Shigeo Maruyama(丸山 茂夫)Department of Mechanical Engineering, The University of Tokyo
Energy NanoEngineering Lab., AISTCollege of Chemistry and Molecular Engineering, Peking University
ナノカーボン材料を用いたペロブスカイト型太陽電池ナノカーボン材料を用いたペロブスカイト型太陽電池
ワークショップ ‘エネルギー’ @ Tokyo, March 30, 2018
Perovskite
SWCNT + HTM
C60
GlassITO
Organic Thin Film(Normal)
Perovskite(Inverted)
Organic Thin Film(Inverted)
Perovskite(Normal)
PerovskiteCNT for Anodeand Cathode
Acknowledgements
April 20, 2016
FNTG Research SocietyFNTG Research Society
Fullerene
Single-Walled Carbon Nanotubes
(SWNTs)
Peapod
Multi-Walled Carbon Nanotubes Graphene
Nano-Diamond
Bundle of SWNTsDouble-Walled
Carbon Nanotubes
Metallofullerene
http://fullerene-jp.org/
FNTG Research Society1991: C60 Research Association1991: President: Professor Eiji Osawa (Toyohashi Inst. Tech.)1995: The Fullerenes Research Association2002: The Fullerene Nanotubes Research Association2003: President: Professor Hisanori Shinohara (Nagoya University)2005: The Fullerenes and Nanotubes Research Society2011: The Fullerenes, Nanotubes and Graphene Research Society2011: President: Professor Shigeo Maruyama (UTokyo)
Meetings2017/3/1-3: FNTG 52 Symp. @ Tokyo2017/6/25-30: NT17 @ Brazil2017/9/13-15: FNTG 53 Symp. @ Kyoto
2018/3/10-12: FNTG 54 Symp. @Tokyo2018/7/8-12: WONTON2018 @ Hakone2018/7/15-20: NT18 @ Beijing2018/9/11-13: FNTG 55 Symp. @ Sendai
2019/2/??-??: FNTG 56 Symp. @ Tokyo2019/7/21-26: NT19 @Würzburg2019/9/?-?: FNTG 57 Symp. @ Nagoya
H. Shinohara Y. Ohno
E. I. Kauppinen C. Bichara J. WagnerS. Maruyama
Time evolution of SWNT lengths
0 5 100
100
200
CVD time (min)SW
NT
leng
th (µ
m)
growth termination
0 100 2001500
1550
1600
Distance from the tube tip (µm)
Ram
an s
hift
(cm
−1) 0 0 0 01 1 1 1# # #
tube 1
CVD time:12 minLabel interval: 1 minTemperature:800 ˚C
pEtOH:~140 Pacost: < ¥4000 /CVD
Sudden stop of growth (⇔ L = γτ0(exp(-t/τ0) [1]) Different growth rate, incubation time, lifetime
G-band frequency
01#
~1592~1580
~1565~1550 cm-1
30 μm 30 μm
01 # 1 1
0# 130 μm
0
tube1
tube2
catalysts
λex = 532 nm
Ar (+3% H2): 50 sccm
Total ethanol: 5 sccm
K. Otsuka et al., ACS Nano (2018) [DOI: 10.1021/acsnano.8b01630]
NREL solar cell efficiency chart
http://www.nrel.gov/ncpv/images/efficiency_chart.jpg
Organic Thin FilmNormal structure
Inverted structureP3HT Donor PC61BM Acceptor
Glass or PET
ITO or FTO
PEDOT:PSS or MoOx
P3HT or PTB7
PCBM or PC71BM:DIO
Ca or LiF
Al
PC61BM
3.8
6.01
4.8ITO
PEDOT:PSS
5.1 5.1Au
P3HT
3.3
5.2
3.0
e
+ +ZnO
4.2
7.5
e
e
+
e
PC61BM
3.8
6.01
4.3Al4.8
ITO
PEDOT:PSS
5.1
P3HT
3.3
5.2
3.0
2.6LiF
e
++
+
e
e
Glass or PET
ITO or FTO
ZnO
PCBM or PC71BM:DIO
P3HT or PTB7
PEDOT:PSS
Au
CNT for Organic Thin FilmNormal structure
Inverted structure
Il Jeon et al.,JACS
137 (2015) 7982. I. Jeon et al., Sci. Rep., 6 (2016) 31348.
Sandwich HNO3:3.7 % Bridge MoOx:3.1 %
Perovskite Solar Cells
• Use of Perovskite PCE 3.8 %A. Kojima, et al., J. Am. Chem. Soc., 2009
• Solid state solar cell PCE 10.9 %M. M. Lee, et al., Science, 2012
• High PCE 20.1 %N. J. Jeon, et al., Nature, 2014
・PCE record 22.1% 2016
500 nmFTO
dense TiO2
perovskite
HTMAu
GlassFTO
TiO2Perovskite
Spiro-MeOTADAu
Perovskite
3.75
5.35.1Au4.5
FTOTiO2
4.0
7.4
Spiro-MeTAD
2.0
5.2
Ener
gy le
vel (
eV v
s va
cuum
)
e
+ + +
e
e
M = Pb2+, Sn2+, Cs2+, Rb2+
A = Methylammonium (MA), CH3NH3+
Formamidinium (FA), CH3(NH2)2+
Guanidinium (Gua), CH6N3+
X = I-, Cl-, Br-
MAPbI3: CH3NH3PbI3
Perovskite: AMX3
Perovskite Solar Cells
• Use of Perovskite PCE 3.8 %A. Kojima, et al., J. Am. Chem. Soc., 2009
• Solid state solar cell PCE 10.9 %M. M. Lee, et al., Science, 2012
• High PCE 20.1 %N. J. Jeon, et al., Nature, 2014
・PCE record 22.1% 2016
500 nmFTO
dense TiO2
perovskite
HTMAu
GlassFTO
TiO2Perovskite
Spiro-MeOTADAu
Perovskite
3.75
5.35.1Au4.5
FTOTiO2
4.0
7.4
Spiro-MeTAD
2.0
5.2
Ener
gy le
vel (
eV v
s va
cuum
)
e
+ + +
e
e
M = Pb2+, Sn2+, Cs2+, Rb2+
A = Methylammonium (MA), CH3NH3+
Formamidinium (FA), CH3(NH2)2+
Guanidinium (Gua), CH6N3+
X = I-, Cl-, Br-
MAPbI3: CH3NH3PbI3
Perovskite: AMX3
Organic-Inorganic Hybrid Perovskite Solar CellsNormal structure Inverted structure
GlassFTO
TiO2Perovskite
Spiro-MeOTADAu
Perovskite
3.75
5.35.1Au
4.5FTO
TiO2
4.0
7.4
Spiro-MeTAD
2.0
5.2
Ener
gy le
vel (
eV v
s va
cuum
)
e
+ + +
e
e Perovskite
3.75
5.3
PC61BM
3.8
6.01
4.3Al4.8
ITO
PEDOT:PSS
5.1
e
++
+
e
e
GlassITO
PEDOT:PSSPerovskite
PCBMAlM = Pb2+, Sn2+, Cs2+,
Rb2+
A = Methylammonium (MA), CH3NH3+
Formamidinium (FA), CH3(NH2)2+
Guanidinium (Gua), CH6N3+
X = I-, Cl-, Br-
MAPbI3: CH3NH3PbI3
Perovskite: AMX3
Diluted HNO3-SWNTPEDOT:PSSCH3NH3PbI3
Glass/PET Substrate
PC61BMAl
SWNTModified-PEDOT
CH3NH3PbI3
Glass Substrate
PC61BMAl
I. Jeon, T. Chiba, C. Delacou, Y. Guo, A. Kaskela, O. Reynaud, E. I. Kauppinen, S. Maruyama, Y. Matsuo, Nano Lett., 15 (2015) 6665.
Substrate Anode HTL VOC(V)
JSC(mA/cm2) FF PCE
(%)Glass ITO PEDOT:PSS 0.83 16.3 0.64 9.05Glass SWNT IPA-PEDOT:PSS 0.77 11.1 0.50 4.27Glass SWNT Surfactant-PEDOT:PSS 0.61 11.8 0.38 2.71
Glass 70 v/v% HNO3-SWNT PEDOT:PSS 0.77 14.4 0.55 6.09
Glass 50 v/v% HNO3-SWNT PEDOT:PSS 0.76 14.5 0.52 5.84Glass 35 v/v% HNO3-SWNT PEDOT:PSS 0.79 14.9 0.54 6.32Glass 15 v/v% HNO3-SWNT PEDOT:PSS 0.77 13.6 0.39 3.88PET 35 v/v% HNO3-SWNT PEDOT:PSS 0.71 11.80 0.56 5.38
ITO-Free Perovskite Solar Cells
Carbon nanotubes vs graphene for inverted PSC
I. Jeon, J. Yoon, N. Ahn, M. Atwa, C. Delacou, A. Anisimov, E. Kauppinen, M. Choi, S. Maruyama, Y. Matsuo, J. Phys. Chem. Lett., 8 (2017) 5395.
CNT Electrode (PMMA Layer for Stability)CNT Electrode (PMMA Layer for Stability)
Takahiro Sakaguchi,Il Jeon,Takaaki Chiba,Ahmed Shawky, Esko I. Kauppinen,RongXiang,Shohei Chiashi, Nam-Gyu Park*,Yutaka Matsuo*,Shigeo Maruyama*
CNT Electrode in Perovskite Solar CellsCNT Electrode in Perovskite Solar Cells
Namyoung Ahn, Il Jeon, Jungjin Yoon, Esko I. Kauppinen, Yutaka Matsuo*, Shigeo Maruyama*, Mansoo Choi*, J. Mater. Chem. A, 6(2018)1382.
Electrode type Scan direction VOC (V) JSC (mA/cm2) FF PCE (%) Hysteresis Index
CNT + spiro-MeOTADReverse 1.08 23.8 0.66 17.0
0.013Forward 1.07 23.7 0.66 16.8
CNT + PTAAReverse 0.98 22.9 0.68 15.2
0.007Forward 0.98 23.0 0.68 15.3
CNT + P3HTReverse 0.88 21.4 0.66 12.5
0.016Forward 0.88 21.5 0.65 12.3
Bare CNTReverse 0.93 21.8 0.65 13.2
0.038Forward 0.92 21.8 0.63 12.7
Perovskite
SWCNT + HTM
C60
GlassITO
PC61BM-Soaked CNTs as Cathode
Il Jeon, Seungju Seo, Yuta Sato, Clement Delacou, Anton Anisimov, Kazu Suenaga, Esko I. Kauppinen, Shigeo Maruyama*, Yutaka Matsuo*, J. Phys. Chem. C, 121 (2017) 25743.
CNT for both Cathode and Anode Electrodes
Il Jeon, Seungju Seo, Yuta Sato, Clement Delacou, Anton Anisimov, Kazu Suenaga, Esko I. Kauppinen, Shigeo Maruyama*, Yutaka Matsuo*, J. Phys. Chem. C, 121 (2017) 25743.
Metal endohedral fullerene, Li+@C60
I. Jeon, H. Ueno, S. Seo, K. Aitola, R. Nishikubo, A. Saeki, H.Okada, G. Boschloo, S. Maruyama, Y. Matsuo, Angew. Chem.
Int. Ed. 2018, in press. [DOI: 10.1002/anie.201800816].
Thank youThank you
http://www.photon.t.u-tokyo.ac.jp
*IRENA Project by JST-EC DG RTD, Strategic International Collaborative Research Program, SICORP*JSPS KAKENHI Grant Numbers JP25107002, JP15H05760*Project of the New Energy and Industrial Technology Development Organization (NEDO) of Japan.
Perovskite
SWCNT + HTM
C60
GlassITO
Organic Thin Film(Normal)
Perovskite(Inverted)
Organic Thin Film(Inverted)
Perovskite(Normal)
PerovskiteCNT for Anodeand Cathode