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The applications of nanocrystalline

materials in solar cells

Chun-Hui Huang

College of Chemistry and Molecular Engineering,

Peking University, Beijing, China
Department of Chemistry, Fudan University,
Shanghai, China

October 17, 2009

Chang Zhou,China
1. Background

2. The applications of nanocrystalline materials in

solar cells

2.1 The modifications of electrode

2.2 The solidification of electrolyte
2.3 Introduction of ZnO nanowires in
full solid state solar cells

3. Conclusions
1. Background

The two important issues

concerning the sustainable
development of human society:
energy and environment

Environment pollution induced by

consuming traditional energy

The fixed number of mining years for non-renewable energy sources

Petroleum Natural gas Coal Uranium

World 49 57 262 60

China 23 61 102 30

《 High-tech Development Report 2002 》 Chinese Academy of Sciences

The utilization of solar energy is the
important way to solve the problem of the
energy shortage

• Abundant
3∗1024 joule/year, which is 10000
times larger than that consumed by
the whole word.
• Unlimited availability
Solar cells roof
• CO2 free
Abundant solar energy resources in China

Two-thirds of the land

area in China is rich in
solar energy resources.
And the energy of the
solar radiation received
by land surface per year
is equivalent to 1.7 color Radiation Radiation amount per year ( MJ/ Radiation amount per day
Level m2 ) ( KWh/m2 )
trillion tons of standard
red best ≥ 6680 ≥ 5.1
coal, which is one Orange better 5850 - 6680 4.5 – 5.1
thousand times larger red

than the energy Yellow general 5000 - 5850 3.8 – 4.5

consumed in China in Pale blue poor 4200 - 5000 3.2 – 3.8

2007. Dark blue poorer < 4200 < 3.2

source : China PV Industry Development Report, Chinese large-scale renewable

energy development project management office , October 2004
Major ways of utilizing solar energy

Heat energy: Photothermic or thermoelectric conversion

Electrical energy: solar cells

Chemical energy: Hydrogen, Chemicals

Biomass energy : Hydrogen, Grease, Biomass

The utilization of solar energy concerns many subjects such as

chemistry, physics, material science, biology, chemical engineering
science and so on. Among the subjects, chemistry is the
fundamental one.
The types of solar cells

M. Grätzel, Nature, 2001, 414, 338- 344.

2. The applications of nanocrystalline materials
in solar cells
2.1 The modifications of electrode

Electrode Nanocrystal film electrode

with a (nanocrystal size: 15-
TiO2 S* smooth 20nm; film thickness:
- 0.5 surface ~10µm)

Surface area (cm2) 1 780


Counter electrode
Conducting glass

Cell efficiency <1 >7

I- I3-
0.5 Disadvantages:
S0/S+ a. Unsatisfactory cell life and stability
1.0 b. Leakage and volatilization of liquid electrolytes

c. Needing high standard seal techniques

M. Grätzel, Nature, 1991, 353, 737- 740.

2.2 The solidification of electrolyte

Hydroxyl group

High-temperature solid-state


1-Butyl-3-methylimidazolium iodide 1-Butyl-3-methylimidazolium tetrafluoroborate

The liquid electrolyte : BMI⋅ BF4/ I2/LiI-BMI⋅ I

The gel electrolyte : BMI⋅ BF4-SiO2/ I2/LiI-BMI⋅ I
Hybrid electrolytes

1 wt% SiO22 (●),

2 wt% SiO22
3 wt% SiO22 (∆),
4 wt% SiO22 (□),
5 wt% SiO22 (○),
6 wt% SiO22 (∗)

The energy conversion efficiencies of

The ionic conductivities show a
the cells rise with the increase of the
linear dependence on the
temperature and achieve a maximum
temperature, indicating a typical
value when the operation
Arrhenius behavior 。
temperature reaches 60 °C.
19 °C 4.0× 10-4 S cm-1 ,
60 °C , greater than 10-3 S cm-1 .

H. Yang, F.Y. Li,* C.H. Huang*.Chem. Mater., 2006, 18, 5173.

Z.G. Chen, F.Y. Li,* C.H. Huang*. J. Mater. Chem. 2007,17, 1602.
Z.G. Chen, F.Y. Li,* C.H. Huang*. ChemPhysChem, 2007, 8, 1293.
According to the principle of
molecular assembly, the formation BMI⋅ BF4-SiO2/ I2/LiI-BMI⋅ I (60 °C)
of the high-temperature solid-state
electrolyte originates from the self-
assembly of hydrogen bonds
between the OH group of silica
nanoparticles and the strongly BMI⋅ BF4/ I2/LiI-BMI⋅ I
electronegative F atom of BF4-.
 The PV cell based on the solid-
state electrolyte has the high
stability and energy conversion >1000 h
efficiency of ~ 4.7%. And the
performance of the cell is still
satisfying even at the high
temperature up to 60°C.

electrolytes VOC / mV JSC / mA cm-2 FF / % η /%

BMI⋅ BF4/I2/LiI-BMI⋅ I 657 7.5 61 4.0
BMI⋅ BF4-SiO2/I2/LiI-BMI⋅ I (25 °C) 655 8.0 67 4.7
BMI⋅ BF4-SiO2/I2/LiI-BMI⋅ I (60 °C) 605 8.6 73 5.1

The viscous quasi-electrolyte can not get into the porous electrode completely
Enlarge the channel in electrode by introducing zinc oxide nanowire

The traditional TiO2 film The ZnO–TiO2–BT film The ZnO–TiO2–AT film

after the acid

Pore size distribution

Traditional Nanocrystalline TiO2 Novel Nanocrystalline TiO2 films

films without textural channels with textural channels
(TiO2-AT) (ZnO-TiO2-AT)

20 nm 41 nm
The performance parameters of the cells

Z. G. Chen, F. Y. Li, C.H. Huang*, et al. J. Power Sour., 2007, 171, 990-998
2.3 Introduction of zinc oxide nanowires to
construct full solid state solar cells

Plan-view and cross-sectional SEM

images of ZnO nanowire arrays on
ITO substrates
ZnO nanowires /CuPc:C60 solar cells

Organic Layer

Compact ZnO Layer


(a) Schematic structure of the proposed PV cell based on ZnO nanowires

(b) Cross-sectional FE-SEM image of the device

The performance of the PV cell ZnO NWs/CuPc:C60 /CuPc

The transportation of
carriers is improved

J. P. Liu, Z. Q. Bian, C.H. Huang*, et al. Appl. Phys. Lett., 2009, 94, 173107
Nanocrystalline materials possess advantage in electric
and optical properties, and when these carefully designed and
fabricated nanostructures serve as a photoelectrode film of
solar cells, they can effectively improve the energy conversion
efficiency by offering a large active surface area, providing
direct pathways for electron transport, or generating light
scattering so as to extend the traveling distance of photons
within the photoelectrode film.

 The Ministry of Science and Technology of the People's

Republic of China ( 973 , 863 )
 National Natural Science Foundation of China
 Science and Technology Commission of Shanghai Municipality

Prof. Fu-You Li, Prof. Zu-Qiang Bian

Dr. Hong Yang, Dr. Zhi-Gang Chen,
Dr. Jun-Peng Liu, Mr. Xin-Yuan Xia
Thank you !