest diff. peak and
hole
Rall = 0.0177, wRall = 0.0519
0.61 and -0.61 e·Å-3
Rall = 0.0662, wRall = 0.1249
0.86 and -0.48 e·Å-3
R = Σ||Fo|-|Fc|| / Σ|Fo|, wR = (Σ[w(|Fo|2 - |Fc|2)2] / Σ[w(|Fo|4)])1/2 and w=1/(σ2(I)+0.0004I2)
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Page 29 of 30
Journal of the American Chemical Society
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Table 2. Photophysical properties of the bulk crystals and the assembled thin film of
the (DAO)Sn2I6 compound. (τav is the average PL lifetime).
9
PLQY
(%)
τav
(ns)
FWHM
(nm)
CCT
(K)
T(K)
CRI
CIE
(DAO)Sn2I6
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystals
Film
298K
298K
20.3
36
582
1114
142
145
75
74
1822 (0.55,0.42)
1529 (0.59,0.40)
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