Excitonic Solar Cells

Etgar Lioz
Laboratoire de Photonique et Interfaces, Institut des Sciences et Ingnierie Chimiques, Ecole Polytechnique Fdrale de Lausanne (EPFL), Station 6, CH-1015, Lausanne, Switzerland.

Outline
Introduction Quantum dots based solar cell Energy transfer in dye sensitized solar cell (DSSC) ZnO NWs as photoanode for DSSC Summary Future perspective

Introduction
Why Solar? More solar energy is absorbed by the earth every minute than issued in fossil fuels every year. Pollution free and wastes/emissions are easily manageable. Effective in providing electricity to remote locations where other forms of energy are difficult or expensive to get.
Fukushima

Pollution

What is a solar cell?

Solar cells convert sunlight directly into electricity. First used in spacecraft and satellites. Traditional types are based on two types of silicon sandwiched together (n-type and p-type). Based on using photons to separate charges: electron-hole pairs Many new types are in research/production stage.

Introduction
First Generation Consist of large-area, high quality and single junction devices. Involve high energy and labour inputs making these very costly. Example: Crystalline Silicon solar cells Second Generation Consist of Thin film cells. Techniques such as vapor deposition and electroplating are advantageous. Expensive production costs. Examples: CdTe, Thin film silicon, CIGS. Third Generation Aim to enhance poor electrical performance of second generation while maintaining very low production costs. o Multi junction solar cells. o Nanostructures solar cells. o ETA cells. (Extremely thin absorber cells) o Dye-sensitized cells. o Polymer-fullerene cells.

Silicon photovoltaic cell

Dye sensitized solar cell

Charge separation by electric field within a p- and n-doped semiconductor material.

Charge separation by kinetic competition like in the photosynthesis

Dye sensitized solar cells

Electrochemical cell

Voc = (EFn EFp ) / q

Introduction

Characterization Standard Power density of 1000 W/m2 Spectral power distribution corresponding to AM1.5
The Air Mass is the path length which light takes through the atmosphere normalized to the shortest possible path length The Air Mass quantifies the reduction in the power of light as it passes through the atmosphere and is absorbed by air and dust.

Solar spectrum

Excitonic Solar cells (XSCs)

e-

Metal Contact Gel QDs

TiO2 NPs film FTO glass

QDs properties:
Quantum size effect, Influence the optical properties. High optical absorption cross section. Multiexciton generation (MEG) A relatively large exciton effective Bohr radius. Relatively high dielectric constants. Surface functionalities by ligand exchange.

Quantum dots solar cells

Chemical bath deposition (CBD) Successive ionic layer adsorption and reaction (SILAR) Colloidal quantum dots attached through molecular linker. CBD,SILAR

QDs through molecular linker

TiO2
FTO Glass FTO Glass

Cell structure
Metal Contact eEnergy (eV) QDs TiO2 NPs film FTO glass

-4.1 TiO2

-3.7 NIRQDs -5.1 -5.1 Au

Advantages

-7.3

h+

1.Solid state device. 2.No hole transport material. 3.Illumination close to the junction. 4.Easy to produce, cost effective. 5.Employ many monolayers of the light absorber due to the charge transporting functionality of the CQD film.

Ligands exchange to MPAPbS QDs deposition by spin coating and ligands exchange to 3-mercaptopropionic acid (MPA).

Cross section of the device

Gold PbS QDs TiO2 NCs FTO Compact layer
Ligands can change: Energy levels. Solubility. Optical properties. Shape of the QDs.

Which factors can affect the QDs solar cell performance?

The thickness of the QDs film.
If the QD layer is too thick, collection of photogenerated charge carriers will be incomplete, while too thin QD layers show poor light harvesting.
e-

QDs Eg (size)

e-

Small QDs - more driving force for electron injection and higher Voc, on the other hand more particle boundaries to cross until the electrons arrive at the TiO2(higher chances for recombination). Big QDs- less driving force for electron injection and lower Voc, but should have less particle boundaries to cross until the electrons arrive at the TiO2

TiO2 thickness
Thick TiO2 film the injected electrons wont reach the conductive glass.

Photovoltaic Performance
Voc=0.543 V Jsc=16.3mA cm-2 Fill factor = 41% (PCE)= 4.04% (under 90mW cm-2)

Cell conditions1. TiO2 18nm NPs, 500nm thickness film. 2. PbS QDs- size of 3.2nm corresponding to frist excitonic peak at wavelength of 920nm. 3. 12 layers of 50mg/ml. (thickness of ca.300nm) Etgar et al., ACS nano, 2012, DOI: 10.1021/nn2048153.

Electrochemical Impedance Spectroscopy (EIS)

Nyquist plots
Two different features were observed, 1. A high frequency arc (frequency range ~1MHz to 100kHz), whose size depends strongly on the applied bias potential. 2. A low frequency arc (frequency range~kHz to mHz). From each feature we can extract the Resistance, capacitance and lifetime.

At low bias potential.

At high forward bias with the indication of the frequencies.

Electrochemical Impedance Spectroscopy (EIS) Low frequency

TiO2/PbS interface Recombination resistance and capacitance

High frequency
PbS/Au interface

Lifetime

OH C O

Voc incresing-

Voc

QDs
C=O

TiO2

SH CO2-

Changing the TiO2 dominant facets

101

001

Exposed (001) anatase TiO2

Standard-Exposed (101) anatase TiO2

Anatase 101 has the most stable surface, its surface energy is the lowest 0.91 Jm-2 Anatase 101 surface is unreactive. Anatase 001 has the higher surface energy (1.43 Jm-2) and its surface is reactive.

Characterization
Intensity [a. u.]
(101)

(200)

[001] d001=0.235 nm
(105) (211) (116) (220) (204) (215)

(004)

10 nm
20 30 40 50 60 70 80

2 [Degrees]

50 nm

100 nm

Cross section

TiO2 nanoplatelets

PbS QDs absorbance

Photovoltaic performance

Etgar et al, Advanced Materials, 2012, 24(16), 2202-2206.

Summary
QDs cell architecture without hole conductor was presented. Around 12 layers of QDs is the optimum thickness for the QDs layer, using PbS QDs with energy gap of 1.38eV. EIS technique helping us to see more deeply into the device electronic properties. Anatase TiO2 nanosheets having 30 and 80nm size, with dominant (001) facets were synthesized and employed in PbS QDs/TiO2 heterojunction solar cell. The best photovoltaic performance was achieved using 30nm TiO2 nanosheets with PbS QDs having Eg of 1.38eV. The photovoltaic parameters give a Jsc of 20.5 mA/cm2, a Voc of 0.545V, a FF of 0.38 corresponding to a solar to electric power conversion efficiency () of 4.73% under 0.9 light intensity. The higher surface area related to the small nanosheets and the high reactivity of the (001) facets contribute to the better performance of the PbS QDs/TiO2 heterojunction solar cell compared to standard TiO2 NPs.

E(eV) -3.57 -3.6 Co+2/Co+3 -5.32

-4.05

-5.38

Advantages: -7.25 No ligands exchange for the QDs TiO2 VG1-C10 CdSe New design dyeNPs Dye QDs electrolyte Co complex electrolyte

-5.6

Overlap spectra

The frster radiusthe distance at which the frster energy transfer (FRET) efficiency is 50%.

9000(ln10) 2QD J 6 R0 = 128 5 n 4 N AV

n is the refractive index of the host : 1.4-1.5 for the electrolyte in DSSC. k2 is the orientation factor -2/3 for random orientation, QD is the quantum efficieny of the donor (28%), Nav is the Avogadro number.

J is the overlap integral, J = I D ( ) A ( ) d

0

R0 = 3.7nm

PL lifetime of VG1C10 +QDs On Glass

QDs emission (Donor)

The arrows indicate the increase of the QD/VG1-C10 ratio.

VG1-C10 emission (Acceptor)

FRET efficiency

E = 1 DA D = 69%

Cell type VG1-C10 dye VG1-C10+CdSe QDs (FRET cell)

Jsc (mA/cm2) 2.73 3.25 +19%

Voc (mV) 542 653.4 +20%

FF 0.536 0.69 +29%

PCE 0.79 1.48 +87%

Etgar et al, RSC Advances, 2012, 2 (7), 2748 - 2752.

Summary
This work presents the enhancement of the light harvesting in dye sensitized solar cell due to Frster resonance energy transfer. The donors are CdSe QDs and the acceptors are a new design squaraine dyes with an additional carboxcilic group and two long hydrocarbon chains as compared to the standard squaraine dye. The use of the cobalt complex (Co+2/Co+3) as electrolyte in the cells permits direct contact between the QDs and the electrolyte without affecting the QDs. PL lifetime measurements showed that FRET is the dominant mechanism from the QDs to the dye. IPCE measurements exhibit a full coverage of the visible region. All the cell photovoltaic parameters were enhanced proving the efficient energy transfer within the QD-dye-sensitized solar cell.

Why ZnO NWs instead of TiO2 NPs?

ZnO
Crystal structure Energy gap (eV) Electron mobility (cm2VS-1) Growth rocksalt,zinc blende and wurtzite 3.2-3.3 205-300(bulk ZnO), 1000 (single NW) Low temperature, milder conditions, controllable conditions NWs-improve charge carrier transportation by providing a facile direct electron pathway

TiO2
rutile, anatase and brookite 3-3.2 0.1-4 High temperature

NPs

Problems??
1. High efficiencies require high dye-loading. Typically TiO2-based DSSCs use semiconducting layers of around 20 m thick to ensure a high amount of dye can be incorporated into the active layer. Growing ZnO NWs of comparable length and internal surface area under hydrothermal conditions is not trivial due to competing of homogeneous and heterogeneous nucleation processes. 2. The surface of ZnO is known to be chemically unstable and contain surface trap states.

ZnO NWs electrochemical cell-

Z960 electrolyte based acetonitrile

High molar absorption coefficient () of 62.7103 M-1 cm-1 at 555nm

O

C218 Dye
N S S CN COOH

C55H 68 N 2O4 S 2 Exact Mass: 884.46

Etgar et al. Energy & Environment Science, 2011, 4, 2903-2908 .

10m length of ZnO NWs-

10m length of ZnO NWsThe overall energy conversion efficiencies of the cell was measured under AM 1.5 solar radiation to be 1.25%. Voc= 524.1 mV; Jsc= 5.49 mA/cm2; ff= 0.43

Core Shell ZnO/TiO2 NWs

Shell thickness optimization

1.0 0.9 0.8 2.0 2.5 0.9

Voltage (V) Fill factor

Efficiency (%)

0.6 0.5 0.4 0.3 0.2 0.1 0 10

1.5

J sc (mAcm )

0.7

Fill factor and V OC (V)

0.8 0.7 0.6 0.5 0.4 0.3 0 10 20 30 40

1.0

Efficiency (%) Jsc

20 30 40

0.5

0.0

Shell thickness (nm)

-2

Shell thickness (nm)

10m thick of ZnO/TiO2 core shell NWs

Open-circuit voltage (Voc) of 819.6 mV Short circuit current density (Jsc) of 5.08mA cm-2 Fill factor of 60.6% Power conversion efficiency of 2.53% under AM1.5

Dark Current

Full-scale semilogarithmic plots in the dark of the ZnO NWs DSC and the ZnO/TiO2 DSC.

Dark current of the bare ZnO NWs DSC is higher than the dark current of the ZnO/TiO2 NWs DSC. A smaller dark current suggest a lower rate of recombination which results an increasing of the Voc and the fill factor.

Summary
DSSC using new type of photo anode, ZnO NWs was presented.

Using 10m thick of ZnO NWs photoanode increase the dye loading and hence increase the efficiency. One of the highest efficiencies using ZnO NWs was received 1.25%. Coating the ZnO NWs with 20nm TiO2 shell increase the fill factor and the Voc dramatically resulting an efficiency of 2.53%.

Summary
PbS Quantum dots/TiO2 heterojunction solar cells were presented achieving

power conversion efficiency of 4.7% with cuurent density of 20.5 mA cm-2.

Energy transfer between CdSe QDs as donors and Squarine dyes as acceptors in dye sensitized solar cell show an enhancement of 87% in power conversion efficiency . ZnO NWs coated with 20nm TiO2 shell as photoanodes in DSSC presenting PCE of 2.5%.

Future Perspective
q Nanostructures oxide films as photoanode for XSCs. q Nanostructured inorganic-organic heterojunction solar cells. q Stability

Acknowledgment
Marie Curie, Intra European Fellowships (IEF), FP7-PEOPLE-2009-IEF.PIEF-GA-2009-252228. Innovasol, FP7-energy-NMP 2008- Novel materials for energy application. Prof. Graetzel Michael. LPI members. (around 50!!)