This slide is for the graduation defense. It's about optimized process via experiment design, including central composite design and mixture design.

1. Optimization for the fabrication of
ternary halide perovskite solar cells via
experimental design
利用實驗設計法進行氯、溴、碘三成分混合型之
鈣鈦礦太陽能電池製程最佳化
龔俊豪 Kung, Chun-Hao

2. Outline
2
Introduction
 Part I
 Using central composite design methods to find
optimized fabrication process
 Part II
 Using mixture design of experiments on ternary
halide perovskite device
Conclusion

3. 3
Exciton
holes
electronsLUMO
HOMOInterface
Exciton diffusion
Charge separation
Charge extraction
Absorber
Introduction
General Perovskite unit(AMX3)
Iodide (I)
Methylammonium(MA)
Lead (Pb)
Advantages:
• Intense light harvesting
• Small exciton binding energy
• Long charge carrier lifetime
• Cost effective
Disadvantage:
• Humidity-sensitive
• Toxicity
MAPbI3

4.  Low procedure temperature
 All solution process
Reference: Sun. et.al Energy Environ. Sci., 7, 399 (2014)
4
Solution process
Reference: T.F Guo, Adv. Mater., 25, 3727 (2013)
Evaporation process
Structure-Conventional Planar heterojunction

5. 5
Reference: Yi-Bing Cheng, Angewandte Chemie, 126, 10056 (2014)
ITO
PEDOT:PSS
Perovskite(MAPbI3)
PCBM
Al
Experimental

6. 6
Reference: Michael Grätzel, Advanced Functional Materials, 24, 3250(2014)
Effect of Annealing Temperature on Film Morphology of Organic–Inorganic
Hybrid Pervoskite Solid-State Solar Cells
Temperature [°C] Time Taken [h] PCE[%]
60 20 1.78
80 3 10.64
100 0.75 11.66
150 0.25 9.66
175 0.17 8.52
200 0.17 0.56
Interaction: Temperature & time
Research purpose Part-I
System: FTO/TiO2/MAPbI3-XClx/spiro-MeOTAD/Au
System: ITO/PEDOT/MAPbI3/PCBM/Al
Solvent washing

7. 7
Reference: Alex K.-Y. Jen et.al Adv. Energy Mater,5, 1400960 (2014)
Voc(V) Jsc(mA/cm2
) FF (%) Eg
MAPbI3 0.85 10.6 0.38 3.4 1.55
MAPb(I0.8Br0.2)3 0.88 10.9 0.38 3.6 1.65
MAPb(I0.6Br0.4)3 0.92 10.5 0.38 3.7 1.74
MAPbIXCl3-X 0.89 16 0.74 10.5 1.61
MAPb(I0.8Br0.2)XCl3-X 0.99 14.9 0.68 10 1.70
MAPb(I0.6Br0.4)XCl3-X 1.06 11.5 0.62 7.6 1.83
High-Performance Planar-Heterojunction Solar Cells Based on Ternary Halide Large-
Band-Gap Perovskites
Cl
BrI
Best recipe
Research purpose Part-II
Solvent washing method
SystemITO/PEDOT:PSS/Perovksites/PC61BM/Bis-C60/Ag
90 °C for 2–3 h

8. 8
 Create a fundamental fabricating process
→ Suitable recipe for fabrication
→ What is the main factor
 Extend single component to ternary system
→ To find the best recipe
→ To know the role of every componets
40 wt% Precursor solution/DMF
Spin-coating Solvent washing
Research purpose
Drying
First part:
Annealing time and temp.
Second part:
Ternary halide precursor

9. 9
Central composite design
methods(CCD)
Mixture design
methods
40 wt% Precursor solution/DMFMethodology
DOE: design of experiment
1. Annealing time and temp. 2. Ternary halide precursor

10. Factorial Points : Estimated main factor & interaction
Axial Points : Estimated pure quadratic form
Center Points : Estimated pure Error
10
→ A tool to build a quadratic response surface for optimization
→ Resolves both main effects and interactions
Central composite design (CCD) Part I

11. Level Temperature (℃) Annealing time (mins)
𝟐 120 5.0
1 115 6.5
0 100 10.0
-1 85 13.5
- 𝟐 80 15.0
11
Run Temp. Time Temp. Time
1 -1 -1 85 13.5
2 -1 1 85 6.5
3 1 -1 115 13.5
4 1 1 115 6.5
5 0 0 100 10
6 0 0 100 10
7 0 0 100 10
8 0 - 𝟐 100 15
9 0 𝟐 100 5
10 - 𝟐 0 80 10
11 𝟐 0 120 10
Design matrix
Reference: Michael Grätzel, Advanced Functional Materials, 24, 3250(2014)
Effect of Annealing Temperature on Film Morphology of Organic–Inorganic
Hybrid Pervoskite Solid-State Solar Cells
120℃
5 mins
15 mins
8𝟎℃
100℃
Fixed parameters
Solution : 40 wt% CH3NH3PbI3
Speed: 5 k r.p.m., 30 sec,
Drip: Chlorobenzene at 4~6 secs(200ul)

12. 1
1
2
2
3
3
4
4
4
4
5
5
5
5
5.5
5.5
5.5
5.5 5.5
5.5
6
6
6
6
6
6
6.5
6.5
6.5
6.5
6.5
7
7
7
7
7.2
Temperatuer(degree)
Annealingtime(mins)
85 100 115
6.5
10
13.5
-1.5 -1 -0.5 0 0.5 1 1.5
-1.5
-1
-0.5
0
0.5
1
1.5
12
Parameter Coefficient
Xtemp
1.16
Ytime
-0.99
XtempXtemp
-1.21
YtimeYtime
-0.63
XtempYtime
0.99
Main factor:
Interaction: Temp.-Time
90℃ 110℃
PCE=6.78+1.16*x-0.99*y-1.21*x2-0.63*y2+0.98.*x*y
>
Regression of PCE (%)

13. -0.2 0.0 0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
CurrentDensity(mA/cm
2
)
Voltage(V)
90
o
c, 12 mins
105
o
c, 12 mins
110
o
c, 12 mins
13
Temp. time Jsc Voc FF PCE(%)
90 12 11.37 0.93 0.59 6.18
105 12 14.40 0.93 0.63 8.48
110 12 11.98 0.93 0.62 6.93
PCE contour plot
Main factor: >
Interaction: Temp.-Time
Verification of PCE contour plot

14. 14
It is consistent with UV-vis
spectra result.
Verification by UV-Vis
Temp. time Jsc Voc FF PCE(%)
90 12 11.37±𝟎. 𝟕𝟐 0.93±𝟎. 𝟎𝟎 0.59±𝟎. 𝟎𝟎6.18±𝟎. 𝟏𝟒
105 12 14.40±𝟏. 𝟔𝟔 0.93±𝟎. 𝟎𝟎 0.63±𝟎. 𝟎𝟎8.48±𝟎. 𝟒𝟒
110 12 11.98±0.34 0.93±𝟎. 𝟎𝟎 0.62±𝟎. 𝟎𝟎6.93±𝟏. 𝟎𝟒
400 500 600 700 800
0
1
2
3
Absorbance(a.u.) Wavelength(nm)
90oC,12mins
105oC,12mins
110oC,12mins
-0.2 0.0 0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
CurrentDensity(mA/cm
2
)
Voltage(V)
90
o
c, 12 mins
105
o
c, 12 mins
110
o
c, 12 mins

15. 15
Temp. ↑
Crystal size↑
500nm
𝟗𝟎℃, 12 mins 𝟏𝟏𝟎℃, 12 mins
𝟏𝟎𝟓℃, 5 mins 𝟏𝟎𝟓℃, 12 mins
Main factor is
temperature.
Verification by SEM

16. It’s effectively to find suitable parameters to
fabricate perovskite device via CCD methods .
The main factor affect the power conversion
efficiency is temperature.
16
Summary Part I
Drying
Voc: 0.93 V
Jsc:14.40 mA/cm2
FF:0.63
PCE:8.48 %

17. Part II
Using mixture design of experiments on
ternary halide perovskite device to find best
recipe
17

18. PbI2 18
Cl-
ITO
PEDOT:PSS
Perovskite
PCBM
Al
Experimental section
Br-
I-
Chloride, Bromide, Iodide
Methylammonium(MA)
Lead (Pb)
Enhance morphology
Enhance bandgap &stable phase
+Fixed parameters
Precursor solution : 40 wt%
Speed: 5 k r.p.m., 30 sec,
Drip: Chlorobenzene at 4~6 secs(200ul)

19. 19
 Model is fixed
 Algebra equation
 Time-consuming
 Model reduction
 SAS regression
 Interaction effect
 Save time
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
IBr
Cl
Binary Design (A) Ternary Design (B)
Modified mixture design methods
Reference: Scheffe (1958, 1963) introduced the simplex
lattice designs and simplex-centroid designs.

20. 20
Research methodology
RegressionExperimental data Contour plot1. 2. 3.
SAS 9.3 MATLAB R2013a
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
IBr
Cl

21. 0
20
40
60
80
Cl Br I Pb
Atomic%
Real Measured
0
20
40
60
80
Cl Br I Pb
Atomic%
Real Measured
0
20
40
60
80
Cl Br I Pb
Atomic%
Real Measured
21
The real mixing ratio is equal to the measured result.
EDS analysis
Cl:Br:I=0.67:0.17:0.17 Cl:Br:I=0.33:0.33:0.33 Cl:Br:I=0.00:0.00:1.00

22. -0.2 0.0 0.2 0.4 0.6 0.8 1.0
-15
-10
-5
0
0.00:0.00:1.00
0.00:1.00:0.00
1.00:0.00:0.00
0.00:0.75:0.25
0.17:0.67:0.17
CurrentDensity(mA/cm2)
Bias (V)
22
J-V curve characteristic Part II
℃ rpm80 6000
MACl
MABr
MAI
in DMF
Spin-coating
Ternary halide precursor
Br
I
Cl
Cl : Br : I

23. 23
Jsc (mA/cm2) Voc (v)
Bromide : Enhance
Voc
Cl
Br I
Cl
Br I
Jsc: Chloride & Iodide
interaction
Mixture Design contour plot

24. 0.55
0.55
0.6
0.6
0.6
0.6
0.65
0.65
0.65
0.65
0.68
0.68
0.68
0.68
0.7 0.7
0.7
0.7
0.7
0.75
0.75
0.75
0.8
0.8
0.85
0.85
0.9
0.9
0
0.25
0.5
0.75
0
0.25
0.5
0.75
1
0 0.25 0.5 0.75 1
24
FF
Cl
Br I
Chloride : Enhance FF
Cl
I
5
5
6
6
7
7
8
8
8
9
9
9
9
9
10
10
10
10
10
1111
11
11
12
12
12
12.5
12.5
12.7
0
0.25
0.5
0.75
0
0.25
0.5
0.75
1
0 0.25 0.5 0.75 1
Jsc (mA/cm2)
Cl
Mixture Design contour plot
Jsc: Chloride & Iodide
interaction

25. -0.2 0.0 0.2 0.4 0.6 0.8 1.0
-15
-10
-5
0
Currentdensity(mA/cm2)
Voltage (V)
0.30: 0.15 : 0.55
0.30: 0.35 : 0.35
Cl : Br : I
0.30: 0.55 : 0.15
1
2
3
3
4
4
5
5
5
5
6
6
6
6
6
6.5
6.5
6.5
6.5
6.5
7
7
7
7.2
7.2
0
0.25
0.5
0.75
0
0.25
0.5
0.75
1
I
0 0.25 0.5 0.75 1
25
PCE Contour plot run Cl Br I Voc Jsc FF PCE
0.30 0.55 0.15 0.97 9.94 0.70 6.77
0.30 0.35 0.35 0.92 14.07 0.73 9.47
0.30 0.15 0.55 0.75 12.67 0.68 6.52
Cl
IBr
Verification by J-V curve

26. 26
7
8
10
9
11
12
12.5
12.7
12
11
10
8
11
10
0
0.25
0.5
0.75
1 0
0.25
0.5
0.75
1
Cl
Br I
0 0.2 0.4 0.6 0.8 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
5
6
7
8
9
10
11
12
1
0.98
0.94
0.9
0.85
0.8
0.75
0.85
0.8
0
0.25
0.5
0.75
1 0
0.25
0.5
0.75
1
Cl
Br I
0 0.2 0.4 0.6 0.8 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.7
0.75
0.8
0.85
0.9
0.95
1
0.6
0.65
0.68
0.7
0.75
0.8
0.850.9
0.55
0.7
0.7
0
0.25
0.5
0.75
1 0
0.25
0.5
0.75
1
Cl
Br I
0 0.2 0.4 0.6 0.8 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.6
0.6
0.65
0.65
0.68
0.68
0.7
0.75
0.8
0.85
0.9
0.75
0.7
0.55
0
0.25
0.5
0.75
1 0
0.25
0.5
0.75
1
IBr
Cl
5
6
6.5
7
7.2
7.2
7
6.5
6
5
6
6.5
0 0.2 0.4 0.6 0.8 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
JscVoc FF PCE
Bromide → Enhance Voc Chloride → Enhance FF
Cl
BrI
Best recipe
Role of halides

27. 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
Normalizedabsorbance(a.u.)
Wavelength(nm)
Cl Br I
0.30:0.15:0.35
0.30:0.35:0.35
0.30:0.55:0.15
400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
Normalizedabsorbance(a.u.)
Wavelength(nm)
Cl Br I
1.00 0.00 0.00
0.00:1.00:0.00
0.00:0.00:1.00
27
Single component Ternary component
Onset value
Cl:800 nm
Br:700 nm
I:800 nm
Bromide enhance Jsc ?
Verification by UV-Vis spectra
Bromide → Enhance
bandgap → Enhance Voc

28. 28
0 0.5 0.50.5 0 0.5
MACl MABr MAIMACl MABr MAI
0.17 0.67 0.170 0 1
More bromide,
more pin holes
10𝜇m
Verification by SEM
Voc↑ FF↓Br

29. 29
Cl Br I
0.30 0.55 0.15
Cl Br I
0.30 0.35 0.35
run Cl Br I Voc Jsc FF PCE
0.30 0.55 0.15 0.97 9.94 0.70 6.77
0.30 0.35 0.35 0.92 14.07 0.73 9.47
0.30 0.15 0.55 0.75 12.67 0.68 6.52
Cl Br I
0.30 0.15 0.55
500nm
Verification by SEM

30. 10 15 20 25 30 35 40 45
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
Pure MAI
Pure MABr
Pure MACl
2Theta (degree) Intensity(a.u.)
10 20 30 40 50
0.30: 0.15 : 0.55
0.30: 0.35 : 0.35
Intensity(a.u.) 2Theta (degree)
Cl : Br : I
0.30: 0.55 : 0.15
30
(110)
(220)
14.1°
28.4°
*
• Diffraction peak:
MAPbI3 : 14.1°, 28.4°, 43.3°
MAPbCl3 : 15.88°
MACl: 17.6°, 35.3°
MABr: 20.2°, 30.3°
PbI2 : 12.67°, 25.34°, 38.01°
Verification by XRD
MAClMABr PbI2
♦
♦ ♦

31. 10 20 30 40 50
0.30: 0.15 : 0.55
0.30: 0.35 : 0.35
Intensity(a.u.) 2Theta (degree)
Cl : Br : I
0.30: 0.55 : 0.15
31
(110)
(220)
14.1°
28.4°
*
• Diffraction peak:
MAPbI3 : 14.1°, 28.4°, 43.3°
MAPbCl3 : 15.88°
MACl: 17.6°, 35.3°
MABr: 20.2°, 30.3°
PbI2 : 12.67°, 25.34°, 38.01°
Verification by XRD
Reference: Yang Yang et.al Science,345, 6196 (2014)
MAClMABr PbI2
♦
♦ ♦

32. -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
1E-5
1E-4
1E-3
0.01
0.1
1
10
CurrentDensity(mA/cm2)
Voltage(V)
32
Cl : Br : I=0.30 : 0.35 : 0.35
Rs=78.23 Ω/cm2
Rp=358.51 kΩ/cm2
-0.2 0.0 0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
P:100mW/cm
2
Voc:0.92 V
Jsc:14.07 mA/cm
2
FF:0.73
PCE:9.47%
Dark
Light
CurrentDensity(mA/cm2)
Voltage(V)
Best recipe
Fixed parameters
Solution : 40 wt% (MACl+MABr+MAI)+PbI2
Speed: 5 k r.p.m., 30 sec,
Drip: Chlorobenzene at 4~6 secs(200ul)

33. 33
It has been known the role of halide in ternary
perovskite solar cells via design of experiment.
It is obtained the best recipe with proper
mixing ratio via design of experiment.
Summary Part II
Ternary halide precursor
Voc: 0.92 V
Jsc:14.07 mA/cm2
FF:0.73
PCE:9.47 %
Cl : Br : I=0.30 : 0.35 : 0.35

34. • It is successfully to employ CCD and mixture
design methods to find optimized recipe on
ternary perovskite solar cells.
34
Know
situation
Design of
experiment
Optimized
process
Conclusion
Voc: 0.93 V
Jsc:14.40 mA/cm2
FF:0.63
PCE:8.48 %
Voc: 0.92 V
Jsc:14.07 mA/cm2
FF:0.73
PCE:9.47 %

35. Thank you for your listening.
35