Flexible Dye-Sensitized Solar Cells on Al Foils

Jon Linville, Tyler Spurlock, Matthew Seitz and Xiaojuan (Judy) Fan Department of Physics, Marshall University, Huntington, WV 25755

http://www.siliconsolar.com/

*Email address: fan2@marshall.edu

STAR Symposium, 2010, WV

Brief Review: Photovoltaic Solar Cells

Si crystals: need to be produced in a vacuum. Thin film solar cells: Si, CdTe; GaAs, GaN, InN,
Cu(In,Ga)Se2 flexible solar cell modules (commercialized)

Dye-sensitized solar cells (DSSC)

ORegan and Grtzel, 1991 Cell Components: Porous nanocrystalline TiO2 Organic dye molecules Iodine/Iodide electrolyte 11% efficiency has been demonstrated in lab Ready to the market Question: Can we make flexible DSSCs?

Yes

The 3rd generation Solar Cells: DSSCs

Dye-sensitized solar cells (DSSCs): electrochemistry

Key components:
Metal oxide nanostructures Organic light sensitizer: dye molecules Electrolyte with I / I3

Advantage:
Low cost, solution process, and environmental friendly

Disadvantage:
Low efficiency (<11%), low stability, high volatility, short lifetime

How DSSC Works

1. Light absorbed by dye 2. Excited electrons injected into nanoparticles 3. Electrons percolate to external load to reach the counter electrode
e

hv
e e e e e

I- I3-+ e I- I3-+ e

TiO2 Dye

e
Load

4. Electrons are transferred to tri-iodide to yield iodide 5. The iodide reduces dye to its original state.

Printed Flexible Dye-Sensitized Solar Cells (DSSC)

Very recently, news from Japan's Toin University of Yokohama DSSC in a flexible A4 sheet. Solar conversion efficiency: 6% (Solar cells on market: 15%) Advantages Cheaper to make Flexibility Simply be printed in air Only 0.4mm-thick, used for a laptop PC or rolled and folded for storage.

Solar Cell Fabrication Technology

High vacuum deposition: p-n junctions Sputtering deposition Thermal evaporation E-beam evaporation Pulsed laser deposition Molecular beam epitaxial
Silicon Solar Inc.

Ribbon and roll-to-roll coating on flexible substrates Dye-sensitized solar cells (DSSCs): no vacuum needed Nanoparticle paste The new organic Sol-gel-dip-coating solar cells are light and flexible. Screen printing Credit: Spray pyrolysis Nicole Cappello, Compression Georgia Institute of Technology Polymer assisted

Mesoporous TiO2
TiO2: must be
Porous: large surface area to attach more dye molecules TiO2 nanoparticles Porosity > 50% Other metal oxides can be used, ZnO, SnO2, 50 nm Nanoparticle paste and hydrothermal at 230C TiO2, easy synthesis, Gratzel, M. J. Photochem. And Photobio. A 164 abundant, inexpensive
(2004) 3-14

Thermal evaporation

500C rf sputtering

Ti anodized in HF

K. M. Gopal, et al, Adv. Funct. Mater,15, 2005, 1291-1296

TiO2: A large band gap semiconductor

A large bandgap semiconductor (~3.2 eV) Absorption edge is in ultraviolet (UV), Not responsible for sun light absorption in solar cells

Rutile

Anatase
National Renewable Energy Laboratory, Golden, Colorado Materials Characterization Laboratory, Penn State

Brookite

Unique route to generate porous TiO2 thin films Our Approach:

Polymer assisted Ti alkoxides Solvents Stable precursors Spin coating (stable in air) Thermal sintering Polymer removed Mesoporous TiO2

Ti n-butoxide

Ti[O(CH2)3CH3]4

PMMA: (MW 350,000) poly(methyl methacrylate)

(C5O2H8)n

solvent

Ti alkoxides

SEM images: double-layer structure

(a) (b)

2 % (w/v) PMMA + 6% (w/v) Ti(OnBu)4

4 % (w/v) PMMA + 6% (w/v) Ti(OnBu)4

(c)

(d)

6 % (w/v) PMMA + 6% (w/v) Ti(OnBu)4

1 m

8 % (w/v) PMMA + 6% (w/v) Ti(OnBu)4

Porous TiO2 Thin Films: Structure and Morphology

X-ray diffraction: anatase phase
AFM image
(a) (b)

25 nm

10

20 nm

Particle size: 25nm Anatase structure is often preferred to rutile in the application of TiO2 in DSSC in terms of lattice packing.
[Park, et al. J. Phys. Chem. B 2000, 104, 8989-8994]

Thin Film X-Ray Reflectivity Analysis

thickness, density, and roughness
Critical angle c Density
10
0

roughness 1 roughness 2 roughness 3

Period of oscillation

density 1 density 2 density 3

thickness d1 thickness d2

10

-1

Thickness d
10
-2

Reflectivity

10

-3

Decay of amplitude Interface roughness

Amplitude of oscillation
10
-4

Contrast of density
10
-5

Decay of reflectivity
0 2 4 2/ (degree) 6 8

Surface roughness

Oscillatory behavior known as Kiessig fringes.

TiO2 thin film thickness, roughness, and density

X-ray Reflectivity

Table 1. Density, thickness and roughness of sample 4 from XRR data.

Relative porosity: Pr = 33%

Pr = 1 / 0
For nonporous anatase TiO2 0 ~ 3.9 g/cm3,

Layer Layer No. 1 2 Name Si TiO2

Density (g/cm3) 2.3300 2.6727

Thickness (nm) N/A 18.506

Roughness (nm) 0.489 0.579

Dye Molecule we used

2.5

Dye: TCPP in EtOH solution

2.0

Absorbance

1.5 1.0 0.5 0.0

450

500

550

600

650

700

Wavelength, nm

Meso-tetra(4-carboxyphenyl)porphyrin (TCPP), T790 Color: Red brown Absorption: 400 450 nm region, 500 700 nm region Adsorbs strongly onto nanoparticulate TiO2 and serves as an efficient photosensitizer. [J. Phys. Chem, 104, 3624 (2000)]

Gel Electrolyte: Polymer Matrix

Advantages:
Avoid liquid leakage Any shape membrane

PEG

C2nH4n+2On+1

Polymer electrolyte we used

Poly(ethylene glycol) (PEG), (MW 20,000) 100 mM KI, 50 mM I2 Solvents including: ethylene carbonate (80% v/v)
o Transparent crystal-like solid, at T = 25 C o Colorless liquid at T = 34 - 37 C

Hydro gel electrolyte

propylene carbonate (20% v/v)

o Colorless liquid

To Characterize Solar Cells

Current Density (mA/cm )
20

Isc

Maximum Power Point

ImVm

Incident Light Power: Ps Cell Maximum Power:

15

Pm = I mVm
Short Circuit Current: Isc Open Circuit Voltage: Voc

10

Voc
0 0.0 0.2 0.4 0.6 0.8 1.0

Bias Voltage (V)

I mVm Fill Factor FF: FF = I scVoc

I scVoc FF Photo electricity conversion efficiency: = Ps

Photo-Electricity Conversion Efficiency

Conversion efficiency:

I SCVOC FF = Plight
Fill Factor:

FF =

I mpVmp I SCVOC

I-V Curves under one Sun (AM1.5 global, 100 mW/cm2) and Dark.

Isc = 3.03 mA/cm2, Voc = 1.18 V, = 2.05%

Efficiency improvement > 200%

8 7 6 5 4 3 2 1 0 0.0 0.2 0.4 0.6 0.8

Current density(mA/cm )

Voltage(V)

Several factors: Nanoparticle imbedded electrolyte Different Dye molecules (N3 instead of T790) Porous TiO2 with high ratio polymer template

Flexible Dye-Sensitized Solar Cells

Anode electrode: porous TiO2 on Al foil

Cheap Dye: Basic Red 1, Rhodamine 6GDN Formula: C28H31CIN2O3, red to brown in color.

Electrolyte: Imidazolium +I2 + PEO, solid texture phase

Photo-Electricity Conversion Efficiency Flexible solar cell on Al Foil

Back Illumination

Conductive PET sheet Solid Electrolyte Porous TiO2 Al foil

Summary
Developed printable precursors for porous TiO2 thin films on metal foils Cheap dyes work well Polymer imidazolium electrolytes is compatible to solid solar cells. Future work: Try more recipes to get better materials to improve the efficiency and figure out what result in the low FF, photo current Explore a new way to remove polymer at low temperature that allows using plastic substrate and illumination from front side

Acknowledgements:
Funding Support: NSF-MU ADVANCE Grant NASA WV EPSCoR Seed Grant NASA Undergraduate Research Grant Marshall University Research Corporate

Undergraduate Researchers: Matthew Seitz, Sophomore Tyler Spurlock, Sophomore Jon Linville, Senior

Thank you for your attention!