A Novel Growth Process for the Deposition of

CH3NH3PbI3-xClx Perovskite Films

Chaminda Hettiarachchi, Nicholas Valdes, Pritish Mukherjee and Sarath

Witanachchi

Laboratory for Advanced Materials Science & Technology (LAMSAT),

Department of Physics,
University of South Florida,
Tampa, Florida, 33620, USA

Laboratory for Advanced Materials

LAMSAT

Science and Technology

Department of Physics – University of South Florida
 Background
Organolead halide perovskites
belongs to ABX3 family of materials
A - MA(methylammonium),
EA(ethylammonium), FA(formamidinium)
B - Pb
X - Cl, Br or I

[Snaith et al., Nature, 398, vol 501, (2013)]

CH3NH3PbI3-xClx Perovskite
direct band gap semiconductor with intense light absorption
ultra-fast charge carrier generation and slow carrier recombination
long charge carrier diffusion lengths and small exciton binding energy
high ambipolar and microsecond-long balanced charge carrier mobility
low temperature processability in thin film form
 CH3NH3PbI3-xClx Perovskite Precursor Preparation

Conventional Method
Mixing 0.88 M lead chloride and 2.64 M methylammonium iodide

Our Approach
Mixing lead iodide and methylammonium chloride

Advantages
Inexpensive materials
Very convenient

Film fabrication method

Spray coating
 Nebulizer Assisted Vacuum Spray (NAVS) process
Nebulizer Assisted Vacuum Spray System

Substrate
Holder
N2 gas
N2 gas
 

Nebulizer

to Vacuum
Precursor pump
Solution

An ultrasonic nebulizer operated at 2.4 MHz is used to atomize the

DMF+MACl+PbI2 precursor solution to produce an aerosol with droplet sizes of 1-2
µm.
The aerosol is carried by N2 gas through a nozzle into the growth chamber.
The flow rate thus the speed of the aerosol into the chamber was controlled by a gas
flow meter.
Nozzle-substrate distance = 6 cm
 Precursor Concentration Dependence

Structural Properties

Sample PbI2 MACl

# Concentration Concentration
(M) (M)
(a) 0.11 0.33
(b) 0.22 0.66
(c) 0.275 0.825
(d) 0.33 0.99
(e) 0.385 1.155
(f) 0.44 1.32

Tetragonal
Sample (d)
Structure
 (a) (b)

Sample PbI2 MACl

# Concentra Concentration
tion (M) (M)
(a) 0.11 0.33
(b) 0.22 0.66
(c) 0.275 0.825
(d) 0.33 0.99
(e) 0.385 1.155 (c) (d)
(f) 0.44 1.32

(e) (f)

Top  view SEM images

of CH3NH3PbI3-xClx
perovskite films on
glass substrates at
different
concentrations  
(a) (b)

(c) (d)

(e) (d)
 EDS Analysis
PbI2 and MACl Pb I Cl
concentrations
3.03 0.61
0.110 M, 0.330 M 1.00
(0.62) (0.59)
3.33 0.61
0.220 M, 0.660 M 1.00
(0.78) (1.41)
3.32 0.15
0.275 M, 0.825 M 1.00
(1.59) (1.78)
3.41 0.23
0.330 M, 0.990 M 1.00
(0.40) (0.53)
3.27 0.14
0.385 M, 1.155 M 1.00
(0.69) (0.89)
3.30 0.27
0.440 M, 1.320 M 1.00
(0.68) (0.96)

EDS analysis confirms the presence of chlorine in fabricated perovskites.

 Optical Properties

Linear absorption spectra of CH3NH3PbI3-xClx perovskite films

Deposition Temperature Dependence
Structural Properties
Optical Properties
 Conclusions

Lead iodide (PbI2) and Methylammonium chloride (MACl) can be used to

synthesize CH3NH3PbI3-xClx perovskite films.

XRD measurements of the NAVS deposited films confirmed the

tetragonal structure of CH3NH3PbI3-xClx perovskite films.

UV-vis absorption measurements confirmed good absorption of

CH3NH3PbI3-xClx perovskite films in the solar spectrum.

XRD and UV-vis measurements confirmed 120 C is the optimum

deposition temperature and 0.33 M PbI2 and 0.99 M MACl precursor
concentrations give the optimum condition to fabricate CH3NH3PbI3-xClx
perovskite films via nebulizer assisted vacuum spray deposition.