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Direct ection n fo for d dev evel elopment ent o of nea f near infr nfrared ed-dy dyes s for or dye ye-se sensit sitiz ized d so sola lar c cells lls from rom the he view ew p point nt of el f elect ectron i n inj

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SLIDE 1

1

Direct ection n fo for d dev evel elopment ent o

  • f nea

f near infr nfrared ed-dy dyes s for

  • r dye

ye-se sensit sitiz ized d so sola lar c cells lls from rom the he view ew p point nt of el f elect ectron i n inj nject ection n and nd cha charge e reco ecombina nation

Kyushu Institute of Technology (National Institute) Kitakyushu, Fukuoka, Japan, 808-0196, Japan Shuzi Hayase

Tokyo

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SLIDE 2

Collaborator

Kyushu Institute of Technology Shyam S. Pandey Yuhei Ogomi Nippon Steel & Sumikin Chemical Co., LTD Yoshihiro Yamaguchi Universidad de Castilla-La Mancha Abderrazzak Douhal Boiko Cohen Marcin Aiolek Gustovo de Miguel Michal Zitnan, Maria Jose Marchena Barriento, Sofia Kapetanaki

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SLIDE 3

3

Dye sensitized solar cells (DSCs)

  • B. O’Regan and M. Graetzel Nature, 1991, 353, 737

Electrolyte I-/I3

  • SnO2 /F

(Acetonitrile, ethylene carbonate, molten salts, etc.)

TiO2

10-20nm

TiO2

Ru N N CO COOH O Ti N N CO HOOC O Ti SCN NCS

OHP257

Dye

TiO2 layer: 10-20 μm Electrolyte layer: 30 μm

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SLIDE 4

Photovoltaic Performance Comparison

Certified efficiency AM1.5G ,1000W/m2

10 20 Efficiency（％）

C-Si

25.0%

Poly-Si

20.4%

a-Si DSC CIGS CIGS: CuInGaS(Se)

19.6% 11.9%

CdTe

16.7%

OPV

Commercially available 10.1 % 10.7%

Organic PV

Sharp Mitsubishi Chem. 15% (target)

  • M. A. Green, K. Emery, Y. Hishikawa, W. Warta, and E. D. Dunlop, Prog. Photovolt: Res. Appl. 2013; 21:1-11.

DSC:Dye-sensitized solar cell OPV: Organic thin film PV

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SLIDE 5

Spectrum matching for DSC to sun light spectrum (AM1.5)

25-26 mA・cm-2 32 mA・cm-2 36 mA・cm-2 FF:0.75 Voc: 0.75 14-15% 18% 20% Ru dye IR dye

Ru N N CO COOH O Ti N N CO HOOC O Ti SCN NCS

OHP257

Increase in Voc Increase in Jsc (New dye, or tandem, hybrid)

5

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SLIDE 6

IPCE 80%, FF 0.75

Efficiency expectation

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SLIDE 7

Wavelength (nm) IPCE

N-719 Black dye 300 400 500 600 700 800 900 1000 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Cocktail dyes A B

New NIR dyes to be developed Conventional Ru dye

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SLIDE 8

e-

hν dye I -/ I 3

  • HOMO

LUMO TiO iO2co cond

  • nd. b

band nd

e- ⊿G1 G1 0. 0.9eV 9eV ⊿G2

Requirement for development of Near Infrared Dye

How to decrease ⊿G1 and ⊿G2 with maintaining fast electron shift Collaboration of solar cell researchers with photo-physics researchers

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SLIDE 9

Dye syntheses Molecular orbital calculation Solar cell performance evaluation Fundamental analyses

  • n solar cells

Time resolved study Analyses of electron injection and dye regeneration

Co Collaboration of J Japan si side with Spain si side

Extraction of items determining sola cell efficiency Propose high efficiency dyes Douhal group (Time resolved study) Hayase group (Solar cell-based research) Samples Substrates Dynamics

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SLIDE 10

A B

10 20 30 40 50 0.00 0.25 0.50 0.75 1.00

No electrolyte ΙΙΙ ΙΙ

Normalized ∆A Time / ps

No electrolyte Ι

1 2 3 4 5 0.00 0.25 0.50 0.75 1.00

Normalized ∆A Time / ps

ΙΙΙ ΙΙ Ι

450 500 550 600650 700 750

  • 0.2
  • 0.1

0.0 0.1

700 725 750 775

  • 0.02
  • 0.01

0.00

0 ps 1 ps 3 ps 7 ps 42 ps

∆A Wavelength / nm

∆A Wavelength / nm

Ground State Bleaching

Femto-second Transient Absorption: SQ-41

) ( ) ( *

2 2 1 − +

  • +

→ + e TiO SQ TiO S SQ

Electrolyte Life-tim I 6.7 ps II 11.1 p III 4.9 ps No 2.5 ps

( ) exp[( ) ] f x A t

β

τ = −

SQ radical cation formation; Electron injection Change in spectral shape at longer delay. Signal beyond 2 ns.

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SLIDE 11

Research Collaboration

✓ Research discussions: 5 times March 2010 (Spain), May 2011 (Spain), Aug. 2011 (Japan),

  • Sep. 2011 (Spain), June 2012 (Sweden)

✓ Dr. Gustovo de Miguel visited us in Japan and joined the research in Aug. 2011. ✓ Provided 15 dyes and 15 substrates (encapsulated) to Douhal Lab.

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SLIDE 12

Development of near IR dyes for combination with TiO2 (~900 nm)

e-

hν dye I -/ I 3

  • HOMO

LUMO

✔HOMO-LUMO energy level adjustment ✔ LUMO orbital shape ✔Electron injection energy barrier ✔Excitation life time ✔Molecular orbital calculation ✔Dye syntheses tech. ✔Cell structure and cell analyses

TiO iO2co cond

  • nd. b

band nd

e- 0. 0.2eV 2eV 0. 0.9eV 9eV

12

✔ Time resolved spectroscopy

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SLIDE 13

Simulation results of molecular orbital on organic dye

13

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SLIDE 14

Side chain effect

HOOC N+ O O- N COOH

R R SQ dyes

Model dyes: Sharp absorption spectra

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SLIDE 15

HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH

SQD-2 (alkyl chain=2) SQD-4 (alkyl chain=4) SQD-8 (alkyl chain=8) SQD-12 (alkyl chain=12) SQD-18 (alkyl chain=18)

HOOC N+ O O- N COOH

SQD-0 (alkyl chain=0)

N O O N F F F F F F COOH HOOC

SQD-4F3

Designing of molecular structures after MO calculation

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SLIDE 16

Energy vs EVac (eV) Alkyl chain length

TiO2 CB I3

  • /I-

SQ-Fluoro SQ-Fluoro 5 10 15 20

  • 6
  • 5
  • 4
  • 3

HOMO-LUMO level of synthesized dyes

HOMO-LUMO level can be controlled within 0.6 eV by varying substituents ΔG1 LUMO HOMO ΔG2 TiO2 CB I-/I3

  • HOMO

LUMO Introduction of F alkll decreases HOMO and LUMO

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SLIDE 17

0.00 0.40 0.80 1.20 1.60 2.00 2.40 2.80 2 4 6 8 10 12 14 16 18 20

Efficiency [%] Alkyl Chain Length

Effic fficie iency vs y vs. Alk lkyl yl chain ain le length th

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SLIDE 18

HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH HOOC N+ O O- N COOH

SQ-2 (alkyl chain=2) SQ-4 (alkyl chain=4) SQ-8 (alkyl chain=8) SQ-12 (alkyl chain=12) SQ-18 (alkyl chain=18)

Adsorption scheme for SQ dyes

N+ O O- N N+ O O- N N+ O O- N N+ O O- N N+ O O- N N+ O O- N N+ O O- N

TiO2 TiO2

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SLIDE 19

Main structure responsible for near IR dyes

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SLIDE 20

(SQD2)

N O

  • O

N COOH

SQ-12

Chemical Formula: C36H40N2O4 Exact Mass: 564.2988

Dyes with extended conjugation

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SLIDE 21

0. 0.4 0. 0.8 1. 1.2 500 500 600 600 700 700 800 800 900 900

Absorbace (Norm.) Wavelength (nm)

8 27 31 16 70

21

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SLIDE 22
  • 7.3
  • 6.3
  • 5.3
  • 4.3
  • 3.3

TiO2 8 27 31 16 70

Vacuum level [eV]

I-/I3

  • Model SQ dyes

LUMO LUMO LUMO LUMO LUMO HOMO HOMO HOMO HOMO HOMO Redox potential Conduction band TiO2

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SLIDE 23

One of results of collaboration research

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SLIDE 24

Model Squaraine Sensitizers

  • 1. Chain length ----- SQ-2 and SQ-4
  • 2. Nature of substituents----SQ-4 and SQ-26
  • 3. Molecular Asymmetry------------- SQ-26 and SQ-41
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SLIDE 25

Electronic Absorption Spectra

550 600 650 700 750 0.0 0.2 0.4 0.6 0.8 1.0

Normalized absorbance Wavelength / nm

SQ 41 SQ 26

SQ 4

SQ 2

ε = 2-3 X 105 dm3.mole-1.cm-1

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SLIDE 26

Energy Band Diagram

CB TiO2 I-/I3

  • SQD8

SQ4/4F3 SQD4F6 LUMO change: Electron injection HOMO change: Dye generation Anchor group: Substitution effects: ⊿G1 ⊿G2

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SLIDE 27

Photovoltaic Characteristics

Pho hotocur current ent Act ction n Spect pectra

Wavelength (nm) IPCE

SQ-2 SQ-4 SQ-26 SQ-41 400 500 600 700 0.1 0.2 0.3 0.4 0.5 0.6 0.7

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SLIDE 28

Time Resolved Investigations

Time-resolved techniques

Femtosecond Transient Absorption Spectroscopy Nanosecond Flash Photolysis

Experimental Conditions:

  • SQ-dyes adsorbed on TiO2
  • SQ-dyes adsorbed on ZrO2

To determine the electron injection efficiency !

  • Time resolved investigations in

the presence of electrolyte

  • Time-resolved investigations

in the absence of electrolyte To determine the Dye Regeneration efficiency !

  • 3

SQ Dye

  • 4
  • 5

I-/I3-

⊿G1 ① ② ③ ④ ⑤ ⑥ TiO2

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SLIDE 29

Electron injection

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SLIDE 30
  • 3

SQ Dye

  • 4
  • 5

I-/I3-

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 ⊿ G Injection rate constant /10(-9)/s

SQ26(SQD4F6) SQ2(SQD2) SQ4(SQD8) SQ41(SQ4F3)

⊿G1 No apparent relation between ⊿G1 and injection rate constant ① ② ③ ④ ⑤ ⑥

Electron Injection (②）

Relationship between ⊿G and injection rate constant Electron injection efficiency is governed by factors other than ⊿G1 Better TiO2

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SLIDE 31
  • 3

SQ Dye

  • 4
  • 5

I-/I3-

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 ⊿ G Injection rate constant /10(-9)/s

SQ26(SQD4F6) SQ2(SQD2) SQ4(SQD8) SQ41(SQ4F3)

⊿G1 ① ② ③ ④ ⑤ ⑥

Electron Injection (②）

Relationship between ⊿G and injection rate constant F facilitates the electron injection with the same ⊿G1 High electron injection can be realized with lower⊿G1 by using dyes with F atoms Better TiO2 Common trend

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SLIDE 32

Dye regeneration

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SLIDE 33

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.2 0.4 0.6 0.8 1 1.2 Gap (redox-HOMO)/eV Regeneration efficiency

SQ41(SQ4F3) SQ26(SQD4F6) SQ4(SQD8) SQ2(SQD2)

Dye generation(⑥）

Relationship between ⊿G2 and dye regeneration

  • 3

SQ Dye

  • 4
  • 5

I-/I3-

⊿G2 ① ② ③ ④ ⑤ ⑥ High dye generation with Low ⊿G2 Better for high efficiency Common trend

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SLIDE 34

Symmetrical-SQ-26

N O O N COOH F F F F F F HOOC

Chemical Formula: C36H34F6N2O6 Exact Mass: 704.23

TiO2

I-

HOMO

Possible explanation for high efficiency dye generation with low ⊿G2

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SLIDE 35

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 0.50 0.52 0.54 0.56 0.58 0.60 0.62 Rrel (I3-/I-) Voc (V)

SQ4 SQ4F3 SQ18 SQ4O2 SQ4O4 SQ4F6

I3-

e

TiO2

e

TiO2

I3-

30 nm 30,000 nm

N O O N HOOC COOH

R1 R2

R1 = R2 = Butyl SQ4 R1 = R2 = Dodecyl SQ12 R1 = R2 = Octadecyl SQ 18 R1 = R2 = Trifluorobutyl SQ 4F6 R1 = R2 = Methoxybutyl SQ4O2 R1 = R2 = Ethylbutanoate SQ4O4 R1 =Butyl & R2 = Trifluorobutyl SQ4F3

  • F
  • O-
  • A. Hayat, S. S. Pandey, Y. Ogomi, and S. Hayase, J. Electrochem. Soc., 158, B770-B771 (2011).

Porous TiO2 sheet TiO2 F O Dye I3

  • e
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SLIDE 36
  • 3

SQ Dye

  • 4
  • 5

I-/I3-

⊿G ① ② ③ ④ ⑤

⑥ Ei eff: Electron injection efficiency: ②/②+③ Reg eff: Regeration efficiency: ⑥/④+⑥

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.2 0.4 0.6 0.8 1 IPCE Ei eff x Reg eff

SQ4(SQD8) SQ41(SQ4F3) SQ26(SQD4F6) SQ2(SQD2)

Explanation on IPCE (④）

IPCE can be explained by product of electron injection efficiency and regeneration efficiency

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SLIDE 37

TiO2

I-

HOMO LUMO Polar substitute interacting with I- High dye generation efficiency with low ⊿G2 High electron injection efficiency with low ⊿G1 High Coupling

Proposed structure realizing high efficiency dye generation with low ⊿G2 and high electron injection with low ⊿G1

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SLIDE 38

Concl nclus usions ns

  • 6 model Squaraine dyes were synthesized to investigate the role, of

alkyl chain length, nature of substituents and molecular asymmetry on the photovoltaic performance.

  • Electron injection and dye regeneration are not always governed

by energy gap (⊿G) and influenced by substituents and molecular structure. This suggests that high electron injection with low ⊿G becomes possible.

  • Creation of molecular asymmetry and introduction of longer alkyl

chain leads to facile electron injection.

  • Introduction of electron withdrawing Fluor-alkyl substituent leads

to facile dye regeneration.

  • Order of IPCE value was explained by the product of charge

injection efficiency and dye regeneration efficiency.

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SLIDE 39

List of Publications in Academic Journals:

[1] Alkyl and Fluoroalkyl Substituted Squaraine Dyes: A Prospective Approach Towards Development of Novel NIR Sensitizers; Shyam S. Pandey, Takafumi Inoue, Naotaka Fujikawa, Yoshihiro Yamaguchi and Shuzi Hayase, Thin Solid Films, Vol. 519, pp. 1066-1071 (2010). [2] Substituent Effect in Direct Ring Functionalized Squaraine Dyes on Near Infra-Red Sensitization of NanocrystallineTiO2 for Molecular Photovoltaics ; Shyam S. Pandey, Takafumi Inoue, Naotaka Fujikawa, Yoshihiro Yamaguchi and Shuzi Hayase, Journal of Photochemistry and Photobiology A: Chemistry, Vol. 214, pp. 269-275 (2010). [3] Synthesis and characterization of squaric acid based NIR dyes for their application towards dye-sensitized solar cells ; Inoue, Takafumi, Pandey, Shyam S., Fujikawa, Naotaka, Yamaguchi, Yoshihiro, Hayase, Shuzi; JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY Volume: 213 Issue: 1 Pages: 23-29 (2010). [4] Fine tuning the structure of unsymmetrical squaraine dyes towards the development of efficient dye sensitized solar cells; Shyam S. Pandey, Rie Watanabe, Naotaka Fujikawa, Yuhei Ogomi, Yoshihiro Yamaguchi and Shuzi Hayase; Proc. SPIE Vol. 8111 Page 811116 (2011).

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SLIDE 40

[5] Femto to millisecond observations of indole-based squaraine molecules photodynamics in Solution.; G. de Miguel, M. Marchena, M. Ziolek, M, Zitnan, S. S. Pandey, S Hayase and A. Douhal. Physical Chemistry and Chemical Physics; Vol. 14, Pages 1796-1805 (2012). [6] Photophysics of H-and J-aggregates of Indole based squaraines in solid state.; G. de Miguel,

  • M. Ziolek, M, Zitnan, J. A. Organero, S. S. Pandey, S Hayase and A. Douhal; Journal of Physical

Chemistry-C; Vol. 116, No.-17, Pages 9379-9389 (2012). [7] Femto to Millisecond Photophysical Characterization of Indole-based Squaraines Adsorbed

  • n TiO2 Nanoparticle Thin Films. de Miguel, Gustavo; Marchena, Maria Jose; Ziolek, Marcin;

Pandey, Shyam; Hayase, Shuzi; Douhal, Abderrazzak; Journal of Physical Chemistry-C;

  • Vol. 116, No.-22, Pages 12137-12148 (2012).

[8] Novel unsymmetrical squaraine dye bearing cyanoacrylic acid anchoring group and its photosensitization behavior; Gururaj M. Shivashimpi, Shyam S. Pandey, Rie Watanabe, Naotaka Fujikawa, Yuhei Ogomi, Yoshihiro Yamaguchi and Shuzi Hayase ; Tetrahedron Letters;

  • Vol. 53, No.40, Pages 5437-5440 (2012).

[9] Relating the Photodynamics of Squaraine-Based Dye-Sensitized Solar Cells to the Molecular Structure of the Sensitizers and to the Presence of Additives; G. de Miguel, M. Marchena,

  • B. Cohen, S. S. Pandey, S. Hayase and A. Douhal; Journal of Physical Chemistry-C; Vol. 116,

No.-42, Pages 22157-22168 (2012).

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SLIDE 41

[10] Dye-Sensitized Solar Cells based on Novel Far-red Sensitizing Unsymmetrical Squaraine Dye containing Pyrroloquinoline Moiety.; Shyam S. Pandey, Naotaka Fujikawa, Rie Watanabe, Yuhei Ogomi, Yoshihiro Yamaguchi and Shuzi Hayase; Japanese Journal of Applied Physics;

  • Vol. 51, No.-10, Issue-2, pages 10NE12-1-10NE12-5 (2012).

[11] Solution processable thin film organic photovoltaic cells based on far red sensitive soluble squaraine dye; Shyam S. Pandey, Takafumi Mizuno, Sandeep K. Das, Yuhei Ogomi and Shuzi Hayase; Thin Solid Films; Vol. 522, pages 401-406 (2012). [12] Effect of extended p-conjugation on photovoltaic performance of dye-sensitized solar cells based on unsymmetrical squaraine dyes; Shyam S. Pandey, Rie Watanabe, Naotaka Fujikawa, Gururaj M. Shivashimpi, Yuhei Ogomi, Yoshihiro Yamaguchi and Shuzi Hayase; Tetrahedron,

  • Vol. 69, No. 12, pages 2633-2639 (2013).

[13] Effect of anchoring groups on photosensitization behavior in unsymmetrical squaraine dyes’ Gururaj M. Shivashimpi1, Shyam S. Pandey1, Rie Watanabe1, Naotaka Fujikawa1, , Yuhei Ogomi1, Yoshihiro Yamaguchi2, Shuzi Hayase; Synthetic Metals (Submitted). [14] Real-Time Photodynamics of Squaraine-Based DSSCs with Iodide and Cobalt Electrolytes; Maria Jose; de Miguel, Gustavo; Cohen, Boiko; Hayase, Shuzi; Pandey, Shyam; Douhal, Abderrazzak; Journal of Physical Chemistry-C (Submitted).

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SLIDE 42

Thank you for your attention !