1938-11

Workshop on Nanoscience for Solar Energy Conversion

27 - 29 October 2008

Impedance Spectroscopy of Nanostructured Dye-Sensitized and Organic Bulk Heterojunction Solar Cells

Juan BISQUERT Departament de Fisica, Universitat Jaume 1 Avda. Sos Baynata sn 12071 Castello de la Plana Spain

Impedance spectroscopy of nanostructured dye sensitized and organic bulk heterojunction solarcells
JuanBisquert
Departament deFsica Universitat JaumeI 12071Castell Spain
Trieste,Italia,28october 2008

Fundamentalmodel of asolarcell

Fundamentalmodel for asolarcell

1. Generation 2. Recombination (radiative) 3. Extraction
The necessary spatial extension of the light absorbing material makes it necessary to consider electron diffusion Diffusion competes with recombination as described by diffusion length

J. Bisquert, D. Cahen, G. Hodes, S. Rhle, A. Zaban Journal of Physical Chemistry B, 108, 8106-8118 (2004)

Fundamentalimpedance model for asolarcell

Fundamentalimpedance model for asolarcell

Chemical capacitance converts excess carriers number into a potential (Fermi level)

Recombination resistance is unavoidable. Prevents the internal loss of photogenerated carriers

Fundamentalimpedance model for asolarcell

Diffusionrecombination transmission line model

Diffusionrecombination transmission line model

Impedance spectroscopy gives all parameters of electronic processes at once:

Conductivity Chemical capacitance Recombination resistance

J. Bisquert, J. Phys. Chem. B 106, 325-333 (2002) F. Fabregat-Santiago, J. Bisquert, G. Garcia-Belmonte, G. Boschloo, A. Hagfeldt Solar En. Mat. Sol.Cells, 87, 117-131 (2005).

Transmission line for diffusionrecombination

chemical capacitance transport recombination

Transmission line for diffusionrecombination Electron Lifetime

LD much longer than thickness (low recombination)

RW Rk Z = 1 + i / k

1/ 2

coth ( k / d )1 / 2 (1 + i / k )1 / 2

Diffusion coefficient

Siliconsolarcell
Lifetime = Rrec C

Siliconsolarcell

Lifetime

Chemical capacitance Recombination resistance

Some results on dyesensitized solarcells with different hole conductors with impedance spectroscopy

Impedance of 11%efficiency dye solarcell

This solar cell shows ideal characteristic of diffusionrecombination model with recombination resistance much larger than transport resistance R3 >> R1

Recombination arc R3
Michael Grtzel, Francisco Fabregat-Santiago, Juan Bisquert et al., J. Phys. Chem. B. 110, 25210-25221 (2006)

Diffusion Warburg R1/3

Electron diffusion coefficient

L2 Dn = ( Rt C )
Parameters of 11% DSC
Temperature dependence of electron diffusion coefficient in a DSC, as a function of potential This data concordates with the prediction of the multiple trapping model

Michael Grtzel, Francisco Fabregat-Santiago, Juan Bisquert et al., J. Phys. Chem. B. 110, 25210-25221 (2006)

Impedance characteristics of DSCs

DSC with ionic liquid Ion diffusion in electrolyte Electron recombination Charge transfer at CE

Stability Upscaling

Steadystate characteristics of 11%DSC

Photocurrent-voltage curve of 11% efficiency DSC obtained at AM 1.5 solar radiation. The dots show the calculated values based on impedance measurements carried out at different voltage bias of the cell with the same illumination. Dashed line represents the simulated curve after subtraction of the series resistance contribution. A 10 % increase in the fill factor is obtained.

DSCcellwith spiroOMeTAD ashole conductor

F. Fabregat-Santiago, J. Bisquert et al JPCC (2007), 111, 6550

F. Fabregat-Santiago, M. Grtzel, J. Bisquert et al (2008), submited

DSCcellwith spiroOMeTAD ashole conductor

ConductivityinTiO2

Rt = rt L

L Rt S (1 p) EFn Ecb kT

= 0 exp

= e n

DSCcellwith spiroOMeTAD ashole conductor

Chemical diffusion coefficient of electrons in TiO2
(1 ) Dn = D0 exp ( EFn Ecb ) kT

DSC cell with spiro-OMeTAD as hole conductor

Lifetime

n = Rct C
100 10 1 0.1 0.01 0.001 0.0

V decay Voc oc decay

oc decay = kT dt
OMeTAD liquid

e dV

(s)

0.2

0.4

0.6

Potential (V)

A. Zaban et al. ChemPhysChem, 4 (2004) 859 F. Fabregat-Santiago et al. J. App. Phys. 100 (2006) 034510

DSC cell with spiro-OMeTAD as hole conductor

Diffusion length of electrons

LD = Dn

Evolution of DSCatUJI
DSC record laboratorio UJI: 7.2% eficiencia referencia con N719 rea 0.3 cm2
Evolucin Eficiencias DSC en la UJI
7

Eficiencia (%)

1
Julio 07 Sept 07 Nov 07 Febr 08 Mayo 08 Julio 08

Tiempo (meses)

CdSe quantumdotsensitizedSC
Ivan Mora-Ser

Universidad de Alicante Roberto Gmez Teresa Lana

CdSe quantumdotsensitizedSC

3electrodesmeasurements Closedcell
e j = j 0 exp (V Vref kT (1 ) e ) exp (V Vref kT )

j0 (Polysulfide) = 11.4 nA/cm2 j0 (I3-/I- ) = 40.7 A/cm2

Impedance spectroscopy of P3HT:PCBM organic solarcell

The standard model the pinmodel

The pinmodel for amorphous Si

The pinmodel for amorphous Si

ResultsofimpedanceonP3HT:PCBMsolarcells

Juan Bisquert,

Germ Garcia-Belmonte, Antoni Munar

Henk J. Bolink, Michele Sessolo, Alejandra Soriano (ICMol Valencia)

Irati Ugarte, Roberto Pacios

Characteristics of P3HT:PCBMsolarcell

Schottky barrier Diffusion-recombination of electrons (minority carrier

G. Garcia-Belmonte, A. Munar, E. M. Barea, J. Bisquert, I. Ugarte, R. Pacios Organic Electronics 9, 847-851 (2008)

Impedance measurements in the dark varying forward bias ITO/PEDOT:PSS/P3HT:PCBM/Al

V. D. Mihailetchi et al. Avd. Funct. Mater. 13, 43-46 (2003)

ITO/PEDOT:PSS/P3HT:PCBM/Al

n = eDn / k B T ~210-3 cm2 V-1 s-1

cm V s ) Electron mobility (10

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.2 0.4 0.6 0.8 1.0 illumination dark

-3

-1

-1

Bias voltage (V)

G. Garcia-Belmonte, A. Munar, E. M. Barea, J. Bisquert, I. Ugarte, R. Pacios Organic Electronics 9, 847-851 (2008)

Dopingof P3HTSchottky barrier

Forward bias Minority carrier storage (electrons)

Oxidation of P3HT p-doping level ~51016 cm-3

M. S. A. Abdou et al. J. Am. Chem. Soc., 119, (1997)

G. Garcia-Belmonte, A. Munar, E. M. Barea, J. Bisquert, I. Ugarte, R. Pacios Organic Electronics 9, 847-851 (2008)

Shift of MottSchottky plot

Forward bias

J.Bisquert,G.GarciaBelmonte,A.Munar,ASoriano,M.Sessolo,H.J. Bolink Chem.Phys.Lett.465 5762(2008)

Shift of MottSchottky plot

Kelly-Memming J. Electrochem. Soc. 75, 085316 (1982)

Kinetic limitation

J. Li and L.M. Peter, J. Electroanal. Chem. 193 (1985) 27.

Photovoltaic model

F. El Guibaly, K. Colbow and B.L. Funt, J. Appl. Phys. 52 (1981) 3480.

Negative capacitance insolarcells

CdS/CdTe solar cell

Forward bias

I. Mora-Ser, J. Bisquert, et al. Nano Letters 6, 640, (2006)

ModelofelectroninjectioninorganicLEDs

1.Equilibrium 2.Equibriumbetweenmetalandsurfacestate 3.Decreaseoftheoccupationoftheintermediatestateat increasingforwardbias duetohigherkineticsoftransferat higherforwardbias

movie

J. Bisquert, G. Garcia-Belmonte, A. Pitarch, H. J. Bolink, Chem. Phys. Lett. 422, 184 (2006)

Negative capacitance in OLEDs

OC4H9 OC4H9 OC4H9 OC4H9

y
OCH3

z *

100 nm 80 / 150 nm 0 / 200 nm

OCH3

cathode

ITO/PEDOT:PSS/SY/Al

-2

LEP (Super Yellow) PEDOT ITO Glass substrate

Abs(Capacitance) [F cm ]

10-6

10-7

10-2

1.0 V 2.0 V 3.0 V 3.6 V 4.0 V 4.6 V

Current density [A cm-2]

10-3 10-4 10-5 10-6 10-7 10-8 0 1 2

Au

Ag Mg

10-8 (b) 10-9 100 101 102 103 104

Geometric Capacitance 105 + SCLC

Bias voltage [V]

Frequency [Hz]
Interface states: transit from positive to negative capacitance

Model

J.Bisquert,G.GarciaBelmonte,A.Munar,ASoriano,M.Sessolo,H.J. Bolink Chem.Phys.Lett.465 5762(2008)

Model
2n x 2 n n0 Ln 2 +

Dn

e x = 0

J n (0) = J n ( w) + e w 1

Generation, recombination, diffusion in neutral region, collection in scr

Transference through ss

C d Vd C scVsc = N I q
Electrostatic at the interface

J 12 = N I k12 {(1 ) A B}
J 23 = N I k 23 {N cC n(0)(1 ) H }

Model

The solution of the model provides the following expression for the photocurrent

J n (0) = N I k 23

Jg Ln Dn n 0 qVsc / k BT (1 ) He NcC + Ln Dn tanh y L 1 + N I k 23 Ln (1 ) He qVsc / k BT Dn tanh y L

2 2 L n J g = 1 e w + 2 2 1 L n

e L 1 w w tanh y L e e cosh y L L n

This allows to determine ss occupancy and therefore, the distribution of potential and Fermi level at the interface

Potential in space charge region and dipole layer

0.4

0.2

E Fn

dark light

voltage voltage

0.0

- 0.2

- 0.4

Voltage= =-0.1 0 Voltage = Voltage 0.1

-4 -2

0 position

Model simulation of current-potential curve

dark light

Shift of Mott-Schottky plot

dark light

Electron density in equilibrium [10^12 cm-3] : The total density (per unit area) of interfacial levels [1012 cm-2]

J.Bisquert,G.GarciaBelmonte,A.Munar,ASoriano,M. Sessolo,H.J.Bolink Chem.Phys.Lett.465 5762(2008)

Acknowledgments

Funding: MCINN,ESF,Fundaci Caixa Castell Bancaixa

Homepage:www.elp.uji.es/jb.htm Email: bisquert@uji.es

Acknowledgments

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