POLARIZATION MEASUREMENTS OF

BTO:PEROVSKITE NANOCOMPOSITES
FOR PEROVSKITE SOLAR CELLS

CHAD WILDER – USF DEPT. OF CHEMICAL AND BIOMEDICAL ENGINEERING

GRADUATE MENTOR: CHAMINDA HETTIARACHCHI – USF DEPT. OF PHYSICS
FACULTY ADVISOR: SARATH WITANACHCHI – USF DEPT. OF PHYSICS

This project is supported by the NSF REU grant # 1560090

OVERVIEW

• Introduction
• Theory
• Aerosol Assisted Chemical Vapor Deposition
• Polarization Measurements
• Nanoparticle Tracking Analysis
• Scanning Electron Microscopy
• Challenges
• Conclusion
• Future Works
INTRODUCTION

• Topic of Research
–Embedding Barium Titanate (BTO) nanoparticles within a perovskite solar cell to reduce bimolecular
charge recombination.
–Bimolecular charge recombination arises from direct band-to-band electron-hole charge carrier
recombination
• Project Objectives
– Determine if BTO nanoparticles retain ferroelectric properties when embedded in perovskite solar absorber.

– Determine the optimal ratio of BTO : CH3NH3PbI3-xClx concentrations for producing most efficient solar cell.

– Determine if AACVD fabrication method is capable of producing highly crystalline thin films.

• Importance
– Validate a new, efficient, and inexpensive source of renewable energy.
INTRODUCTION

• Topic of Research
– Embedding Barium Titanate (BTO) nanoparticles within a perovskite solar absorber to reduce bimolecular charge recombination.
– Bimolecular charge recombination arises from direct band-to-band electron-hole charge carrier recombination

• Project Objectives
– Determine if BTO nanoparticles retain ferroelectric properties when embedded in perovskite solar absorber.

– Determine the optimal ratio of BTO : CH3NH3PbI3-xClx concentrations for producing most efficient solar cell.

– Determine if AACVD fabrication method is capable of producing highly crystalline thin films.

• Importance
– Validate a new, efficient, and inexpensive source of renewable energy.
INTRODUCTION

• Topic of Research
– Embedding Barium Titanate (BTO) nanoparticles within a perovskite solar cell to reduce bimolecular charge recombination.
– Bimolecular charge recombination arises from direct band-to-band electron-hole charge carrier recombination

• Project Objectives
– Determine if BTO nanoparticles retain ferroelectric properties when embedded in perovskite solar absorber.

– Determine the optimal ratio of BTO : CH3NH3PbI3-xClx concentrations for producing most efficient solar cell.

– Determine if AACVD fabrication method is capable of producing highly crystalline thin films.

• Importance
– Validate a new, efficient, and inexpensive source of renewable energy.
INTRODUCTION

• Topic of Research
– Embedding Barium Titanate (BTO) nanoparticles within a perovskite solar cell to reduce bimolecular charge recombination.
– Bimolecular charge recombination arises from direct band-to-band electron-hole charge carrier recombination

• Project Objectives
– Determine if BTO nanoparticles retain ferroelectric properties when embedded in perovskite solar absorber.

– Determine the optimal ratio of BTO : CH3NH3PbI3-xClx concentrations for producing most efficient solar cell.

– Determine if AACVD fabrication method is capable of producing crystalline thin films of BTO : Perovskite composites.

• Importance
– Validate a new, efficient, and inexpensive source of renewable energy.
INTRODUCTION

• Topic of Research
– Embedding Barium Titanate (BTO) nanoparticles within a perovskite solar cell to reduce bimolecular charge recombination.
– Bimolecular charge recombination arises from direct band-to-band electron-hole charge carrier recombination

• Project Objectives
– Determine if BTO nanoparticles retain ferroelectric properties when embedded in perovskite solar absorber.

– Determine the optimal ratio of BTO : CH3NH3PbI3-xClx concentrations for producing most efficient solar cell.

– Determine if AACVD fabrication method is capable of producing crystalline thin films of BTO : Perovskite composites.

• Importance
– Validate a new, efficient, and inexpensive approach to increase device parameters of solar cells.
 THEORY

• BTO (BaTiO3) is a known ferroelectric material

• Dipoles align in the direction of the applied field.
• Retain dipole orientation in the absence of an external electric
• Dipole orientation can be reversed.
field.
• Internal electric field guides charge carriers to their respective
electrodes.
 THEORY CONTINUED

Standard Device Proposed Device

Cu – Top Contact Cu – Top Contact

Electron

Hole
- - Increased
Photocurrent
Photons
+ +

Photons

ITO – Bottom Contact ITO – Bottom Contact

 AEROSOL ASSISTED CHEMICAL VAPOR DEPOSITION
Fabricating BTO: Perovskite Composites
- PbI2 Micro Droplets Micro Droplets Evaporate and/or Decompose
- CH3NH3Cl (4-5 µm) on the Substrate Making Precursor Vapors
- BTO
Atomization Surface Reaction Micro-Particle
with Mesh Coating
Nebulizer

Precursor Heated Substrate

Solution

N2 gas Substrate
Holder

 
N2 gas

 Growth Parameters of Nanocomposites

Nebulizer • Precursor concentration: variable
Precursor
to Vacuum
pump
• Substrate Temperature: 120 oC
Solution
• Chamber Pressure: 550 Torr
• Nozzle-Substrate Distance: 4.5 cm
 THERMAL EVAPORATION
Depositing Cu Electrodes

 Pressure = 10-6 Torr

• Initial 5 min – increase power input from 0% - 5%

• Then, increase power by 1% every 3 minutes
• Dwell time (5 min) – let thermal evaporator sit at
12% power
• Deposition (15 min ~ 100 nm) – 12% power
• Decrease power by 1% every 3 minutes
POLARIZATION MEASUREMENTS
• Electrical Hysteresis – frequently used test to determine a material’s
ferroelectric properties

– Radiant Technologies Ferroelectric Tester with Microprobe

Station

• Allows us to determine the spontaneous and remnant polarizations

A Typical P-E data for 50 nm BTO Nanoparticles

• Film thickness ~ 5µm
• Applied electric field: 1 kV/cm
• Remnant Polarization: 0.017 µC/cm2
• Coercive field: 0.12 kV/cm

Dielectric Characteristics of a Barium Titanate Film Deposited by Nano Particle Deposition System (NPDS) (Yang, Seungkyu, Kim, Pawar, Ahn, Caroline, Lee) [2015]
 POLARIZATION MEASUREMENTS CONTINUED

• Film thickness ~ 2- 7 µm
• Remnant Polarization: 0.04 – 0.07 µC/cm 2

100% BTO 70% BTO

0% Perovskite 30% Perovskite
Polarization

Polarization
(µCcm-2)

(µCcm-2)
0.08
0.3
0.06
0.2
0.04

0.02 Pr 0.1
Pr
0
-8 -6 -4 -2 0 2 4 6 8 0
-10 -8 -6 -4 -2 0 2 4 6 8 10
-0.02 Voltage (V) Voltage (V)
-0.
-0.04

-0.
-0.06

-0.08 -0.
 NANOPARTICLE SIZE ANALYSIS
Nanoparticle Tracking Analysis

Total Concentration Particle Size 40.5 nm - 60.5 Percentage of Total

[particles / ml] nm [particles / ml] Particles In Size Range [%]

24.311 E+7 18.577 E+6 7.641

NANOPARTICLE TRACKING ANALYSIS

• Possible clustering of
nanoparticles
• Impurities (e.g. dust, dirt)

• Contains 50 nm
nanoparticles
Total Concentration Particle Size 40.5 nm - 60.5 Percentage of Total
[particles / ml] nm [particles / ml] Particles In Size Range [%]

24.311 E+7 18.577 E+6 7.641

NANOPARTICLE TRACKING ANALYSIS

• Possible clustering of
nanoparticles
• Impurities (e.g. dust, dirt)

• Contains 50 nm
nanoparticles
Total Concentration Particle Size 40.5 nm - 60.5 Percentage of Total
[particles / ml] nm [particles / ml] Particles In Size Range [%]

24.311 E+7 18.577 E+6 7.641

• Impurities
• Not likely to be
nanoparticles
NANOPARTICLE TRACKING ANALYSIS

BTO 50nm 2hr sonic 2017-07-21 Clip #1

NANOPARTICLE TRACKING ANALYSIS

BTO 50nm 2hr sonic 2017-07-21 Clip #1 BTO 50nm 2hr sonic 2017-07-21 Clip #2
 SCANNING ELECTRON MICROSCOPY
• Optimal BTO concentration
 30% – 40%
• Based on SEM, XRD, and
absorption measurements

• At higher BTO concentrations,

nanoparticles tend to form clumps
 CHALLENGES
• Delayed arrival of Kr gas to run PLD chamber (~ first 3 - 4 weeks) to
fabricate Y2O3 dielectric layer

• Unavailability of PLD process due to complete flushing of Kr gas (~

last 2 weeks)

• Poor polarization measurements without Y2O3 dielectric layer

• Rapid deterioration of perovskite solar absorber due to humidity, O2,

and UV light on our samples
• Rewiring of mechanical pump’s electrical connections
• Malfunctioning pressure gauge of thermal evaporator
 CONCLUSION
• AACVD technique is capable of fabricating crystalline thin films of BTO :
Perovskite nanocomposites.
• BTO nanoparticles retain ferroelectric properties when embedded in
perovskite solar absorber.
• AACVD method can be extended to fabricate any solution-processable solar
absorber : BTO nanocomposite thin films
 FUTURE WORKS

• Fabricating nanocomposite thin films of 30 – 40% BTO concentration(based on structural and

optical data) on top of Y2O3 dielectric layer

• Perform polarization measurements and EFM (Electron Force Microscopy) to confirm

polarization of the composite
• Fabricating a fully functional perovskite solar cell with embedded 40 % BTO nanoparticles and
without nanoparticles and perform J-V measurements to study the effect of BTO nanoparticles
in solar cells
– Unfortunately LAMSAT is not currently equipped to do this
ACKNOWLEDGEMENTS
Thank You
Questions?