Tetraphenylporphyrin/Polyaniline

Complexes as Optic Active Layer in Organic Optoelectronic

Applications

1

Veinardi Suendo1,6, Suprijadi2,6, Sparisoma Viridi3, Brian Yuliarto4,6, Phutri Milana1, Ferdinand Hidayat1, Koutaro Takeyasu6, Kanta

Asakawa6, Shohei Ogura6, Katsuyuki Fukutani6

1Kelompok Keahlian Kimia Anorganik dan Fisik, Jurusan Kimia, Fakultas Matermatika dan Ilmu Pengetahuan Alam, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132, Indonesia

2Kelompok Keahlian Fisika Teoritik dan Energi Tinggi, Jurusan Fisika, Fakultas Matermatika dan Ilmu Pengetahuan Alam, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132, Indonesia 3Kelompok Keahlian Fisika Nuklir dan Biofisika, Jurusan Fisika, Fakultas Matermatika dan Ilmu Pengetahuan Alam, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132, Indonesia

4Kelompok Keahlian Teknik Fisika, Jurusan Teknik Fisika, Fakultas Teknologi Industri, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132, Indonesia

5National Research Centre for Nanotechnology, Jalan Ganesha 10, Bandung 40132, Indonesia 6Institute of Industrial Science, The University of Tokyo, 4-6-1 komaba meguro-ku, tokyo 153-8505, Japan

Plan of Presentation

Introduction Experiments Results and Discussion Conclusions

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INTRODUCTION

Tetraphenylporphyrin/Polyaniline Complexes as Optic Active Layer in Organic Optoelectronic Applications

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Global Energy Demand

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Solar Energy

Obstacles : High production cost Expensive components All components are

imported

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A cheaper photovoltaic technology has to be

developed in Indonesia

DSSC (Dye-Sensitized Solar Cell) Simple Fabrication Dye/sensitizer can be

obtain locally: natural pigments, i.e. photosynthetic pigments from green plants, anthocyanins, etc.

Very suitable to be implemented in Indonesia.

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DSSC components

Porphyrin

A potential dye/sensitizer for DSSC that covers a certain range of light radiation

High quantum efficiency Has a unique molecular junction with a

wide-band gap semiconductor that depends on how it was immobilized

High molecular symmetry with point group of D4h (metalloporphyrin) or D2h /C2V (free-base porphyrin)

.

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Porphyrin

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Several porphyrins are available abundantly in nature: chlorophyll a, heme B (in hemoglobin), heme C (pada cytochrome c).

N

N N

N

Mg

H

O

O

H

O

H

COOCH3

CH3 H CH3 H

chlorophyll a

Heme B

Heme C

Chlorophyll

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Meso-Tetraphenylporphyrin (TPP)

Synthetic pigment with a simple synthesis pathway and high yield

High absorption coefficient in visible light

Gives a strong photoluminescence in red

Simple to vary its properties through the insertion of metal ions, protonation and addition of linker molecules

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Polyaniline

• Low production cost • Covers a wide range of

electrical conductivity (10-10

S/cm - 100 S/cm) • High environmental and

thermal stability

Advantages :

Aniline

POLYANILINE

Leucoemeraldine Base (LEB), Y = 1

Emeraldine Base (EB), Y = 0.5

Pernigraniline Base (PNB), Y = 0

Molecular Junction in TPP/PANI Blend

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NH+

NH NH+ NH

NNNNZn

π Stacking interaction

NH+

NH NH+ NH

NNNNZn

covalent coordination with type (η6, L3), (η4, L2) or (η2, L), between π electrons and central metal ion

Molecular Junction in TPP/PANI Blend

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NH+

NH NH+ NH

NNNNZn

covalent coordination with type (η2, L) between lone pair and central metal ion

N N N N

H H

HH

N

N

N

N

M

N

N

N

N

n

Lewis acid-base interaction

EXPERIMENTS

Tetraphenylporphyrin/Polyaniline Complexes as Optic Active Layer in Organic Optoelectronic Applications

15

16

Synthesis of Porphyrins

Acidic Silica Gel AldehydePyrrole

Mixture on Silica

Variation of aldehyde:1. Benzaldehyde2. p-methoxybenzaldehyde3. p-dimethylaminobenzaldehyde

Porphyrin

Microwave radiation (10 minutes)

Synthesis of Polyaniline

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Rinsed three times with 100 mL HCl 1 M Rinsed three times with acetone Dried in vacuum oven at 60 oC

Added 50 mL Aqua dm, then stored for 1 hour at polimerization temperature

Added 50 mL HCl 1M, then stored for 1 hour at polimerization temperature

20 mmol of Aniline

25 mmol of (NH4)2S2O8

Solution of (NH4)2S2O8

PANI

Solution of Anilin-HCl

PANI HCl (ES)

Stirred for 24 hours at 250 rpm, then filtered

Blending of TPP/PANI

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PANITPP in

dichloromethane

TPP/PANI Pellets

Concentration of TPP:1. 2.0% (% w/w)2. 1.5% (% w/w)3. 1.0% (% w/w)4. 0.5% (% w/w)

Blending TPP solution into PANI powder,then compressed Into a pellet

Characterization of TPP/PANI

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TPP/PANI Pellets

UV-Vis Reflectometry

UPS AC Impedance analysis

Data Analysis and Interpretation

Schematic of UV Photoelectron

Spectroscopy (UPS)

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Focused UV beam He I line (21.22 eV)

Solid sample

UV Photoemission Spectrometer in IIS/The University of Tokyo

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UV Photoemission Spectrometer in IIS/The University of Tokyo

RESULTS AND DISCUSSION

Tetraphenylporphyrin/Polyaniline Complexes as Optic Active Layer in Organic Optoelectronic Applications

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meso-Tetraphenylporphyrin synthesis

TPP spot

Rf = 0,775

Purple fraction (TPP)

Yellow fraction

Green fraction

Orange fraction

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meso-tetraphenylporphyrin crystals

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UV-VIS absorption and emission spectra of TPP in chloroform

2.0 2.5 3.0 3.5

0

2

4

2,2622,108

1.906 2,98

1,919

Energy (eV)

Abso

rban

ce

Absorpsi

0

50

100

150

∆E = 0,356

TPP in chloroform

Emisi

Inte

nsity

(a.u

)

1.8 1.9 2.0 2.1 2.2 2.30.00

0.05

0.10

0.15 1,906 2.262

0

50

100

150

27 a) As synthesized in silica gel , b) crude extract in chloroform, c) purification using column chromatography, d) several franctions after purification.

meso-Tetra(p-dimethylaminophenyl)porphyrin synthesis

meso-Tetra(p-dimethylaminophenyl)porphyrin synthesis

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400 500 600 700

0,0

0,2

0,4

0,6

0,8

1,0

1,2

418

513 545 588 644

669570525

436,5

Abso

rbans

i (a.u)

Panjang gelombang (nm)

TPP TDMAPP (strategi 3)

meso-Tetra(p-dimethylaminophenyl)porphyrin synthesis

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669570525

436,5

443,8

685,91

400 500 600 700 800 900

0.0

0.2

0.4

0.6

0.8

1.0

1.2 Spektrum UV Spektrum Fluoresensi

Panjang gelombang (nm)

Abso

rban

si (a

.u)

0.0

0.2

0.4

0.6

0.8

1.0

Intensitas (a.u)

Polyaniline synthesis

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UV Photoelectron spectra

0 5 10 15

0

1x103

2x103

3x103

PANI TPP/PANI (0.5 % w/w) TPP/PANI (1.0 % w/w) TPP/PANI (1.5 % w/w) TPP/PANI (2.0 % w/w) Substrate holder TPP Film

Norm

alize

d In

tens

ity (a

.u.)

Binding Energy (eV)

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Surface workfunction

0.0 0.4 0.8 1.2 1.6 2.04.40

4.45

4.50

4.55

4.60

4.65

4.70

4.75

4.80

Substrate holder (Ta)

Wor

k Fu

nctio

n (e

V)

[TPP] (%w/w)

PANI (CHCl3)

PANI:TPP (CHCl3)

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UV-Vis reflectance spectra

1 2 3 4 5

0

2

4

6

8

10

12

14

1.67 eV

1.41 eV

3.34 eV

2.72 eV

3.09 eV

F(R)

(a.u

.)

Energy (eV)

TPP/PANI 0.5% TPP/PANI 1.0% TPP/PANI 1.5% TPP/PANI 2.0% TPP PANI

2.87 eV

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Electrical conductivity

102 103 104 105 106

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

σ (S

cm

-1)

Frequency (Hz)

TPP/PANI 0.5% TPP/PANI 1.0% TPP/PANI 1.5% TPP/PANI 2.0% PANI

CONCLUSIONS

Tetraphenylporphyrin/Polyaniline Complexes as Optic Active Layer in Organic Optoelectronic Applications

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Conclusions Both UPS and UV-Vis reflectance results show that the

presence of TPP in TPP/PANI blend adds some electronic states in PANI valence band.

A certain concentration limit is necessary to alter the properties of the blend significantly with respect to the pure PANI.

Interesting doping feature was also observed in the electrical conductivity as a function of frequency of TPP/PANI blend, where the presence of TPP improved the high frequency part of electrical conductivity significantly.

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Future Plans Ab initio study on the interaction between TPP

and PANI in TPP/PANI blend and its electronic properties.

Photoluminescence measurements of TPP/PANI blends in their resonance wavelengths.

Raman/FTIR measurements to reveal the interaction between TPP and PANI in TPP/PANI blend

Applying TPP/PANI blends as a simple PV device.

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Thank you

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