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