에너지소재특론

Solar Cells

Jong Hak Kim

Chemical & Biomolecular Engineering
Yonsei University
Energy Problem

Humanity’s 10 Problem for next 50 years

1. Energy
2. Water
3. Food
4. Environment
5. Poverty
6. Terrorism & War
7. Disease
8. Education
9. Democracy
10.Population 2003 6.3 Billion People
Richard Smalley in 2003
2050 9-10 Billion People
Renewable Energy

Konarka (http://www.konarkatech.com)
Nanosolar (http://www.nanosolar.com)
Why Solar Cells ?

If installed 5kWp solar

array for a typical home,
over a single year,
it would prevent:

20000 lit of water

3.3 tones of coal from being burned

300 kg of ash from being disposed of landfills
30 kg of SO2 and 25 kg of NOx from causing acid rain
8.5 tones of CO2 from enhancing the greenhouse effect
Solar light

γ-ray/x-ray (9 %), visible (43 %), IR/microwave (48%)

=> Light in 0.15-4.0㎛: 99 %

Overall efficiency is not very high despite high value at a given

wavelength.
 Solar Energy
● At earth surface, average solar energy : 4 x 1024 J / year
● Global energy consumption (2001) : 4 x 1020 J / year
(increasing ~ 2% annually)

DOE: US Department of Energy

N. Lewis (Caltech)

- In US, average power requirement : 3.3 TW

- With 10% cells, need 1.7% of land area devoted to PV (~ area occupied
by interstate highways)
Land surface area
Science, 2005, 339, 548

Global need: the amount of land needed to generate 20 TW w/ 10% cells

Electricity production cost

Average cost per watt of PV module 1985-2010

(Source: Earth Policy Institute, 2007)

Electricity production cost
Real module prices and Annual global PV installation
(1985-2010)
Solar Cell Market
[Solar Annual 2007 (http://www.photon-consulting.com)]
[World Semiconductor Trade Statistics (http://www.wsts.org)]

World Market (2011): $121.0 billion

World Semiconductor (2008): $260.0 billion
Terminology
• Photovoltaic : light + Alessandro Volta = light electricity
• Air Mass (AM)
- degree of light decrease by absorption, reflection, refraction
- AM = 1/cosφ
- AM0: 1367 W/m2 (136.7 mW/cm2)
- AM1 (at φ = 0), AM1.5 (at 48.2o), one sun (100 mW/cm2)
태양전지의 역사
연 대 특 징
1839 년 E. Becqurel, Photovoltaic (PV) effect 발견

1883 년 C. Fritts, 최초의 Se 태양전지 제작

1930 년 L. Grohndahl, Cu2O/Cu 태양전지 연구

1941 년 R. Ohl, Si 태양전지 연구

1950 년대 반도체 기술 발전

1954 년 Bell Lab., 결정질 Si 태양전지 (효율 4%) 개발성공

1958 년 미국 우주선(Vanguard I) 보조전원 사용 (5 mW), 태양광 산업 태동

1970 년대 석유파동으로 지상용 전원으로 활용모색

1974 년 일본, 션샤인 계획 시작

1980 년대 태양전지 개발 본격화, 신재료 개발 (CdTe, CuInSe2, TiO2 등)

1991 년 M. Grätzel, 고효율 저가 광감응 염료 태양전지 발표 (Nature)

1999 년 환경친화적 발전기술로 부각, 전세계 연간 생산량 200MWp

2001 년 De Pauli, 고분자 전해질 염료감응 태양전지 최초 발표 (Adv. Mater.)

Types of Solar Cells
Single crystal η>28%, very expensive
Crystalline
Silicone SC Polycrystal η~18%, expensive
Amorphous

η>12%, firstly successful thin films in commercial use

II· VI 족 (CdS,CdTe..) η>10%, easily synthesized

Solar III· V 족 (GaAs,InP..) η>30%, very expensive

Semiconductor
Cells Compounds
I· III· VI 족 (CuInSe2..) η~17%, alloy with other metal

Liquid electrolytes Cheap, η~10%, low durability

DSSC Cheap, η<5%

Polymer Electrolytes High durability
Mechanical property
Organic SC
Generation of Solar Cells
Photovoltaics: from physics to nature
- 1st Generation: Silicon crystalline
- 2nd : Silicon amorphous, thin films
- 3rd : Nanotechnology & Biomimetics
- 4th : Biological
單結晶
Silicon
多結晶 SiGe, SiC 等

Amorphous

單結晶 GaAs, InP, GaAlAs, GaInAs

Solar Cell 化合物 (Ⅲ-Ⅴ족 화합물系)
多結晶 CuInGaSe2, CdS, CdTe,ZnS
(Ⅲ-Ⅳ족 화합물系)

적층형 화합물/Ⅵ족계 GaAs/Ge, GaAlAs/Si, InP/Si

염료감응 태양전지 (DSSC)

유기
3rd 태양전지
유기 반도체
태양전지 비교

반도체 태양전지 광감응 염료 태양전지

장점 장점
고효율 (30% 이상) 태양전지 제조 가능 기존 비정질 실리콘 태양전지에 버금가
는 에너지변환 효율 (습식 태양전지)

단점 제조단가는 실리콘 태양전지의 5분의 1

고효율 태양전지 제조 시 원료비용 및 수준
제조비용 부담이 매우 큼
환경친화적 제조공정
고순도를 요하는 공정이므로 제조공정
이 복잡하고 어려움
단점
환경에 유해한 물질 발생 습식 태양전지의 경우, 용매의 휘발 및
누출에 따른 내구성 저하 문제
Principles of Inorganic SC
Semi-conductor (p-n junction) SC e-
~
+ - - + + + - - + +
+ + + +
- - + - - - - + - - N-type

- + - - + - - - - - - - - - - - - - - -
+ - - + + - + + - - - + + - + + - + + + + + + + + + + + + + +
+

+ hole P-type
- electron

N type: e- transfer, e- acceptor

P type: hole transfer, e- donor

Band gap E = ECB – EVB

CB: conduction band, 전도띠

VB: valence band, 가전도띠
Organic Solar Cells
e– • Organic molecules
LUMO
- D-A heterojunction
e– LUMO
- dispersed heterojunction

HOMO h+ Acceptor Donor

Fullerene Conducting P
HOMO
Conducting P Conducting P
Anode Electron Hole Cathode
acceptor acceptor Nano-inorganics Conducting P
Types of Solar Cells
Bulk Heterojunction Solar Cell
Bilayer Bulk Heterojunction

Donor / acceptor blend

3.0eV
3.7eV 3.3eV

4.2eV
3.7eV 4.2eV
ITO PEDOT: PCBM Al
PSS Poly(3 hexyl thiophene) ITO PEDOT: P3HT:PCBM Al
4.7eV PSS
5.2eV P3HT 4.7eV
5.9eV 5.2eV
6.1eV 5.2eV
6.1eV

1-(3-methoxycarbonyl)
propyl-1-phenyl[6,6] C61-
butyric acid methyl ester
(PCBM)
Organic Solar Cells
● Organic Solar Cells
- Cheap, efficient
- Improved stability
- Transparent, flexible, colorful
Principles of Solar Cells
Dye-Sensitized Solar Cells (DSSC)
Principles of Solar Cells
Dye-sensitized solar cells
Ru Dye (sensitizer)/TiO2
~
e-
HO O
C

I3-
O
C
O
NCS

hn TiO2 Ru
NCS
O
C
O

C O

I-
HO

S → S+ + e-
ITO ITO or
Pt
: dye
: semiconductor Redox couple : 3I- ↔ I3 - + 2e-

: electrolyte
 Structure of Solar Cells
Pt-coated glass
I- / I2 electrolyte Nanocrystalline semiconductor
e–
Dye/TiO2 layer
(10 – 15 µm)

SnO2-based
TCO

Film surface

HO C O

C
O N
N NCS
Ru
N NCS

O N
C
O

C O
HO
Principles of Solar Cells
Dye-sensitized solar cells (DSSC)
~

S I 3-
e-
e-
e-
S+ I-

S → S*
S* → e-(TiO2)cb + S+
2S+ + 3I- → 2S + I3-
I3- + 2e- → 3I-
Performance of Solar Cells
Typical J-V curve of solar cell
Vmax ⋅ J max
Jsc
Pmax FF =
Jmax Voc ⋅ J sc

Vmax ⋅ J max
η (%) = × 100
Pin
Voc ⋅ J sc ⋅ FF
= × 100
Vmax Voc Pin

☞ Solar cell performance

 Voc : Open-Circuit Voltage, Jsc : Short-Circuit Current
FF: Fill Factor, η : Overall Conversion Efficiency
Characteristics of DSSC
- promising candidates for renewable clean energy source

Low Costs : 1/3 ~1/5 of conventional Si S/C

Green Technology: non-toxic mater.
Transparent: Power window, smart window
Coloration: Rainbow cell
Flexibility: Flexible Battery & Device

TOYOTA-AISIN精機

TiO2 Heating Dye adsorption electrolyte

paste
SAIT
Trends in Industry
INAP, Gelsenkirchen, Grmany
DSSC
ECN, Petten, Netherlands
Manufacturers Solaronix, Aubonne, Swiss
IMRA-Europe, France
Konarka, MA

Japan
50 companies

STI, AU
Key Components
1. Nanocrystalline Semiconductor
- surface area, porosity, pore size distribution, light scattering,
electron percolation, Anatase (TiO2), ZnO, SnO2, Nb2O5

2. Sensitizers (Dye)
- Distribution on semiconductor surface, spectral properties,
redox properties in ground and excited states
anchoring groups (carboxylate or phosphonate)

3. Electrolyte
- ionic conductivity, electron barrier and hole conductor,
redox potential, mechanical separator, interfacial contact for
dye, TiO2 and counter electrode (I-/I3–)

4. Transparent conductive oxide (conductivity, transmittance),

sealing, metal grid, counter electrode
Semiconductor layer

■ Basic Requirements
- Proper energy level of conduction band for electron injection
from excited dyes
- Wide band gap for no absorption of visible light
- Large surface area for large amount of dye adsorption
- High porosity for deeper penetration of electrolyte solution
- High electron conductivity for high current density and voltage
- Slow recombination for high current density and voltage
Semiconductor layer

TiO2 : Ecb (- 3.9 V), Eg (3.2 V)

- high efficiency: ~10.5 % at AM 1.5 (100 mW/cm2)

- high electron conductivity

- good connectivity and necessary porosity crystal formation

with small defects

- good adhesion to electrode

- slow recombination (related with surface state or defects)

Dyes

■ Basic Requirements

1. Light absorption from whole visible light (400 ~ 900 nm)

2. High IPCE (incident photon-to-current conversion efficiency).

3. Good interaction with semiconductor surfaces such as TiO2.

4. Good interaction with electrolytes

5. Long-term chemical stability

6. Low cost
Dyes

IPCE (incident photon-to-current conversion efficiency)

Electrolytes

● Redox couples:
I- /I3-, Br- /Br3-, Cu, phthalocyanine, SCN, ferrocyanine,
dissolved in a solvent.

- Energy level lower than that of the counter electrode but

higher than that of dye HOMO.

- Fast ionic conduction

- Fast redox reactions
- Small charge transfer resistance at the interfaces
- Slow recombination of electrons in the TiO2 layer.
Roles of Electrolytes

Electrolytes:
• I- and I3- conductor
• interfacial contactor for dye
• electron barrier or hole conductor
• electrochemical reaction media
• mechanical separator
Contact of electrolyte with dyes:

HO O
C

I3-
C
N
O

TiO2 N NCS
Ru
N NCS
O
C
N
e-
e-
O

I-
C O
HO
Why Polymer Electrolyte DSSC ?

Cheap (1/5 of Silicone solar cell)

Environmentally friend.

Thin, Flexible, light

Higher durability using solid or gel type solar cell

World-wide great attention very recently

Polymer Electrolytes Example

☞ Epychlomer(1.3M)/NaI/I2
 High efficiency
: 2.6 % at 10mW/cm2
 Successful penetration
- due to nature and viscosity
of polymer electrolytes

☞ PEO(2M)/TiO2/LiI/I2
 Reduced crystallinity
 Enhanced the mobility of I-/I3-
 outstanding efficiency (4.2%)
Why Low Efficiency ?
Pore Size Distribution – BET
1.5
Average pore diameter = 16.5 nm
Surface area = 76.9 m2/g FE-SEM image of
TiO2 electrode
Pore Volume (cm3/g)

1.0

0.5

PEO (Mw=1,000,000)
d ≈ 126 nm

0.0
1 10 100
Pore Diameter (nm)
Why Low Efficiency ?

0.5 ± 0.1
Rg = c ⋅ M w (nm)
PEO (Mw=1M g/mol)

● Poly(ethylene oxide) (PEO)

c=0.063 (in diluted solution)
TiO2 layer
c=0.042 (in molten state)

● Example: PEO (Mw=1,000,000)

Rg= 63 nm (in diluted solution) > TiO2 pore size
Rg= 42 nm (in molten state) (~16.5 nm)
- Poor penetration
- Low conductivity
FE-SEM images – Size balance

Mw=1K Mw=4.6K Mw=8K

(Rg=2.0 nm) (Rg=4.3 nm) (Rg=5.6 nm)

Mw=10K Mw=100K Mw=600K

(Rg=6.3 nm) (Rg=19.9 nm) (Rg=48.8 nm)
Size balance vs. Efficiency

η= 0.01 %

Low Mw PEs η= 1.25 %

- better penetration
- high conductivity
- poor mechanical property
η= 3.84 %
Oligomer Approach

• Oligomer : Mw 1000, liquid (Rg < 3 nm)

• To enlarge the interfacial contact area

between dyes and electrolyte
• To improve the ionic conductivity

during preparation after preparation

(liquid oligomer ) (solid polymer )

in situ solidification
during solvent evaporation
HB Polymer Electrolytes
☞ PEO + Silica Nanoparticles
10 MPII
Current density (mAcm-2)

8
KI

2 (a) Bare TiO2 layers

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Potential (V)

Efficiency 4.5%
Fill factor 70.0%
at 100 mW/cm2 (b) TiO2 with PEs
Quadruple HB Polymer (QHBP)
PEG: 1,000 g/mol
Design of Electrolytes

Solution-state Solid-state

CH3
CH3

H OCN
H polyethylene glycol/
C6H12 NCO N O dibutyltin dilaurate
N
C C6H12 NCO
reflux, 16h O N N N
O N NH2 reflux, 16h
H H

CH3
H H
H O O
N O N N
H2 H2 N O
C6H12 NH C O C C NH C6H12 C
C C
O N N N O
O C C O N
H H H2 H2 H
n CH3
Recent Research Trends

Higher
Efficiency !!
Current Issues

1. Understanding electron dynamics in DSSCs

2. Electrolyte evaporation and degradation
 Quasi or solid state DSSCs
3. New sensitizers (dye or quantum dot)
4. Recombination in the oxide layer
 Preparation of the second oxide layer for passivation
5. Flexible DSSCs
6. Increasing efficiency and performance
7. Long-term performance