MSE 131 Ceramic Materials

Razonabe, Junio, Sible

Synthesis and
Characterization of
CsSnI
3
Thin Films
(Shum, et al, 2010)
introduction
1974 structural information of CsSnI
3

compound (Scaife,et al.)

few years later yellow needlelike
CsSnI
3

synthesized (Mauersberger and
Huber)

1991 black polymorph of CsSnI
3

(Yamada et al.)

Yellow CsSnI
3
raise temperature
above 425K Black CsSnI
3

introduction
Black CsSnI
3

450K ideal cubic perovskite (B-)
426K tetragonal perovskite (B-)
< 351K orthorhombic perovskite
(B-)

All three structures direct band gap
(E
g
) at Z, R, and points

E
g
(B-)< (B-) < (B-)

CsSnI
3
IS A LONG-OVERLOOKED
SEMICONDUCTOR
objective of study
This study:

Effective and inexpensive method
of synthesizing high quality CsSnI
3

thin films on large-area substrates
(glass, ceramics and silicon)

Characterize the CsSnI
3
thin films
bandgap
surface characteristics, domain
size SEM and TEM
crystal structure ED and XRD
optical property-- PL

bandgap
Two step synthesis: The synthesis of
its high optical quality polycrystalline
thin lms is demonstrated
Alternate deposition of high purity SnI
2

(or SnCl
2
) and CsI layers in vacuum
(105 Torr) on glass, ceramics, and
silicon substrates by a thermal and e-
beam evaporators
Rapid thermal annealing was
followed in a dry N
2
environment to
activate a self-limiting chemical
reaction of CsI with SnI
2
Photoluminescence
CsI /SnI
2
and CsI /SnCl
2
layered thin lm
samples characteristic PL around 950nm.
Possible side products for the CsI /SnCl
2

layered samples:
CsSnCl
3
CsSnICl
2
,
CsSnI
2
Cl.
rst two have much larger band gaps than
CsSnI3
last one has a smaller band gap than CsSnI3.
CsI /SnCl2 layered sample
very weak PL relative to 950 nm emission
PL peak positions are consistent with
calculated band gaps for CsSnCl
3
and CsSnICl
2
.
No PL or absorption around 1.5 m observed
(CsSnI
2
Cl band gap)
Hence these possible side products from CsI
/SnCl2 layered samples do not affect the
intense band edge emission of CsSnI
3
reported
synthesis
surface characteristics
CsSnI
3
film on glass
substrate with triple
domain region

Polycrystalline
Domain size
~300nm
Different Lattice
Spacing
Different Crystal
Orientation
electron diffraction
Ring-like pattern (Bottom Left inset)
Large Domain Areas (Top Left Inset)
Single Crystal Feature
Red dots Theoretical Crystal Structure
Perovskite Structure

crystal structure
Sn-I-Sn bond in
(1) a-direction
(2) b-direction
(3) c-direction
XRD
peaks
match
optical property
CsI /SnCl
2
thin film layers on glass
substrate
Typical annealing temperature:
190C (with time duration of 15s)
Good polycrystalline lm, having very
intense PL at 950nm

CsI /SnI
2
film layers
Annealing temperature is higher than
190C since the melting temperature
of SnI
2
at 320C is higher than that of
SnCl
2
at 247C.
optical property
optical property
optical property
Absorption spectrum reflects nature of
inhomogeneity of film (composition and
domain sizes)

Absorption coefficient steeply takes off after
PL emission peak and is zero below it
direct bandgap characteristic

Shoulder riding on the absorption curve
50meV away from PL peak CB2

More work is needed to fully understand
nature of absorption in CsSnI
3
thin films


conclusion