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: sgyoon@cnu.ac.kr, mdkim@cnu.ac.kr

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