Nanowire Solar Cells

Peidong Yang
Department of Chemistry
University of California, Berkeley
Materials Science Division
Lawrence Berkeley National Laboratory
Materials Sciences Division
 Emerging PV

• Low cost
• Intermediate efficiency
• Environmental benign
• Possible solar paint

Materials Sciences Division

MRS Bulletin, Jan 2005
 Emerging PV

Grätzel, M. Nature 414, 2001.

Alivisatos et al. Science 2002, 295, 2425.

Why nanowires are important?

Materials Sciences Division
PV Performance Metrics

J MV M
FF =
J SCVOC

Pout FF × Voc × J sc
Efficiency = =
Pin Pin
Materials Sciences Division
η A = (1 − e −αd
) η ED = e − d / L D

IQE(λ) = ηA(λ) ηED ηCT ηCC

Pout
∫
FF x VOC
ηPCE = = q F(λ)IQE(λ)dλ
Pin Pin
Materials Sciences Division
S. Forrest. MRS Bulletin, Jan 2005
 Emerging PV

ƒ Use of solar at terawatt levels requires drop in $/Wp

ƒ 3N: New materials, New designs, New tricks

“dirty” semiconductors quantum effects

organics dye-sensitized cells carrier multiplication
oxides
frequency shifting
absorbers bulk heterojunction cells
biological subunits (polymer, organic-inorganic) Interface engineering

Materials Sciences Division

 Dye-sensitized Photoelectrochemical Cell

electron diffusivity: 10-4 cm2/s

Poor charge collectors?

Grätzel, M. Nature 414, 2001.

MLCT
Absorbanc

DSC characteristics
ƒ surface area of 800 – 1000 cm2 per cm2

ƒ η of 5 -10% with TiO2 nanoparticles

e

ƒ electron transport via trap-mediated diffusion

Wavelength(nm) ƒ Low efficiency at long wavelength

Materials Sciences Division
The three ways to improve DSC efficiency

1) Find dyes that function efficiently across the visible and near-IR
2) Raise open-circuit voltage closer to its theoretical maximum
3) Increase the electron diffusion length in the oxide anode, Ld = (Deτ)1/2

speed up electron transport slow recombination

adopt a nanowire geometry engineer the active interface

Nanoparticle DSC Nanowire DSC

random, polycrystalline network oriented single-crystalline channels

slow diffusive transport fast band conduction (field-assisted)

efficient for films ~10 μm thick in principle, efficient for much thicker cells

high internal surface area smaller internal surface area

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Nanowire DSC: Design Principle

high nanowire density

long, thin nanowires

electrode length (μm) diameter (nm) density (x1010 cm-2) SA

nanoparticle 8 - 10 15 - 30 n/a 800 - 1000

ideal nanowire 20 60 3 1080

achieved NW 20 130 0.3 ~200

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 Large-Scale Nanowire Array Synthesis

1st: dip-coat to get ZnO quantum dots 2nd: grow nanowires from QD seeds

zinc salt
hydrolysis,
HMTA

60-90 °C

L. Greene et al. Angew Chem. Int. Ed. 42, 3031, 2003 .

ƒ Nanowire densities of 1-40 billion cm-2
ƒ Single-crystalline wires in direct contact with the substrate
ƒ Inexpensive and environmentally benign
ƒ Compatible with arbitrary substrates of any size
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Control of Nanowire Aspect Ratio
300
without PEI
250 with PEI
Poly-ethylenimine (PEI):

diameter (nm)
200

H2N-(CH2CH2N)x-(CH2CH2NH)y-]- 150

100
CH2CH2NH2
50
Hybrid DSC
0
0 5 10 15 20
length (microns)

500 nm
5 μm

Hybrid: aspect ratio = 10 DSC: aspect ratio > 150

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Alignment Control

500 nm

200 nm

Greene, L.E., Law, M. et al. Nano Letters 5, 1231 (2005).

Materials Sciences Division
 High Optical Quality

5K
25 K
45 K
65 K
85 K
105 K I/a.u.
125 K
145 K
165 K
185 K
215 K
I/a.u. 245 K
A / a.u. E / a.u. 275 K
350 360 370 380 390 400 410
300 K
λ/nm

300 400 500 600 360 370 380 390 400

λ / nm λ /nm

ƒ TEM shows that the nanowires are single crystals

ƒ Wire surfaces are clean (Raman, EELS) after 400 °C treatment

Materials Sciences Division

 Characterization of Nanowire Arrays
Electrical: Ohmic wire-substrate contacts FETs: Wires have high e- mobility
1.5 125
VSD = 100 mV 40 V
100
75 20 V
1.0

ISD (nA)
50
0V
25
-20 V
0.5 0 -40 V
-50 -25 0 25 50
VG (V)

ISD (μA)
0.0

-0.5

-1.0

-1.5
-1.0 -0.5 0.0 0.5 1.0
VSD (V)
ƒ Individual wires are electrically conductive
ρ = 0.1 - 1 Ω cm
mobility: 1-5 cm2V-1s-1
electron diffusitivity: Dn=0.05-0.5 cm2s-1 [D = kBTμ/e ]
Ensure larger electron diffusion length, avoiding possible
interfacial recombination Law, M., Greene, L. et al.
Nature Mater. 4, 455 (2005).
Materials Sciences Division
Nanowire based DSC

Black = 12 nm TiO2 NP
Blue = 30 nm ZnO NP
Green = 200 nm ZnO NP
Red = ZnO nanowires

• NW cells are competitive with thin TiO2

nanoparticle cells (ηcc ~ 100%)
ηPCE = 1.5% under AM • NW cells outperform ZnO nanoparticle cells
1.5 G conditions
Law, M., Greene, L. et al. Nature Mater. 4, 455 (2005).
Materials Sciences Division
Nanowire DSC

Faster electron injection in NW cell

Bi-exponential (<250fs, 3ps)

vs.

Tri-exponential (<250fs, 20ps, 200ps)

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Time Scale for Electron Injection and Transport

Grätzel, M, MRS Bulletin, Jan 2005

Materials Sciences Division
Engineer active interface to reduce recombination

Core-sheath Nanowire Cells

Overcoat the nanostructured electrode with an insulating or semiconducting oxide

Reduce recombination
ƒ Physically separate electrons and holes

ƒ Form a tunneling barrier

Substrate

ƒ Passivate recombination centers on oxide surface

Shift band edge to increase Voc

ƒ Use an oxide with a higher band edge energy
Redox
Dye ƒ Form dipole layer that bends band upwards

Gregg, B. NREL.
Materials Sciences Division
Atomic Layer Deposition (ALD)

Oxides: Al2O3, TiO2, Ta2O5, Nb2O5, ZrO2, HfO2, SnO2, ZnO, La2O3, Y2O3, CeO2, Sc2O3, Er2O3, V2O5, SiO2, In2O3, ...
Perovskites: SrTiO3, BaTiO3, LiNbO3, LaMnO3 …
Nitrides: AlN, TaNx, NbN, TiN, MoN, ZrN, HfN, GaN, ... Fluorides: CaF2, SrF2, ZnF2, ...
Metals: Pt, Ru, Ir, Pd, Cu, Fe, Co, Ni, ... Carbides: TiC, NbC, TaC, ...
Mixed structures: AlTiNx, AlTiOx, AlHfOx, SiO2:Al, HfSiOx, ... Sulfides: ZnS, SrS, CaS, PbS, ...
Nanolaminates: HfO2/Ta2O5, TiO2/Ta2O5, TiO2/Al2O3, ZnS/Al2O3, ATO (AlTiO) ...
Doping: ZnO:Al, ZnS:Mn, SrS:Ce, Al2O3:Er, ZrO2:Y, ... rare earth metals (Ce3+, Tb3+ etc.) also co-doping

Example: ZnS

Planar Systems, Inc.

Materials Sciences Division

Core-sheath Nanowire Dye-sensitized Solar Cells

Materials Sciences Division

Nanowire-polymer Hybrid Cell

Poly(3-hexylthiophene)
C6H13

0 vacuum
-] ]-

-2.5 S
2LD ~ 20 nm
-3.5
~2.1 eV H3C H3 C H 3C
H3C H 3C

-4.5 ZnO
ITO Ag )- S

H3C
S
S

H3C
S
S

H 3C
S
S
S
S

P3HT
H3C H3 C

CH3 CH3
CH3 CH3

S S S S
S S S S S
H3C H3C H 3C
H3C H3 C

Target nanowire array

a
CH3 CH3
CH3 CH3

2LD S
S
S
S
S
S
S
S
S )-

1) ultrahigh nanowire density

CH3 CH3
CH3 CH3
c
2) short, thin nanowires
3) nanowires normal to substrate
Materials Sciences Division
Nanowire-polymer Composite Film

Aligned wires
Inter-wire spacing is 10-50 nm
2LD for P3HT ~ 20 nm
Thickness 200-300 nm

200 nm

Materials Sciences Division

 The Ideal Nanowire Cell

• Low cost
• Intermediate efficiency
• Environmental benign
• Possible solar paint

• Fully interdigitated donor-acceptor interface

• Acceptor wire array: high density, smaller band gap

• Donor: polymer/nanoparticles, maximize absorption

• Interface engineering: reduce recombination.

• Applicable to DSC, hybrid, and conventional semiconductor cells. N. Lewis

Materials Sciences Division
 Acknowledgement

Dr. Matt Law

Lori Geene
Dwaud Tan

Funding
DOE
ITRI
Materials Sciences Division