Dye-Sensitized Solar Cell (DSSC)

http://bp.snu.ac.kr

http://bp.snu.ac.kr

Photoelectrochemical Cells (Solar Cell and Water Cleavage)

M. Grtzel, Nature (2001)

Solar Cell

Changwoo

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Electrode Potential (E0) vs. Vacuum Potential (eV)

M. Grtzel, Nature (2001)

Solar Cell/Semiconductor

Chunjoong

http://bp.snu.ac.kr

Dye-Sensitized Solar Cells (DSSCs)

< >

Prof. Kyo Han Ahns group (POSTECH) http://www.postech.ac.kr/chem/mras

Solar Cell
Chunjoong

http://bp.snu.ac.kr

Dye-Sensitized Solar Cell

Michael Grtzel (Ecole Polytechnique) Inorg. Chem. 44, 6841 (2005)

1. Dye electrons are excited by solar energy absorption. 2. They are injected into the conduction band of TiO2. 3. Get to counter-electrode (cathode) through the external circuit. 4. 5.
I3 2e 3I - : Redox regeneration at the counter-electrode (reduction).

3I - I 3 2e : Dye regeneration reaction (oxidation).

6. Potential used for external work:

Solar Cell
Hongsik

Vext E F Vredox
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Exciton Binding Energy

Dye-Sensitized Solar Cells

Jinsang Kims group (University of Michigan) Adv. Funct. Mater. (2012)

Organic Solar Cell

P3HT: Poly(3-hexylthiophene) Carsten Deibels group (Julius-Maximilians-University of Wrzburg) Phys. Rev. B 81 085202 (2010)

Solar Cell

Hongsik

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Dye-Sensitized Solar Cell

< Introduction > Dye-sensitized solar cells (DSSC) were invented by Michael Grtzel and Brian O'Regan [Nature, 353, 737 (1991)] . The DSSC is formed by a combination of organic and inorganic components that could be produced at a low cost. The DSSC offers the prospect of a cheap and versatile technology for large scale production of solar cells. The basic element of a DSSC is a nanostructured material, an assembly of TiO2 nanoparticles about 20 nm diameter, well connected to their neighbors. TiO2 is the preferred material since its surface induces highly effective electron transfer. However, TiO2 only absorbs a small fraction of the solar photons (those in the UV). Molecular sensitizers (dye molecules) attached to the semiconductor surface, are used to harvest a great portion of the solar light. The main dye molecules consist on one Ru metal atom and a large organic structure that provides the required properties (wide absorption range, fast electron injection, and stability).

Solar Cell

Hongsik

http://bp.snu.ac.kr

Dye-Sensitized Solar Cell

Homepage in Grtzels group

Solar Cell

Jongmin

http://bp.snu.ac.kr

The Benefits of DSSC

Silicon Solar Cell - Costly fabrication process - Expensive raw materials - Toxic gases

Dye Sensitized Solar Cell - Easy to be fabricated - Low cost - Friendly to the environment

Solar Cell

Hongsik

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Dye-Sensitized Solar Cell (DSSC)

M. Grtzels group, Nature (1991)

Solar Cell

Changwoo

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TiO2 Nanoparticles for DSSC

hydrothermal method ~20 nm size, anatase phase ~10 m thickness for efficient photon absorption
M. Grtzels group, J. Am. Ceram. Soc. (1997)

Solar Cell

Changwoo

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TiO2 Phase Dependency for DSSC

Rutile phase DSSC , anatase phase . . Rutile phase nanoparticle 20 nm 80 nm rod , spherical anatase nanoparticle 20 nm . rutile nanoparticle anatase nanoparticle dye , photocurrent . N.-G. Park et al., J. Phys. Chem. B (2000)

Solar Cell

Changwoo

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Dyes for DSSC

proton detachment chemical bonding with TiO2

M. Grtzel, Inorganic Chemistry (2005)

Solar Cell

Changwoo

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Dyes for DSSC (N719)

Chemical Structure of N719 dye

M. Grtzel, Inorganic Chemistry (2005)

Solar Cell

Changwoo

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Dyes for DSSC (N719)

Ti bonding . dye adsorption to TiO2

Chemical Structure of N719 dye cf) Chemical Structure of N3 dye Bu4N: tetrabutylammonium

Solar Cell

Changwoo

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Optimizing Dyes for DSSC

Anchoring LUMO
N3

HOMO

Organometallic dye: charge separation

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anatase (001)

anatase (101)
the most stable plane

A. Selloni Nat. Mater. 7, 613 (2008) H. G. Yang et al. Nature 453, 638 (2008)
Anatase TiO2 chemical adsorption , Ti bonding . Solar Cell
Changwoo

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anatase (101) N719 dye dye

Ti

Ti

M. Graetzels group JPCB (2003)

, dye-coated TiO2 film FT-IR , TiO2 Ti dye chemical bonding .

Solar Cell

Changwoo

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Dyes for DSSC (N719)

3-D Structure of Ru complex Solar Cell

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Changwoo

Operation of DSSC
M. Grtzel, Inorganic Chemistry (2005)

_______

IPCE (%)

good photon absorption, good charge separation IPCE: Incident Photon to Current Conversion Efficiency

Solar Cell

Changwoo

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Dye-Sensitized Photovoltaic Cells

M. Grtzel, Inorganic Chemistry (2005)

_________________________________

_________________

Solar Cell

Changwoo

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Kinetic and Energetic Paradigms

10 electrons per TiO2 particle under AM1.5. More than 90% of electrons in TiO2 are trapped and <10% in the conduction band. There are -10,000 adsorption sites for H+ on an 18 nm (diameter) TiO2 particle. A TiO2 particle (18 nm) has 600 dye molecules on the surface. (0.59 dyes/nm2) Each dye molecule absorbs one photon per second. The flux of electron injection into the TiO2 particle is 600 s-1. 1 dye per 150 TiO2 particles is in its oxidized state.
Brian C. ORegan,s group, Account of Chemical Research (2009).

Anders Hagfeldts group, Chemistry Review (2009).

Solar Cell

Chohui

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Kinetic and Energetic Paradigms

Brian C. ORegan,s group, Account of Chemical Research Open-Circuit Potential The two main determinants of Voc are the recombination rate constant and the TiO2 conduction band edge offset relative to the I-/I3- redox potential. (2009).

Short-Circuit Current This efficiency depends upon the diffusion constant (mobility) and recombination rate of the electrons in TiO2.
Solar Cell
Chohui

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Brian C. ORegan,s group, Account of Chemical Research (2009).

Solar Cell

Chohui

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TiO2 Nanotubes for DSSC

C. A. Grimess group, Nano Letters (2006)

Ti deposition by sputtering (500 nm) Anodizing Ti film at constant potential, 12 V. (HF condition) Pore diameter: 46 nm Wall thickness: 17 nm Length: 360 nm

Solar Cell

Changwoo

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TiO2 Nanotubes for DSSC

= 2.9%

360 nm

C. A. Grimess group, Nano Letters (2006)

Solar Cell

Changwoo

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TiO2-Electrode / Electrolyte Interface Problem

Solutions Core-shell Structure wide bandgap materials Surface Treatment Ar or O2 plasma, TiCl4 treatment Nanoscale Coating on the TCO

Solar Cell

Changwoo

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CaCO3-Coated TiO2 Nanoparticles

CaCO3-coated TiO2 nanoparticle (core-shell)
CaCO3: basic than TiO2 carboxyl group of dye can adsorb more easily

CaCO3 is insulator (band gap: 6 eV) thick shell of CaCO3 block electron transfer from dye to TiO2
K. Hongs group, Sol. Energy Mater. Sol. Cells (2006)

Solar Cell

Changwoo

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CaCO3-Coated TiO2 Nanoparticles

Solar Cell

Changwoo

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MgO-Coated TiO2 Nanoparticles

K. Hongs group, Langmuir (2005)

MgO-coated TiO2 nanoparticle (nanoporous structure)

Jsc enhancement: increase of the dye adsorption Voc enhancement: suppression of the charge recombination

Solar Cell

Changwoo

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MgO-Coated TiO2 Nanoparticles

K. Hongs group, Langmuir (2005)

Solar Cell

Changwoo

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Metal-Oxide Coating on TiO2 Nanoparticles

Coating Layer Effect of TiO2 Coating Layer 1. The insulating layers with wide band gap and high conduction band edge can retard the back transfer of electrons from TiO2 to the electrolytes or dye molecules (decrease trap state). 2. The enhanced dye adsorption by the oxide layers can improve the cell performance The coated surface favors the dye adsorption through the carboxylic acid group of the dye.

Sujuan Wu et al. (Wuhan University) Nanotechnology 19, 215704 (2008)

Solar Cell

Hongsik

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MgO-Coated TiO2 Nanoparticles

Sujuan Wu et al. (Wuhan University) Nanotechnology 19, 215704 (2008)

Excessively thick MgO layer beyond the tunneling distance plays a negative role in the photoelectron conversion process.

Dye adsorption increase with sputtering time Solar Cell Hongsik

Resistance at the TiO2/dye/electrolyte increase with sputtering time http://bp.snu.ac.kr

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MgO-Coated TiO2 Nanoparticles

Solar Cell

Hongsik

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FTO / Blocking Layer / Porous TiO2

Introduction
Porous interfaces between FTO substrate and TiO2 layers can be electron recombination site, i.e., electron leakage sites exist especially when solid or highly viscous redox species such as ionic liquid iodides once infiltrate into the interfaces.

Blocking layer can suppress back electron transfer from FTO to electrolytes.

Shozo Yanagida Group (Osaka University) J. Phys. Chem. C 111, 8092 (2007) Solar Cell
Hongsik

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FTO / Nb2O5 / Porous TiO2

Sputtering method has the merits of good reproducibility, of homogeneous coverage and suitability for the large scale production. Excessively thick blocking layers beyond tunneling distance would play a negative role in the photoelectron conversion process.

Shozo Yanagida Group (Osaka University) J. Phys. Chem. C 111, 8092 (2007)

Solar Cell

Hongsik

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FTO / Nb2O5 / Porous TiO2

Solar Cell

Hongsik

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FTO / TiO2 Thin-Film Layer / TiO2 Nanoparticles

FTO/TiO2 compact layer/TiO2
Efficiency (1 Sun) With compact layer : 1.6% Without compact layer : 1.0 %

Efficiency (1/10 Sun) With compact layer : 1.6% Without compact layer : 0.6 %

Recombination rate decrease between FTO / Electrolyte JSC , VOC increase Solar Cell

Michael Grtzel et al. (Ecole Polytechnique) Nano Lett. Vol. 8, No. 4, (2008) http://bp.snu.ac.kr
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Hongsik

FTO / TiO2 Thin-Film Layer / TiO2 Nanoparticles

Solar Cell

Hongsik

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New Methods for TiO2 Nanostructures

Inverse-Opal Ti Anodization
100 nm

Hyunjung Lees Group (KIST) Adv. Funct. Mater (2009)

500 nm

~ 4.2% ~ 3.5%

P. Schmukis Group (Univ. Erlangen-Nuremberg, Germany) Angew. Chem. Int. Ed. (2009)

Solar Cell

Changwoo

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New Methods for the TiO2 Nanostructures

Hyunjung Lees Group (KIST) Adv. Funct. Mater (2009)

P. Schmukis Group (Univ. Erlangen-Nuremberg, Germany) Angew. Chem. Int. Ed. (2009)

Solar Cell

Changwoo

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Aggregates/Nanocrystallites Mixed TiO2 DSSCs

Guozhong Caos group, Electrochimica Acta, (2011).

Solar Cell

Chohui

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Guozhong Caos group, Electrochimica Acta (2011).

Solar Cell

Chohui

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I- Free Electrolyte

M. Graetzels Group Nat. Chem. (2010)

new electrolyte

conventional I-/I3electrolyte

Licheng Suns Group (Dalian Univ. of Tech.) Angew. Chem. Int. Ed. (2010)

Solar Cell

Changwoo

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I- Free Electrolyte
M. Grtzels Group Science (2011)

______

___________ _____________________________ ______________

Licheng Suns Group (Dalian Univ. of Tech.) Angew. Chem. Int. Ed. (2010)

Solar Cell

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DSSC Exceeding 12% in Efficiency

M. Grtzels Group Science (2011)

YD2-o-C8 dye

Solar Cell

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DSSC Exceeding 12% in Efficiency

M. Grtzels Group Science (2011) Solar Cell

Changwoo

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Characteristics of ZnO-Based DSSCs

Advantages

Easy to fabricate various nanostructures. Nanoflower Nanodisk Nanosheet

S. Fujiharas group, J. Electrochem. Soc. (2011).

C. M. L. Wus group, J. Phys. Chem. C (2010).

K.-C. Hos group, Energy Environ. Sci. (2011).

Nanowire

Nanotube

J. S. Bendalls group, Energy Environ. Sci. (2011).

W.-G. Diaus group, Energy Environ. Sci. (2011).

Single-crystal ZnO has carrier mobility of 115 - 155 cm2/Vs, which is 2 orders of magnitude higher than that of TiO2 (2 - 4 cm2/Vs).

Solar Cell

Chohui

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Characteristics of ZnO-Based DSSCs

Disadvantages Formation of Zn2+/Dye Aggregates

G. Caos group, Adv. Mater. (2009). Without Dye With Dye for 12 h

200 nm

200 nm

G. Caos group, J. Phys. Chem. C (2007).

G. Caos group, J. Phys. Chem. C (2007).

High acidity of the ruthenium-based dye can lead to dissolution of ZnO. Precipitation of dissolved Zn2+ ions and dye molecules is attached on the surface.
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Solar Cell

Chohui

G. Caos group, J. Phys. Chem. C (2007).

____________

Solar Cell

Chohui

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ZnO Aggregates DSSCs

Guozhong Caos group, Angew. Chem. Int. Ed. (2008).

Desired specific surface area for dye loading + light scattering = High conversion efficiency in dye-sensitized solar cells
Solar Cell
Chohui

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Guozhong Caos group, Angew. Chem. Int. Ed. (2008).

Solar Cell

Chohui

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Effect of an Ultrathin TiO2 Layer

-

_______

Guozhong Caos group, Adv. Mater. (2010).

Solar Cell

Chohui

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Guozhong Caos group, Adv. Mater. (2010).

Solar Cell

Chohui

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MgO- or ZrO2- Coated ZnO Nanowire DSSCs

N. O. V. Plank, J. Phys. Chem. C (2009).

Solar Cell

Chohui

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N. O. V. Plank, J. Phys. Chem. C (2009).

Solar Cell

Chohui

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Lithium Ions on ZnO DSSCs

Guozhong Caos group, Chem. Mater. (2010).

Solar Cell

Chohui

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Guozhong Caos group, Chem. Mater. (2010).

____________________

Solar Cell

Chohui

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Surface-Plasmon Resonance in Metal Nanoparticles

Oscillation of Free Electrons in Metal Nanoparticles

Unique Optical Properties of Au

[L. M. Liz-Marzan, Langmuir (2006)]

Solar Cell
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Surface-Plasmon Resonance in Metal Nanoparticles

L. M. Liz-Marzn (Univ. de Vigo, Spain) Langmuir (2006)

Solar Cell

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Field Enhancement vs. Scattering

Field Enhancement Scattering

h
h Active Material
Metal Contact

<Metal Nanoparticles at the Surface of Solar Cell>

I: Light Intensity E: Amplitude of E-Field

[H. A. Atwater et al., Nat. Mater. (2010)]

Both field-enhancement and scattering effects can contribute to the improvement of photovoltaic properties.
Solar Cell
Changwoo

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Field Enhancement vs. Scattering

H. Atwater et al. (Caltech) Nat. Mater. (2010)

Solar Cell

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Electric-Field Enhancement by Surface-Plasmon Resonance

4 3

H0

Relative Position (r/a)

2 1 0 -1 -2 -3 -4 -4 -3 -2 -1 0 1 2 3 4

h
| E |2

E0

at hv = 550 nm

Au Au

0.10 0.20 0.50 1.0 1.5 2.0 3.0 5.0 10 20 50

Relative Position (r/a)

Field Enhancement Light Absorption
Solar Cell

Photocurrent
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E-Field Enhancement by One Metal Nanoparticle

K. Tanabe (Univ. of Tokyo) JPCC (2008)
Ag NP in air

(at = 0)
inside the sphere outside the sphere

(Boundary Condition)

(at any r and )

in water, at r=a Solar Cell

Changwoo

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E-Field Enhancement by Metal Nanoparticle

K. Tanabe (Univ. of Tokyo) JPCC (2008)

Solar Cell

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Metal Induced Dye-Sensitized Solar Cells (DSSCs)

eeElectrolyte

Au-SiO2 Core-Shell Nanoparticle for DSSC

Au

[H. J. Snaiths group, Nano Letters (2011)]

Pt TCO

TCO

SiO2-Ag Core-Shell Nanoparticle for DSSC

Dye

SiO2

Metal-Oxide Nanoparticles
Solar Cell
Changwoo

[Jung-Kun Lees group, Adv. Energy Mater. (2011)]

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Metal Induced Dye-Sensitized Solar Cells (DSSCs)

Henry J. Snaiths group, (Univ. of Oxford) Nano Letters (2011) Solar Cell http://bp.snu.ac.kr
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Changwoo

Metal Induced Dye-Sensitized Solar Cells (DSSCs)

____________

___

Jung-Kun Lees group (Univ. of Pittsburgh) Adv. Energy Mater. (2011) Solar Cell
Changwoo

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DSSC + Surface Plasmon Resonance

J. T. Hupps group, (Northwestern Univ.) JACS (2009)
Ag NP deposition TiO2 ALD Dye adsorption

dyes on the glass substrate

<TiO2 Shell Thickness & Crystallinity Variation>

Absorption Difference Spectra (Ag + TiO2 + dye) (Ag + TiO2) Ag evaporation on glass substrate dye solution drop dye amount increase

TiO2 thickness increase

M. Iharas group, (Univ. of Tokyo) JPCB (1997)

Ag enhance the absorption rate of dye.

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Solar Cell

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DSSC + Surface Plasmon Resonance

J. T. Hupps group, (Northwestern Univ.) JACS (2009) Solar Cell http://bp.snu.ac.kr

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Changwoo

DSSC + Surface Plasmon Resonance

M. Iharas group, (Univ. of Tokyo) JPCB (1997)

Solar Cell

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Metal Nanosize Effect

The size of metal nanoparticles used in the previous researches on DSSCs was limited to 10 - 30 nm.

rAg = 50 nm

Scattering
Backward Scattering

<Ag-Diameter Variation>
Total Total

Absorption

2r =
Scattering

2r =
Scattering

rAg = 10 nm

Intensity

rAg = 30 nm

Absorption

Absorption Scattering
(nm)

Absorption

Absorption
(nm)

[Y. A. Akimovs group, Plasmonics (2009)] Theory (with One Nanoparticle)

[G. Chumanovs group, J. Phys. Chem. B (2004)] Experiments

Solar Cell

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Metal Nanosize Effect

Y. A. Akimovs group, (Institute of High Performance Computing, Singapore) Plasmonics (2009) Solar Cell
Changwoo

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Metal Nanosize Effect

G. Chumanovs group, (Clemson Univ., U.S.A.) JPCB (2004)

Absorptance + Reflectance + Transmittance = 1 Extinction = -log T

Solar Cell
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Scattering vs. Absorption by One Metal Nanoparticle

90

Absorption (or Scattering) Efficiency

Ag (100 nm) Au (100 nm)

Scattering Efficiency (%)

80 70 60 50 40 30 20 10 0 500

Cabs (or Csca) Cabs + Csca

<Calculation of Cross Section>

d = 2 + 0i

(assumption)

Ag (20 nm) Au (20 nm)

600

700

800

Wavelength (nm)

m: dielectric function of metal d: dielectric function of dielectric material V: volume of metal nanoparticle

Higher imaginary part of dielectric function of Au Dominant absorption-nature of Au Nanoparticle

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Solar Cell

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Quenching by Surface Plasmon vs. DSSC Kinetics

Exciton Quenching by Metal
Exciton

Kinetic Parameters in DSSC

Au
Au Diameter :12 nm Quinone Molecule

TiO2

Dye
M. Grtzels group, Inorg. Chem. (2005)

Quinone Molecule

A. O. Govorov et al. Nano Lett. (2007)

metal: over 100 picosecond

e-h separation: sub-picosecond

metal >> e-h separation

Quenching reaction by Au is negligible in DSSC.
Solar Cell
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Exciton Quenching by Metal Nanoparticles

A. O. Govorovs group (Ohio Univ.) Nano Lett. (2006)

dielectric function of metal dipole moment of semiconductor

Solar Cell

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Exciton Quenching by Metal Nanoparticles

A. O. Govorovs group (Ohio Univ.) Nano Lett. (2006)

Solar Cell

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Molecules near the Metal Nanoparticles

Field Enhancement Quantum Efficiency

Y=

Quantum Yield for Charge Generation

time constant for recombination

A. O. Govorovs group (Ohio Univ.) Nano Lett. (2007)

Solar Cell

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Molecules near the Metal Nanoparticles

A. O. Govorovs group (Ohio Univ.) Nano Lett. (2007)

Solar Cell

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Schematic Figure

Localized surface plasmons induce the electromagnetic-field amplifications.

B. Parks group (SNU) APL (2011)
Solar Cell
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Au Nanoparticle-Embedded DSSC

B. Parks group (SNU) APL (2011)

Solar Cell

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p-type Sensitized Solar Cell

<p-type Sensitized Solar Cell: NiO Electrode> Schematic energy diagram for p-type sensitized solar cell

(1)

(1) Electron transfer from the excited sensitizer to the oxidized species in the electrolyte. (2) Electron transfer from valence band of p-type NiO to the HOMO level of the sensitizer.
Errol Blarts Group (Universit de Nantes) Acc. Chem. Res. 48 1063 (2010)

(2)

Advantage

p-n junction solar cell

Combine an n-type TiO2-based photoanode with a p-type NiO-based photocathode Improving open circuit voltage (Voc)
Solar Cell
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p-n Junction Solar Cell

Scheme for the electron-transfer processes occurring in the dye-sensitized tandem solar cell TiO2 (0.8 m ) NiO (3.3 m)

In the case of TiO2 DSSCs, the maximum Voc is limited to about 1 V. Larger Voc (> 1 V) can be achieved by p-n junction solar cell
U. Bachs group (Monash University) Nat. Mater. 9 31 (2009) Solar Cell
Hongsik

Voc = EF (n-TiO2) EF (p-NiO)

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p-n Junction Solar Cell

Solar Cell

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Limitation for p-type Sensitized Solar Cell 1. Low open-circuit voltage (~0.1 V)
Small difference in potential between the Femi level in the NiO photocathode and the redox potential of electrolyte (iodide system) Solution: 1. New electrolyte system (sulfur system) 2. Modify NiO electrode (tuning p-type characteristic)

2. Low hole diffusivity in NiO

Rapid recombination of photogenerated hole Hole diffusion coefficient of NiO film (~10-8 - ~10-7 cm2/s) Electron diffusion coefficient of TiO2 (~10-5 - ~10-4 cm2/s) Solution: 1. Metal oxide (Al2O3) coating on NiO electrode (suppress recombination) 2. Graphene / NiO composite (Improve conductivity)

Solar Cell

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Modification of p-type DSSC: Al2O3 coating

Suppression of the carrier recombination by Al2O3 coating layer

Carrier collection efficiency increased by Al2O3 coating

Yiying Wus Group (Ohio State University) Langmuir 28 950 (2012) Solar Cell

Charge transfer resistance at the NiO/dye/electrolyte increase by Al2O3 coating layer http://bp.snu.ac.kr
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Hongsik

Modification of p-type DSSC: Al2O3 coating

_________________
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Modification of p-type DSSC: Graphene / NiO Composites

Synthesis Procedure for NiO/Graphene Composite Films

Solid arrows: charge transport (desired) Dashed arrow: recombination (undesired)

Charge recombination is significantly suppressed due to the enhanced hole transport by the presence of graphene. NiO/Graphene Composite Higher conductivity than the bare NiO film Jsc, Voc
Solar Cell
Hongsik

Chang Ming Lis Group (Nanyang Technological University) JPCC 115 12209 (2011) http://bp.snu.ac.kr
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Modification of p-type DSSC: Graphene/ NiO composite

Solar Cell

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