Heterojunction effects in OPV cells

 Categories of heterojunctions  OPV cells using WEG films  Optimization towards smart cells

Donghang Yan ( 闫东航 )
State key laboratory of polymer physics and chemistry, Changchun Institute of Applied Chemistry, CAS, Renmin Str. 5625, Changchun 130022, China

H.B. Wang, D.H. Yan, Science in China B39, 1 (2009).

 Categories of heterojunctions

Typical organic systems ZnPc/C60 CuPc/F16 CuPc, BP2T/F16 CuPc, P3HT/C60
F16 CuPc/SnCl2Pc p-6P/VOPc, p-6P/CuPc, 3PTh/VOPc


F16 CuPc CuPc Ta2O5 Heavily doped silicon wafer


Au Au

Gate-source voltage =0,-10V -30V -50V 0V -10V -30V -50V CuPc/F16CuPc heterojunction CuPc single layer

Drain current (A)


-1.0x10 -2.0x10 -3.0x10 -4.0x10




Normally-on OFET



-40 -30 -20 -10 Drain-source voltage (V)


Free holes accumulated at CuPc films

Semiconductor-Device Electronics, 1991 Oxford University Press

PN Junctions
doping n-type Si p-type Si

Free e

Ion residual

Free h

No free e or h

- Diffusion theory


Space charge region

Organic PN Junctions

n-type Si

p-type Si

- Diffusion theory

n-type F16 CuPc


p-type CuPc

- NEW theory ? !

D.H. Yan, H.B. Wang, B.X. Du, Introduction to Organic Semiconductor Heterojunctions, 2008

Thermal equilibrium conditions – a theoretical view
3.0 3.12 3. 5 3. 6 4.6 4.8 5.16 6.1 6.3 6.66 n-F16 CuPc EFn

Energy (eV)


EFp 4.82

According to thermal equilibrium conditions, the electrons prefer to flow from the high energy work function position to low energy work function position when two semiconductors are brought into contact.


5.0 5.2 p-CuPc




C. Shen, A. Kahn, JAP90,4549,2001 H. Peisert et al, JAP 93, 9683 (2003). K.M. Lau et al, APL 88, 173513 (2006). A.Kahn, JAP. 86,4515,1999

Depletion HJ

HJ effects in typical OPV systems

Molecular model

Band model Working mechanism

 OPV cells using WEG films
Weak epitaxy growth

(Accumulation HJ) Mismatch of charge and exiton transport, is an intrinsic problem for OPV cells ?

Of MPc WEG films

• Depletion heterojunction with C60
Al EBL C60

• Space charge thickness ~ 40 nm • Charge carrier mobility as single crystal - No effective deep traps at RT - Shallow traps of 0.056 eV at low T • Exciton diffusion length should be longer

Inducing layer ITO Glass

WEG films may over come the mismatch of charge/exiton transport in OPV cells



N N Cu N N N



10µ mx10µ m p-6P(2nm)/ZnPc(30nm) SiO2/ZnPc(30nm)




TFT transfer curves

Quality of WEG films is good as single crystal.

High quality of WEG films

No effective deep traps observed


eNd 2 = 2ε

Density of deep traps is about 2.6× 1016 /cm3.

Deep traps dominates electrical behaviors of organic crystalline films.

Hall effect
Lakeshore 7707, van der Pauw

delocalized transport


At the room temperature, the ratio of thermal activated charges to charges located at conductive band is ∼ 10 to 1 for WEG films.

Advanced Materials, adma.200903023, in press

OPV cells using WEG films
•Planar heterojunction (PHJ) device


AM 1.5G

Cell structure Ref PHJ WEG PHJ

Voc (V) 0.52 0.56


FF 0.55 0.65

PCE (%) 1.19 2.10

Saturation factor

4.16 5.76

1.27 1.07

Free electrons and holes can be collected efficiently.

Exciton diffusion length of MPc WEG films

20nm<λ E< 40nm

Space charge field ~ 40nm

ZnPc WEG films

C60 films

Exciton diffusion length of WEG films is not longer enough.

• Planar-mixed heterojunction (PM-HJ) device


High efficient cells are in optimization.

 Optimization toward smart cells
Larger VOC cell NIR cell

(PCE 10%)

Performance : Double Voc
Tunnel junction

WEG sub cell 2

Connecting unit
(Accumulation OHJ)

Connecting unit WEG sub cell 1

• OHJ supplies a view angle to understand and develop OPV cells. • We realized WEG ZnPc films, and applied to OPV cells. - high charge carrier mobility, low deep traps - exciton diffusion length is comparable to the absorption - moderate efficiency • Potential space for improving efficiency of OPV cells, - NIR absorbing materials, and - smart tandem cells

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