Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Outline
• Advanced Optoelectronic Materials Laboratory in NTHU,
MSE
• Small Molecule Organic Photovoltaics (OPV) and
Organic Light Emission Devices (OLED)
–
–
–
–
Why small molecules?
Device structures and optical designs
Molecule structures and designs
Recent Progress
• 大學部專題研究規劃
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
I.
Advanced Optoelectronic Materials
Laboratory (AOML)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Brief History
2012
2011
2010
•
2009
•
•
•
Lab established
- 1 Group Leader
- 2 Master
Student
Fabrication and
measurement
facilities move-in
Keep working
and keep
Very high efficiency growing
device (OPV,
OLED,…)
demonstrated
- 1 Group Leader
- 1 Group Leader
- 4 PhD Student
- 1 PhD Student
- 7 Master Student
- 5 Master Student
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Facilities
2010
•
Fabrication and
measurement
facilities movein
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Facilities (Fabrication)
2010
•
Fabrication and
measurement
facilities movein
Room 319, MSE building, NTHU
• Vacuum evaporator integrated with N2 glove box
• Sputter
• Spin coater (one in N2 glove box and one in air)
• Blade coating facilities
• Hood
• Temperature gradient sublimation system
• Deionized water system
• Microbalance
• Humidity Cabinets
• Dispenser, UV lamp for encapsulation
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Facilities (Measurements)
Room 332-1, MSE building, NTHU
2010
•
Fabrication and
measurement
facilities movein
•UV-Vis spectrometer with absorption/reflection option
•Solar cell testing station
(Solar simulator, Semiconductor parameter analyzer)
•Photoresponse measurement system
(Xe lamp, Monochromator, Current preamplifier,
Lock-in amplifier with chopper, GPIB computer interface)
•Multi-core CPU high-speed computer for
multi-physics and quantum chemistry simulation
•OLED testing station
(Semiconductor parameter analyzer,
Spectrophotometer with fiber collector,
Probe station, Large area blue-enhanced Si-detector)
•Time of flight measurement system
(oscilloscope, high power Q-switch pulsed laser,
2nd and 3rd harmonic generation optics,
cryostat, high voltage source)
•Organic laser measurement system
•Absolute quantum yield measurement system
•Time resolved PL / EL measurement system
•Transient absorption spectroscopy
•Transient photocurrent / photovoltage spcetroscopy
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Main Theme
Solution Processed
SMOLED
Small Molecule
OSC (SMOSC)
Inverted
OSC
Host materials for
PHOLED
Solution Processed
SMOSC
Organic
Solar Cell
OLED
Microcavity
OSC
Crosslinkable HTL
for OLED
Os(II) PHOLED
Organic ThinFilm Laser
Organic ThinFilm Sensor
Organic
Photodetector
AOML
Novel OE
Device
Photophysics
Exciton & Carrier
Dynamics in OSC
Device physics of
DSSC
Light outcoupling
of OLED
Plasmonic effect
Organic-Inorganic
Hybrid Device
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Group Members
Organic
Solar Cell
OLED
AOML
Novel OE
Device
Photophysics
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
II.
ORGANIC SMALL
MOLECULE SOLAR CELLS
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Why Small Molecules for OSCs?
Polymer OSC
•
•
•
•
•
•
Small Molecule OSC
Defined molecule structure
Purification by vacuum sublimation
Very good batch-to-batch reproduction
More advanced layer structures
Ready for tandem configuration
Vacuum & solution process are all possible
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Fundamental Research of Small Molecule
Solar Active Thin Films
Intermolecular Charge Transport
 Electronic transitions
 Photoinduced electron transfer
 Exicton dynamics
 Geminate & Non-geminate recombination
1200
E.Q.E.
(%)(a.u.)
EQE
(%)
Absorbance
J (a.u.)
1400
Hole
Electron
80
DTDCTP
2nm in CH2Cl2
TPDCDTS
1.0
50
Bimolecular recombination
5nm thin film
TPDCDTS
DTDCTB
2800
Monomolecular
75
0.8
60
40
recombination
60
13nm
-0.5 v
20nm
2100
experimental
Solid: Right
800
600
400 0.720.4
200
1E-5
0.6
30
40
0
20
20
0.1
0.2
stored in dark
heated
heated &
illuminated
|z| (ohms)
1E-4
V oc (V)
1000 0.78
0
0
Morphology
30
15
700
10
0
0
00.66
500
0.00 1000 1500 2000 2500
300Z400
400 500
500 600
600
re (ohms)
500 600 700 800 900
1000
HOMO
1/2
[Eletric Field (V/cm)]
45
Dash: Left
1400
-1
10
0
10
1
10
2
10
10
500
24004 0.1
6 8600
10 12 14 16 18
1
Wavelength
Wavelength
(nm)
Time (
s) (nm)
Intensity
(sun)
Wavelength
 Spectroscopy Ellipsometry
 Absorption spectroscopy
 Time-resolved spectroscopy
 Photoresponse spectroscopy
 Impedance spectroscopy
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
4
10
(Hz)
700 700
800 Frequency
900
800
700
800
900
Spectroscopy
 Interpenetration bulk heterojunction networks
 Surface topology
 Molecular self-assembly (crystallization,
aggregation)
3
5
10
6
10
Phase of Z (deg)
1.2
60
0.841
Zim (ohms)
1E-3
2
Mobility (cm /V s)
 Space-charge-limited-current and time-of-flight
technique
 Molecular structure and stacking
 Electronic structure
 Morphology
Photophysics
Simulation
Fully Optical and Electrical Simulation
Optical Simulation
Electrical Simulation
Rigorous classical electrodynamics
Exciton diffusion dynamics and carrier transport behavior
•General layered media (wavelength dependent
•Exciton diffusion meet with criteria of boundary
conditions in organic neat films
optical constants, anisotropic)
•Both optically “thin” and “thick” layers
•Carrier transports with recombination
•Full angle, full polarization and full spectrum
•Current density in target spectra can be modeled
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
D-π-A molecule
NC
CN
N
S
S
TP DC D TS
3.0
TPDCDTS thin film
TPDCDTS in CH2Cl2
1.0
TPDCDTS thin film
2.5
0.8
2.0
n, k
Si
Absorbance (a.u.)
1.2
0.6
1.5
no
0.4
1.0
ko
0.2
0.5
0.0
300
400
500
600
700
800
900
ne
ke
0.0
300
400
600
700
800
900
Wavelength (nm)
70
0
60
-2
Bilayer
D-M-A with C60
50
D-M-A with C70
-4
40
EQE (%)
2
Current Density (mA/cm )
Wavelength (nm)
500
-6
-8
Bilayer
D-M-A with C60
-10
D-M-A with C70
0.0
0.2
0.4
0.6
Voltage (V)
0.8
η = 3.8 %
30
20
10
0
400
500
600
700
800
900
Wavelength (nm)
ChemChomm 47, 7872 (2011)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
A-A-D-A-A molecules
η = 3.7 %
Org. Lett. 13, 4962 (2011)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
D-A-A molecules (DTDCTB)
S
N
N
N
S
CN
NC
DTDCTB
1.0
DTDCTB in CH2Cl2
(b) 2.5
DTDCTB thin film
2.0
0.8
0.6
n, k
Absorbance (a.u.)
(a)
0.4
1.5
DTDCTB n
DTDCTB k
C60 n
1.0
C60 k
0.2
0.5
0.0
300 400 500 600 700 800 900 1000
Wavelength (nm)
0.0
C70 n
C70 k
400
500 600 700 800
Wavelength (nm)
900 1000
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
D-A-A molecules (DTDCTB)
(a)
DTDCTB:C70
100
10
1000
CPS
0.0
2
Current Density (mA/cm )
1000
DTDCTB
100
10
1000
Substrate
100
-2.5
-5.0
-7.5
-10.0
-12.5
-15.0
0.0
10
0
20
40
60
80
100
Two Theta (degrees)
Voc: 0.79 V
Jsc: 14.68 mA/cm2
FF: 0.50
0.2
0.4
0.6
Voltage (V)
0.8
(b) 70
60
EQE (%)
50
η = 5.8 %
40
30
20
10
0
JACS ASAP (2011)
400
500 600 700 800
Wavelength (nm)
900 1000
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
0.0
-2.5
-5.0
-7.5
DTDCTB
DTDCTP
Voc: 0.79 V
Jsc: 14.68 mA/cm2
FF: 0.50
Voc: 0.95 V
Jsc: 12.1 mA/cm2
FF: 0.56
η = 5.8 %
η = 6.4 %
-10.0
DTDCTB
DTDCTP
-15.0
-0.2
0.0
0.2
0.4
0.6
Voltage (V)
0.8
1.0
100
EQE
Absorption
IQE
Simulated EQE
80
100
80
60
60
40
40
20
20
0
400
Submitted (2011)
500
600
700
800
Wavelength (nm)
EQE (%)
-12.5
IQE and Absorption (%)
2
Current Density (mA/cm )
D-A-A molecules (DTDCTP)
0
900
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
On-going Progress
New donor with optimized
HOMO/LUMO level
η~7%
-5.0
-7.5
η>7%
-5.0
Solution processed SMOSCs
-7.5
-10.0
-12.5
2
-2.5
0.0
-2.5
-15.0
-10.0
-0.2
0.0
-12.5
0.2
0.4
0.6
Voltage (V)
0.8
1.0
-15.0
0.2
0.4
0.6
Voltage (V)
0.8
1.0
2
0.0
Current Density (mA/cm )
-17.5
-0.2
0.0
-7.5
-10.0
-12.5
-15.0
-0.2
0.0
0.2
0.4
0.6
Voltage (V)
0.8
1.0
-5.0
-7.5
-10.0
-12.5
DTDCTB
DTDCTP
-15.0
-0.2
0.0
0.2
0.4
0.6
Voltage (V)
0.8
ITO-free SMOSCs
1.0
2
)
2
Inverted SMOSCs
2
-7.5
-10.0
-12.5
-0.2
0.0
0.2
0.4
0.6
Voltage (V)
0.8
1.0
0.0
η>5%
-2.5
(mA/cm
η~5%
-5.0
-7.5
0.0
η>5%
-2.5
-5.0
Current Density
-2.5
Current Density (mA/cm )
(mA/cm
η>5%
-5.0
0.0
-5.0
Current Density
0.0
-2.5
-2.5
)
Flexible SMOSCs
Current Density (mA/cm )
2
Current Density (mA/cm )
0.0
2
Current Density (mA/cm )
Optimization of
device structure
-7.5
-10.0
-12.5
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Voltage (V)
-10.0
-12.5
-0.2
0.0
0.2
0.4
0.6
Voltage (V)
0.8
1.0
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Best Cell Efficiency
South China Uni.of Tech.
Solarmer
NTHU
(in preparation)
Efficiency (%)
8
6
Plextronics
Konarka
Siemens
4
UCSB
NTHU
Uni. Cologne & Wurzburg
NTHU
Uni. Michigan & USC
Uni. Tokyo Heliatek
Konarka
Groningen
Polymer
Small molecule
University Linz
2
2000
2004
2008
Year
2012
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
2016
III.
SMALL MOLECULAR
ORGANIC LIGHT EMITTING DIODE
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Visible Light
• Visible Light is electromagnetic radiation of a wavelength that is
visible to the human eye
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Blue OLED Device
15
10000
TmPyPB 20nm
TmPyPB 30nm
TmPyPB 40nm
TmPyPB 50nm
Luminance (cd/m )
1000
Efficiency (lm/W)
2
100
10
1
TmPyPB 20nm
TmPyPB 30nm
TmPyPB 40nm
TmPyPB 50nm
0.1
0.01
1E-3
0
FIrPic
2
4
6
8
10
5
0
10
Voltage (V)
100
1000
2
Luminance (cd/m )
10000
12
1.0
10
EL
0.8
EQE (%)
Intensity (a.u.)
10
0.6
0.4
0.2
8
6
4
TmPyPB 20nm
TmPyPB 30nm
TmPyPB 40nm
TmPyPB 50nm
2
0.0
400
500
600
700
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
0
1
10
100
1000
2
Luminance (cd/m )
10000
Green OLED Device
CF3
10000
TCTA
26DCzPPy
1000
Os
P
Ph2
N
N
N
CF3
100
Efficiency (lm/W)
N
2
Ph2
P
Luminance (cd/m )
N
N
N
40
10
TCTA
26DCzPPy
1
0.1
0.01
1E-3
0
A Y U -1203
2
4
6
8
30
20
10
0
0.1
10
1
Voltage (V)
Intensity (a.u.)
10
100
1000 10000
2
Luminance (cd/m )
15
1.0
TCTA
26DCzPPy
EL
0.8
0.6
EQE (%)
N
0.4
10
0.2
5
0.0
400
500
600
700
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
0.1
1
10
100
1000 10000
2
Luminance (cd/m )
Red OLED Device
CF3
20
10000
S
N
2
Luminance (cd/m )
P
Os
P
N
N
N
S
C F3
100
10
1
Os(fptz)2(PPhMe2)2
0.1
AYU-1195
0.01
1E-3
0
A Y U -1 1 9 5
2
4
6
8
Efficiency (lm/W)
1000
N
N
15
10
AYU-1195
0
10
Os(fptz)2(PPhMe2)2
5
1
Voltage (V)
1.0
N
N
N
Os
N
N
N
N
P
F 3C
Intensity (a.u.)
P
N
0.8
0.6
0.4
0.2
10
Os(fptz)2(PPhMe2)2
AYU-1195
5
Os(fptz)2(PPhMe2)2
0.0
AYU-1195
500
[O s(fp tz) 2 (P P h M e 2 ) 2 ]
10000
15
EQE (%)
CF3
10
100
1000
2
Luminance (cd/m )
550
600
650
700
750
0
1
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
10
100
1000
2
Luminance (cd/m )
10000
Binary White OLED
100 nits ~ 1000 nits CIE = (0.33, 0.34)
1.2
6V
7V
8V
9V
4.5V
4.7V
5V
5.5V
1.0
normalized a.u.
0.8
0.6
(0.33 , 0.34)
0.4
0.2
0.0
400
500
600
700
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Trinary White OLED
CIE Values lie on CCT Curve!
Color rendering index (CRI) achieve 79
Ir(mppy)3
1.2
RGB = 3 : 1 : 3
RGB = 3 : 1 : 4
RGB = 3 : 1 : 8
RGB = 3 : 1 : 16
Normalized a.u.
1.0
0.8
Ayu-1195
FIrpic
0.6
0.4
0.2
0.0
400
500
600
700
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
High CRI White OLED
CRI enhances up to 84!
Os(bpftz)2(dppb)
1.4
RYB = 1 : 1 : 2
RYB = 1 : 1 : 3
RYB = 1 : 1 : 4
RYB = 1 : 1 : 6
1.2
Normalized a.u.
1.0
0.8
Ayu-1195
FIrpic
0.6
0.4
0.2
0.0
400
500
600
700
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Color Tuning OLED
Intensity (a.u.)
1.5
7V
8V
9V
10 V
11 V
12 V
13 V
14 V
1.0
0.5
0.0
500
600
700
y
Color temperature 4600~1600 K
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
white
10 : 0.75 : 0.25
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
x
Wavelength (nm)
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
OLEDs In Near Future
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
IV.
大學部專題研究
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Some Successful Examples
• 專題成果刊登於Organic Electronics
(IF = 3.998)
• 專題成果刊登於Organic Letters (IF =
5.250)
• 專題成果本月準備投稿
• 專題成果獲國科會大專學生專題研究
補助
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Schedule
• 一月底～二月
– 開始專題研究
– 認識材料基本光學性質(n, k)，利用Silicon n, k計算反射率（Matlab基礎實習
），並認識反射頻譜儀及基本光纖式光譜儀
助教：陳昶文
• 三月
– 觀摩有機薄膜沈積，量測有機薄膜附著在Si基板之反射率推算薄膜厚度與光
學性質（Matlab進階實習） 助教：林偉桀、黃正宇
• 四月
– 量測OLED與OPV基本特性（光電量測儀器實習）
誌偉
助教：范嘉展、呂
• 五月
– 量測儀器電腦控制與記錄（Labview）基礎實習
助教：范嘉展
• 六月
– 光電元件基板準備與固態薄膜沈積
助教：陳奕宏、張容浩
• 七月以後
– 開始前瞻研究！
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
What You Should Participate?
• Group Meeting (weekly)
• 專題生基本研究進度 Meeting (Bi-weekly, with
T.A.)
• 實驗室公共事務 (值週生)
• After having you own project: Join one of the subgroup meeting, literature report in group meeting
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
What You Can Gain from This Project?
What you can learn:
•基礎材料光電特性量測
•基礎科學工程軟體使用與程式撰寫
•有機光電薄膜與元件製程
If you stick with us long enough…
•屬於你自己的最先進有機能源元件研究題目
•自己動手做世界上從來沒有人做過的實驗、成為世界上發現
某自然界奧妙的第一人
•發表你的work在國際上重要的期刊，開始在世界舞台上嶄露
頭角！
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Some New Projects
• Functional Organic Nano Structure
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
Some New Projects
• Alternative Fabrication Technique
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin
THANK YOU FOR YOUR
ATTENTION
Advanced Optoelectronic Materials Lab (AOML)
www.mse.nthu.edu.tw/~hwlin