The Effect of PEDOT:PSS and ITO Treatment in Excitonic Solar Cells: A Nanoscopic Investigation P. Alexander Veneman, Adam G.

Simmonds, Neal R. Armstrong

Abstract
Indium Tin Oxide (ITO) is the most commonly used anode in Organic Photovoltaics (OPVs) due to its optical transparency and relatively high electrical conductivity. ITO is an imperfect electrode, and electron transfer between the ITO and adjacent organic layers is hampered by heterogeneous coverage of surface contaminants and the fact that the oxide itself is most likely a heterogeneous mixture of phases with varying electrical properties. ITO for organic Light-Emitting Diodes (OLEDs) and OPVs is often treated by methods such as detergent or solvent cleaning, oxygen plasma or ozone cleaning and/or coating with poly(3,4ethylenedioxythiophene) heavily doped with poly(styrenesulfonic acid) (PEDOT:PSS). The effect of these modifications at the nanoscopic level is still not fully understood, and although the effect of current-voltage properties of the devices has been studied, a working model describing their physical effects at the relevant length scales are lacking. In this work we use Conducting-Probe Atomic Force Microscopy (C-AFM) to study these surface modifications at the nanometer length scale, and compare these results to current-voltage data for macroscopic OPVs. Our results indicate that PEDOT:PSS is a band-aid fix for the deeper problem of heterogeneity of the ITO surface. PEDOT:PSS electrically wires over dead spots on the ITO, making an electrically uniform electrode, but it also introduces another energy barrier to the device that increases the diode quality factor and thus decreases fill factor. We also find that aggressive acid etching of the ITO surface results in increased homogeneity, and much improved repeatability in the manufacture of devices.

Conducting Tip Atomic Force Microscopy (C-AFM) and ITO Surface Treatments
These C-AFM images demonstrate the 15nm electrical heterogeneity of the ITO surface. This lack of uniformity is due to carbonaceous impurities and hydroxide species 0nm contaminating the surface. Additionally it -5 nA is unclear whether the ITO is composed of a single or multiple phases of varying electrical activity. Modification of the ITO surface can increase the electrical activity 0 nA of the film by removing contaminant species and possible changing the relative ratio of phases present on the surface.

Organic

Height Image

ITO In C-AFM a metal-coated cantilever is moved back and forth across a samples surface. The vertical deflection of the cantilever is measured by monitoring the deflection of a laser beam reflected off the back of the cantilever, giving a topographic map of the surface. By applying a voltage to the tip and measuring the current flow we generate corresponding maps of sample topography and electrical properties. It is also possible to obtain current-voltage curves at a single point with an area of ~20 nm2.

Current Map (-5mv) 500 nm

Detergent Cleaned ITO O2 Plasma Treated ITO 12M HCl-0.2M FeCl3 Etched ITO

Heterogeneity of ITO/CuPc I-V Behavior as a Function of PEDOT:PSS Use and ITO Pretreatment
Detergent Cleaned ITO/CuPc/Pt Tip O2 Plasma Treated ITO/CuPc/Pt Tip 12M HCl-0.2M FeCl3 Etched ITO/CuPc/Pt Tip
1e+8 1e+8 1e+8 1e+7 1e+7 1e+7

Current Density (mAcm-2)

Current Density (mAcm-2)

Current Density (mAcm-2)

(+) Pt
Tip

Treated ITO

1e+6

1e+6

1e+6

1e+5

1e+5

1e+5

CuPc (-)
-0.5 0.0 0.5 1.0

h +

1e+4

1e+4

1e+4

ITO

1e+3 -1000

-500

500

1000

1e+3 -1000

-500

500

1000

1e+3 -1.0

Tip Bias (mV)

Tip Bias (mV)

Tip Bias (mV)

Detergent Cleaned ITO/PEDOT:PSS/CuPc/Pt Tip

1e+8 1e+8

O2 Plasma Treated ITO/PEDOT:PSS/CuPc/Pt Tip

1e+8

12M HCl-0.2M FeCl3 Etched ITO/PEDOT:PSS/CuPc/Pt Tip

1e+7

Treated ITO With PEDOT:PS S

Current Density (mAcm-2)

1e+6

1e+6

Current Density (mAcm-2)

Current Density (mAcm-2)

1e+7

1e+7

(+)

Pt Tip h+

1e+6

CuPc
1e+5

1e+5

1e+5

PEDOT

1e+4

1e+4

1e+4

(-)
-1.0 -0.5 0.0 0.5 1.0

ITO

Each semi-log plot on the left shows current-voltage curves at several different ~20 nm2 areas on the same organic film. The data indicate that the electrical heterogeneity of the ITO affects the current flowing through the above Copper Phthalocyanine layer (top row). The addition of a PEDOT:PSS mediator layer (bottom row) makes the electrode electrically uniform by allowing current to pass over any insulating regions on the ITO surface. The PEDOT:PSS/CuPc interface is also rectifying in such a manner as to collect photocurrent and suppress dark current. It should also be noted that the acid etch produces a surface that is already very uniform and is actually hindered by the addition of the PEDOT:PSS layer (right column).

1e+3 -1000

-500

500

1000

1e+3 -1000

1e+3 -500 0 500 1000

Tip Bias (mV)

Tip Bias (mV)

Tip Bias (mV)

Detergent Cleaned ITO

O2 Plasma Treated ITO

12M HCl-0.2M FeCl3 Etched ITO

Equivalent Circuit Model for Excitonic Heterojunction Solar Cells

PEDOT:PSS

Macroscopic OPV Current-Voltage Behavior

ITO/CuPc/C60/Alq3/Al
Photovoltaic Devices
10
O2 Plasma Treated (Dark) O2 Plasma Treated (Illuminated)

ITO

CuPc

C60

Al

ITO/PEDOT:PSS/CuPc/C60/Alq3/Al
Photovoltaic Devices
10
O2 Plasma Treated (Dark) O2 Plasma Treated (Illuminated) Acid Etched (Dark) Acid Etched (Illuminated) Detergent Cleaned (Dark) Detergent Cleaned (Illuminated)

ITO

CuPc

C60

Al

Current Density (mAcm )

-2

Electrically Dead Spots

Current Density (mAcm )

-2

Acid Etched (Dark) Acid Etched (Illuminated) Detergent Cleaned (Dark) Detergent Cleaned (Illuminated)

-5

-5

? 3.8eV 3.8eV

-10 0.0 0.1 0.2 0.3 0.4 0.5 0.6

-10 0.0 0.1 0.2 0.3 0.4 0.5 0.6

Bias (V)
Detergent Cleaned Oxygen Plasma Acid Etched 4.73 +/- 0.87 6.02 +/- 0.64 5.71 +/- 0.57 0.399 +/- 0.069 0.38 +/- 0.02 0.379 +/- 0.019 0.486 +/- 0.11 0.39 +/- 0.08 0.521 +/- 0.052 0.93 +/- 0.37 0.91+/- 0.3 1.12 +/- 0.14 0.39 +/- 0.8 4 +/- 2.8 0.04 +/- 0.06 3.13 +/- 0.75 3.388e-3 +/- 6e-4 2.09 +/- 0.05

Bias (V)
Detergent Cleaned Oxygen Plasma Isc (mAcm^-2)= 5.69 +/- 0.72 5.9 +/- 0.57 Voc (V)= 0.456 +/- 0.004 0.47 +/- 0.02 FF= 0.37 +/- 0.02 0.34 +/- 0.05 Effieciency (%)= 1.0+/- 0.14 0.9 +/- 0.14 i0 (mAcm^-2) n 0.05 +/- .01 6.3 +/- 0.66 Acid Etched 5.4 +/- 0.4 0.46 +/- 0.01 0.41 +/- 0.01 1.01+/- .06

4.3eV ~4.5eV

4.3eV ~4.5eV

4.3eV

4.3eV

Isc (mAcm^-2)= Voc (V)= FF= Effieciency (%)= i0 (mAcm^-2)= n=

5.2eV 5.4eV 5.4eV

0.02733 +/- 6e-4 0.011 +/- 0.002 4.20 +/- 0.05 3.8 +/- 0.14

6.3eV

6.3eV

The basic equivalent circuit model for a bilayer excitonic solar cell is a light driven current source in parallel with a diode and a shunt resistance, all existing at the donor-acceptor interface. There is another resistance in series with this circuit branch, due to the low conductivities of the transport layers and the resistance associated with carrier injection at the electrical contacts. As shown above, the ITO surface is electrically heterogeneous and so each unit area of the ITO may be thought of as its own photocell, the full solar cell being made up of all the individual area units electrically connected in parallel by the electrodes. Due to its much higher conductivity compared to the transport layers, PEDOT:PSS effectively shunts current over the dead spots in ITO. As long as large areas of the ITO electrode are not insulating, the PEDOT:PSS ameliorates the poor surface properties of ITO, at the expense of adding an additional energy barrier (diode) to the system.

These current voltage curves demonstrate the effect of surface treatment and/or additional PEDOT:PSS layer. The curves on the right (PEDOT:PSS layer) exhibit poor fill factor. This is due to an increase in the diode quality factor (n) relative to the curves on the left (no PEDOT:PSS) caused by the additional energy barrier in series with the Donor-Acceptor interface. PEDOT:PSS increases the short-circuit current of the detergent-cleaned ITO, which suffers the most from electronically inactive regions. For the acid etched ITO and O2 plasma treated ITO the surface is already fairly uniform and the PEDOT essentially does not affect the power conversion efficiency (Voc increase offsets decrease in fill factor). It is also worth noting that the acid etched ITO surfaces uniformity results in significantly improved uniformity from device to device (see width of power conversion efficiency confidence interval, above)

THE UNIVERSITY OF ARIZONA

Acknowledgements: The authors would like to thank NSF/STC CMDITR (DMR-0120967) and ONR for their generous financial support