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Supporting Information
CVD-Deposited Hybrid Lead Halide Perovskite Films for High-
Responsivity, Self-Powered Photodetectors with Enhanced Photo Stability
under Ambient Conditions
S.V.N.Pammiaǂ, Maddaka Reddeppabǂ, Van-Dang Trana, Ji-Ho Eoma, Vincenzo Pecunia c,
Sutripto Majumdera, Moon-Deock Kimb*, Soon Gil Yoona*
aDepartment of Materials Science and Engineering, Chungnam National University, Daeduk
Science Town, 34134, Daejeon, South Korea
bDepartment of Physics, Chungnam National University, Daejeon, 34134, Republic of Korea.
cJiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of
Functional Nano & Soft Materials (FUNSOM), Joint International Research Laboratory of
Carbon-Based Functional Materials and Devices, Soochow University, 199 Ren’ai Road,
Suzhou, Jiangsu 215123, PR China
Corresponding author: [email protected], [email protected]
ǂBoth authors were equally contributed to this work
Fig. S1. (a). Schematic diagram of fabrication of perovskite films via CVD(b) Growth rate versus carrier gas flow rate on glass and NiOx/FTO substrates (green box in Fig 1(b) gas flow rate used in the present study).
Fig. S2. Cross-sectional images of CVD fabricated MAPbI3-xClx on (a) glass and (b) NiOx
/FTO substrates respectively.
Fig. S3. Grain size distribution of CVD fabricated MAPbI3-xClx films on (a) glass and (b) on NiOx /FTO substrates respectively.
103 104 105 106 1070
50
100
0
20
40
60
80
100
Frequency (Hz)
Au/MAPbI3-xClx(~ 550 nm)/FTO
r = 64.26 @ 100 kHz
D = 0.072
Diel
ectri
c co
nsta
nt (
r)
Dis
sipa
tion
fact
or (D
)
Fig. S4. Dielectric constant (εr) and dissipation factor of CVD fabricated MAPbI3−xClx films
Fig. S5. (a) Photo current and (b) external quantum efficiency (EQE %) with incident light intensity at different wavelength (475, 516 and 630 nm).
4 6 8 10
0.0
0.2
0.4
0.6
0.8
1.0No
rmal
ized
resp
onse
r = 0
.23
Sec
f = 0
.38
Sec
Time (sec)
Fig. S6. Partial enlargement of normalized photo response under illumination at 632 nm wavelength with an intensity of 152.8 µWcm-2.
.
0 5 10 15 20 25 30 35 40
1
2
0
4
5
as fabricated 15 days 30 days 60 days 90 days
Time (Sec)
3
Phot
o cu
rren
t (m
A)
Fig. S7. Moisture stability of fabricated photo detector at different time intervals and measured under illumination of 632 nm wavelength at an intensity of 152.8 µWcm-2.
Fig. S8. (a) XRD pattern (b) absorbance (c) steady state PL spectra of Cl doped MAPbI3 films on glass substrates before and after illumination with different intervals of time.
Fig. S9. SEM photographs of Cl doped MAPbI3 films on glass substrates after (a) 12 hr and (b) 24 hr illumination.
Fig. S10. FTIR spectra of Cl doped MAPbI3 films on glass substrates before and after illumination with different time intervals.
1000 1500 2000 2500 3000 3500 4000
Fresh MAPbI3-x Clx
Illuminated MAPbI3-x Clx- 6hr
Illuminated MAPbI3-x Clx- 12hr
Illuminated MAPbI3-x Clx- 24hr
wavenumber (cm-1)
Tran
smitt
ance
Table. S1. The fitting parameters of PL decay curves for the measured films.
Sample # τ1 sec
τ2
secτ3
secC α1 α2 α3 χ 2 τavg
sec
MAPbI3-xClx 10.834 ns
106.797 ns
292.805 ns
54.64605
1749.078
6847.944
729.0807
1.112912
1.033413E-07
(103.341 ns)
MAPbI3-
xClx/PCBM6.051
ns64.103
ns0.883
ns85.592
881124.1
48162.9684
4239.737
1.21866
3.798588E-09(3 .79
ns)
Table. S2. Comparison of key figures of merit of photo detectors fabricated using MAPbI3-
xClx films (R- Responsivity & D*- Specific detectivity)
Configuration of devices R(A/W)
D*(Jones)
Test conditions
Stability Reference
SWCNT/MAPbI3-xClx/ Ag
(Planar)
13.8 2.3×1011 532 nm/ 10V
Not reported I. Ka et.al,Sci Rep., 2017, 7,
45543.
MAPbI3-xClx/P3HT/graphene
(Planar)
4.3×109 8.1×1014 895 nm /0.1 V
- F. Yan et.al, ACS Appl. Mater.
Interfaces, 2017, 9, 1569.
MAPbI3-xClx/CYTOP/Au
(Planar)
7.85 - 254 nm 100 days moisture stability
(50-60% R.H)
Y. Guo et. al, J. Phys. Chem.
Lett., 2015, 6, 535.
PbPc/MAPbI3-xClx
/Au(Planar)
1.268 7.09×1012 450 nm - X. Luo et. al, npj Flexible
Electronics, 2017 6.
MAPbI3-xClx/PEDOT: PSS/Au
(Planar)
2×109 1.4×1014 598nm0.5 V
- C. Xie et. al, Light: Science &
Applications, 2017 6, e17023.
ITO/PEDOT: PSS/MAPbI3-xClx/
PCBM: F4-TCNQ/BCP/Au(Vertical)
260 - (532 nm)-1 V
- D. Zhang et. al , Adv. Optical
Mater., 2018; 6, 1701189.
ITO/PEDOT: PSS/MAPbI3-xClx /
PCBM/PFN/ Ag(Vertical)
- 1014 450 nm 0.3 V
- L. Dou et.al,Nat. Commun., 2014, 5, 5404.
FTO/b-TiO2/m-TiO2/ MAPbI3-xClx
/Spiro/Au(Vertical)
620 - 550 nm(−0.7 V)
- H. W. Chen et al.,J. Phys. Chem. Lett., 2015, 6,
1773.
FTO/MAPbI3-xClx/FTO(Vertical)
40 1.63 × 1012 625–635 nm(1.2 V)
- V. Bhatt et al., Materials Research Bulletin, 2018, 99,
79.
ITO/MAPbI3-xClx/Au(Vertical)
0.02 4×1011 405 nm(1V)
Not reported S. Li et.alJ Mater Sci ., 2019
54, 11556.
FTO/ NiOx/MAPbI3-xClx
/PCBM/Au(Vertical)
112 4 × 1014 632 nm (0 V)
Moisture stability- ≥
2000 hr(75% R.H)
Photo stability -500 hr
(≈1000 μW cm−2)
This work
Table. S3. Comparison of measured vibrational modes of CVD fabricated MAPbI3-xclx films
with reported literature.
IR band assignment MAPbI3
reported (cm-1)
Cl-MAPbI3 in this study (cm-
1)
MAPbI3·3H2O
Reported (cm-1)
MAPbI3·3H2O
in this study (cm-
1)
CH3−NH3+ rock, ν12 910 919 N.A N.A
CH3−NH3+ rock,ν5 961 974 N.A N.A
CH3−NH3+ stretch N.A N.A 994/ 1017 984 after 24 hr
Illumination
CH3 − NH3+ rock, ν11 1245 1248 1277 NA
asym. CH3 bend, ν10 1422 1424 1434 1440 after 24 hr illumination
sym. NH3+ bend, ν3 1469 1467 NA NA
asym. NH3+ bend, ν9 1579 1573 1593 1598 after 24 hr
Illumination
ν5 + ν10 2380 2375 NA NA
2 × ν11 2489 2490 NA NA
ν3 + ν11 2712 2713 NA NA
ν9 + ν11 2823 2824 NA NA
sym. CH3 stretch, ν2 2916 2918 NA NA
asym. CH3 stretch, ν8 2958 2972 NA NA
sym. NH3+ stretch 3132 3139 3253 NA
asym. NH3+ stretch 3176 3187 NA
sym. H2O stretch NA NA 3466* 3477 after 24 hr Illumination