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CNRS-Ewha International Research Center Introduction CNRS-EWHA Winter School 2012

Jeong Weon Wu

2

Overview

Quantum Dynamics Imaging Period : 2 years + 4 years 1st stage: September 2010 – August 2012 2nd stage: September 2012 –August 2016

Name CNRS/IPCMS Marc Drillon Director FPI Jean-Yves Bigot Deputy Director Charles Hirlimann Researcher Alain Fort Researcher Stefan Haacke Researcher Jean Pierre Bucher Researcher Christian Meny Researcher Nathalie Viart Researcher Christophe Lefevre Researcher Francois Roulland Researcher Salia Cherifi Researcher Mircea Rastei Researcher Marie Barthelemy Researcher Mircea Vomir Researcher Name Affiliation Jeong Weon Wu Director / Ewha KPI Woun Kang Ewha In-Sang Yang Ewha Kong-Ju-Bock Lee Ewha Seokhyun Yoon Ewha Dong-Wook Kim Ewha Jean Charles Ribierre Ewha Hong-Kyu Park Korea Univ. Hyung Joon Choi Yonsei Univ. Kyungsik Kim Yonsei Univ. Young Woo Son KIAS Seok Bong Choi Seoul National Univ.

Korean Participant French Participant

Participants to the CNRS-Ewha Research Center(CERC)

Opening ening Cerem emony ny of CERC

“Fu Future S e Scient entific C Col

• llabor

aboration bet n between een K Kor

• rea

ea and and Fr Franc ance”

14th October 2010

ST Telecom 3rd Floor 231 m2)

CERC Laboratory

5

• Laboratory l ( 69.3 m2), Laboratory ll (115.5 m2), Office (46.2 m2)
• Space: Total 231 m2

CERC RC Labor

• rat

ator

• ry
• SK Telecom Building at Ewha Womans University
• Laboratory l ( 69.3 m2), Laboratory ll (115.5 m2), Office (46.2 m2)
• Space: Total 231 m2

Ultra rafast Ti:sap sapphire e laser syst aser system

• f
• f C

CERC Labora Laboratory

Ultrafast time-res esol

• lved

ed pump-probe be laser er system em

• SpitfroPro-XP, Ti:sapphire amplifier system, <35fs, 5kHz, 0.8mJ
• MaiTai-SP, Short pulse, one-box Ti:sapphire oscillator
• Empower-30, Pump laser, 527nm, 20mJ, 5kHz
• Liquid Nitrogen cooled CCD and Spectrometer

Dr.

• r. C

Chri hristian M Meny eny ( ( 7th

th Feb.

• eb. – 2nd

nd Mar.

• ar. 2011)

2011)

• Research of spin imaging based on NMR
• Ga2-xFexO3 thin films focusing on anti-ferromagnetic

coupling behaviors

Dr.

• r. C

Chri hristop

• phe Lef

Lefev evre (7 (7th

th Feb.

• eb. – 2nd

nd Apr.

• pr. 2011)

2011)

• Ga2-xFexO3 thin films focusing on anti-ferromagnetic coupling

behaviors

Dr.

• r. Jean

Jean-Yves B Bigot got (F (Feb. eb., M Mar. ar.- Apr. pr. 2011 2011)

• Time-resolved spectroscopy and spin-photonics
• Building pump-probe fs laser experiment
• Lecture on “Journey of Ultrafast Spectroscopy in Condensed

Matter”

• Research on time-resolved

spectroscopy and spin-photonics

• Building pump-probe fs laser

experiment

Dr.

• r. M

Mircea rcea V Vom

• mir

r (F (Feb. eb., M Mar. ar.- Apr. pr. 2011 2011)

Dr.

• r. M

Mari arie B e Bart arthel helemy (3 (3rd

rd-15

15th

th Apr.

• pr. 2011)

2011)

• Research on time-resolved spectroscopy and spin-photonics
• Building pump-probe fs laser experiment

Dr.

• r. A

Alai ain F n Fort

• rt (14

(14th

th – 26

26th

th Jun.

• Jun. 2011)

2011)

• Photo-imaging using quantum holography
• Seminar “Blue-UV Organic Laser Sources”

14

Homepage

http://cnrs-ewha.ewha.ac.kr

15

7-11 Feb. 2011 CERC 10 Lectures International Speakers 5 Lectures Domestic Speakers 3 Lectures

Collaborations

CERC WINTER SCHOOL 2011 (The 4th Winter School) 개최

16

Research Topics Research Contents Ultrafast optical imaging Metal nano-structure ultrafast time-resolved measurement exhibits a structure-dependent ps time-response. Heterocyclic oligomer structure for optoelectronic application Low-dimensional conjugated electronic structure possesses a strong exciton density-dependent ps relaxation time. Multiferroics materials for spintronic application Optimum doping level for the minimum leakage current is identified.

Collaborations in year 2010-2011

Visit to IPCMS/CNRS

17

13 May 2011 Interim Review at IPCMS/CNRS

• Ewha: J.W. Wu, W. Kang, I.S. Yang, K.J.B. Lee, D.W. Kim, Jean Charles Ribierre
• IPCMS: Marc Drillon, Jean-Yves Bigot, Alain Fort, Christian Meny, Christophe Lefvere,

Mircea Vomir, Marie Barthelemy

Collaborations in year 2010-2011

CNRS – Director from Tokyo

18

18 May 2011

• Dr. Guy Faure visit CERC

Director of Regional Office Japan-South Korea-Taiwan from CNRS

• G.H. Choi (Dean of Research), J.W. Wu, W. Knag, S.H. Yoon

Collaborations in year 2010-2011

[1] Project International Scientific Collaboration(PICS)

• W. Jo (Ewha) - C. Meny (CNRS/IPCMS)
• > 2010-2012

19

Other related programs

[2] Science and Technology Amicable Relationship(STAR)

• J. C. Ribierre(Ewha) - A. Barsella, L. Mager, A. Fort (CNRS/IPCMS)
• > 2011-2012

Collaborations in year 2010-2011

 Dr. Christophe Lefevre (Sep.- Dec. 2011, 3 months) Oxide Fabrication by PLD  Dr. Christian Meny (Dec. 2011, 2 weeks) Multiferroic Oxide Characterization  Dr. Alberto Barsella and Dr. Alain Fort (Oct. 2011, 2 weeks) Femtosecond Laser Exp.  Dr. Jean Charles Ribierre Visiting professor to IPCMS/CNRS for 2 months in both 2012 and 2013  GRDC (Global R&D Center) Plenary Speaker (Marc Drillon) 15-16 November 2011  CERC Review and ICAMD (Mark Drillon, Jean-Yves Bigot, Alain Fort, Stefan Haacke, Nathalie Viart, Christian Meny, Christophe Lefevre) Annual Review and 7th International Conference on Advanced Materials and Devices at Jeju in 6th – 9th Dec. 2011

Plan : Sep. 2011 – Aug. 2012

 Ms. Minji Kwon (Sep. 2011- Feb. 2012, 6 months) Physics Dept. of Ewha: long-term stay visit to IPCMS/CNRS for 6 months  Dr. Jaeheun Woo (Sep.-Oct. 2011, 1 month) Physics Dept. of Ewha: short-term stay visit to IPCMS/CNRS for 1 month

Plan : Sep. 2011 – Aug. 2012

 Workshop: Winter school every year 1st week of Feb. in Strasbourg and in Seoul alternately  Conference: submit a proposal of symposium in E-MRS conference in 2013  Research: strengthen collaboration in (1) Organic photonics (J-C. Ribierre) (2) Dynamical processes in bio-molecular systems (S. Haacke) Perspec ectives es

Topic: New Emerging Phenomena in Physics and Chemistry Date: Feb 6(Mon)-8(Wed) morning : Symposium Feb 8(Wed) afternoon -10(Fri) : The 5th Winter School Organizing co-chair : Christophe Lefevre (IPCMS/CNRS) Dong-Wook Kim (Ewha Womans Univ.) Organizing committee member : Cheolmin Park (Yonsei Univ.), Jae-Hyung Jang (Yonsei Univ.), Jean Charles Ribierre (Ewha), William Jo (Ewha), Steering committee : Marc Drillon (IPCMS), Jeong Weon Wu (Ewha), Andre-Jean Attias (Paris), Eunkyoung Kim (Yonsei)

KO KOREA EA-FRANCE Joint nt Sympos posium um 2012 2 (CNR NRS-EW EWHA A Winter er School

• ol 5th )

Fut utur ure P e Plan an of

• f Nex

ext 4 4 Year ears

• Sep. 2012 - Aug. 2016: 2nd stage for 4 years
• UMI from CNRS will be submitted (more long-term

stay of CNRS researchers in CERC and more exchange of PhD students from Korea to France)

• EU Project in a larger scale for program and budget

• Chiral Metamaterials: J.H. Woo, J.H. Lee, M.J.

Kwon, B. Kang, M. Vomir, D.W. Kim, J.-Y . Bigot

• Oligothiophene: J.C. Ribierre, H.Y Shin, J.H.

Woo, M.J. Kwon, D.W. Kim, S. Yoon, J.-Y . Bigot

Size ~ Wavelength Diffraction Interference Size < < Wavelength Effective Medium Size > > Wavelength Geometric Optics

Wavelength of Light and Object Size

Dispersion of Refractive index

Size ~ Wavelength Photonic Crystal Size < < Wavelength Metamaterials

Artificial Structures

Effective Medium Meta-particle in sub-wavelength Control of macroscopic response via Symmetry manipulation

• f meta-particle

geometry and array

33.91 nm

• 25.56

nm

1 1 μm

Chiral Metam aterial

Chirality Coupled Oscillator Helix Molecular Fram e of Reference

1 2 3

2πb a

1 2 3

α α d/2 d/2

Molecular chirality and chiral param eters Review of Modern Physics Harris et al. ( 1 9 9 9 ) Pseudo scalar is the chiral m easure of geom etric object.

x y z σ(xz) C2(y) S2(y)=σ(xz)∗C2(y) C2(z)

x y z

Sym m etry Breaking by Substrate

x y z σ(xz) C2(y) S2(y)=σ(xz)∗C2(y) C2(z)

R (# 4) Left ~ 6 2 5 nm ~ 6 7 0 nm

400 500 600 700 800 40 60 80 100

T (%) wavelength (nm) #3 #4

Right

Pum p induced optical rotatory dispersion

Ultrafast Pum p-probe m easurem ent Pum p: 8 0 0 nm , 4 0 0 nm Circularly Polarized ( Left, Right) Probe: W hite Continuum

I ∥( Parallel polarization) -I ⊥( Perpendicular polarization)

Probe @ 7 0 0 nm

• 1

1 2 3 4 5

• 10
• 5

5 10 15 20 25

Rotation angle (radian) x 10

• 5

time (ps)

Ultrafast Pum p-probe m easurem ent ORD dependent

• n helicity
• f pum p

ps decay tim e

• Chiral Metamaterials: J.H. Woo, J.H. Lee, M.J.

Kwon, B. Kang, M. Vomir, D.W. Kim, J.-Y . Bigot

• Oligothiophene: J.C. Ribierre, H.Y Shin, J.H.

Woo, M.J. Kwon, D.W. Kim, S. Yoon, J.-Y . Bigot

Majority Carrier Type Conversion in a Solution-Processible Organic Semiconductor

QQT(CN)4

S S S S C6H13 C6H13 CN CN NC NC C6H13 C6H13

As Prepared

p-type Ambipolar n type

Thermal Annealing Laser Writing

Patterning of p-n microstructures Logic Gate

J.C. Ribierre et al., Adv. Mater. 2010, 22, 1722–1726

Reversible Majority Carrier Type Conversion

QQT(CN)4

S S S S C6H13 C6H13 CN CN NC NC C6H13 C6H13

As Prepared

p-type Ambipolar n type

Thermal Annealing Laser Writing

p-type Ambipolar n type

Vapor solvent treatment

J.C. Ribierre et al., Adv. Mater. 2010, 22, 4044. J.C. Ribierre et al., Adv. Mater. 2010, 22, 1722–1726

Absorption and HOMO/ LUMO levels in QQT(CN)4

500 1000 1500 2000 2500 0.0 0.2 0.4 0.6 0.8 in solution as-prepared thermally converted solvent vapor-treated

Absorbance Wavelength (nm)

• 5

5 10 15 2 4 6 8 10 12 14 16 As prepared After thermal annealing After vapor treatment

Intensity (a.u.) Energy (eV)

UPS spectra Nearly transparent in the visible Strong absorption in the near IR Very broad absorption in neat films

S0 S1

1.57 eV (790 nm)

T1

0.019 eV

T2

1.35 eV (919 nm)

ISC (7 ps)

Pump/ probe experiment in QQT(CN)4 solution

• Bleaching can be due to ISC (Chem.Phys.Lett. 292, 607 (1998))
• Determination of a single lifetime of about 7 ps
• Optical limiting of QQT(CN)4 solution due to triplet absorption
• ISC already reported in aromatic thiophene derivatives
• Quantum chemistry calculations show that S1 is energetically close to T2

ISC between S1 and T2 with a time constant of 7ps Optical limiting due to absorption between T2 and Tn (n= 3,4 … ?) Slight influence of the excitation density on the ISC rate. Could be some heating effects…

Tn n=3,4 ?

(~800 nm)

S S S S C6H13 C6H13 CN CN NC NC C6H13 C6H13

Optical limiting in QQT(CN)4 solution

72%−>19% ∆T=74 % @20 MW/cm2

10 100 1000 20 40 60 80

80MHz T_5kHz

Transmission [%] Intensity [MW/cm

2]

@800 nm CERC data

• Optical limiting observed in QQT(CN)4 solution (chloroform)
• At various wavelengths in the range 750 - 800 nm
• At various repetition rates from 80 MHz to 5 kHz

(OL observed only at 80 MHz, 4 MHz and 800 kHz so far, because we do not have enough power at 80 kHz and we hesitate to test it at 5 kHz with a power higher than 1 mW… we will try soon or later but…)

• Input power dependence of the transmission does not vary significantly with the repetition

rate (in the range considered in this work) The results suggest that the optical limiting is due to the absorption of the triplet states. The observed power dependence does not change with the repetition rate, due to the long lifetime of the triplets.

Pump/ probe experiment in QQT(CN)4 solution

Normalized data : ΔT/T

• 40
• 20

20 40 60 80 100 120

• 0.2

0.0 0.2 0.4 0.6 0.8 1.0

∆T/T (normalized) Time Delay (ps) 2011.04.27 Sshort2 Sshort2.3 Sshort2.8 Sshort3.0

Optical Density Decay Time (ps) 0.8 6.71 2.0 6.68 2.3 6.97 2.8 7.26 3.0 7.39 average 7.00

Fitted by a simple exponential decay. Average lifetime ~ 7 ps Slight decrease of the lifetime when increasing pump intensity No residual bleaching observed in that time range after about 40 ps

• 5

5 10 15 20 25

• 0.030
• 0.025
• 0.020
• 0.015
• 0.010
• 0.005

0.000

∆αd time (ps)

Pmol_Short range

• 0.00641
• 0.00554
• 0.01197
• 0.02692
• 0.02527

Pump/ probe experiment in p-type QQT(CN)4 neat films

• Similarly to the results in solution, transient absorption signal exhibits a

strong initial absorption bleaching reflecting that pump-induced ground- state depletion dominates the observed dynamics.

• Two characteristic lifetimes τ1 = (2-4.5 ps) and τ2 ≈ 230 ps
• Decrease of τ1 when increasing the pump intensity

50 100 150 200 250 300 350 400 0.0 0.5 1.0

OD 1.3 OD 1.8 OD 2.0 OD 2.3 OD 2.8 OD 3.0 OD 3.3

∆T/T time (ps)

Pmol_Long range

Pump/ probe experiment in n-type QQT(CN)4 neat films

• 100

100 200 300 400 500 0.0 0.2 0.4 0.6 0.8 1.0

∆T/T (normalized) Time Delay (ps)

NtypeOD1.8 NtypeOD2.0 NtypeOD2.3 NtypeOD2.8 NtypeOD3.0

• 5

5 10 15 20 25

• 0.12
• 0.09
• 0.06
• 0.03

0.00

∆αd Time Delay (ps)

NfilmOD1.8 NfilmOD2.0 NfilmOD2.3 NfilmOD2.8 NfilmOD3.0

• 0.0206
• 0.0214
• 0.0483
• 0.1084
• 0.0981
• Similarly to the results in solution and in the p-type film, transient

absorption signal exhibits a strong initial absorption bleaching reflecting that pump-induced ground-state depletion dominates the observed dynamics.

• Two characteristic lifetimes τ1 = (1.5-4.5 ps) and τ2 ≈ 140 ps
• Decrease of τ1 when increasing the pump intensity (similar to p-type film)
• τ2 faster in the p-type than in the n-type film (230 ps)