Nanochemistry lab:Production and nanoscale characterization

of new materials

Andrea Liscio

COFFEE TALKS @ ISOF

2012, July 2nd

COFFEE TALKS @ ISOF

Project Management Future?

Mophological-electronic characterization of supramolecular structures

Donor-acceptor blends, dielectrics for OFET

Scanning Probe Microscopies(AFM, EFM, KPFM)

Tip-sample interactionsWork Function, HOMO-LUMO

Charge injection(CNR ISOF, Bologna)

Physico-chemical characterization of Surfaces and Interfaces

Advanced Electron SpectroscopiesElectronic correlation in solid state physics

(CNR IMAI-IMIP-ISC, Montelibretti)

COFFEE TALKS @ ISOF

Pre-ISOF years Surface and interface electronic states (2D systems)

Exponential decay

Surface statesMatching the two behaviours

Bloch electrons

Surface crystallographic quality: LEED, RHEELSSurface dielectric behaviours: REELS, ILEEDElectronic surface states: UPS, XPS, AugerElectron density: (e,2e), (, +e), (,2e)

Surface: Bulk-vacuum interface

COFFEE TALKS @ ISOF

Pre-ISOF years Surface and interface electronic states (2D systems)

0.0 0.5 1.0 1.5 2.0-20-18-16-14-12-10-8-6-4-202

E B (eV

)

q// (Å-1)

3

2

1

L

•

Reconstruction of the electronic bands at surface•

Direct measurement of the

surface momentum density:

2ke

Electron wavefunction “deformation” due to the presence of adsorbate

molecules at surface

COFFEE TALKS @ ISOF

ISOF years Scanning Probe Microscopies (AFM, EFM, KPFM...)

V. Palermo, M. Palma and P. Samorì,

Adv. Mater. (Review Article) 2006,

18, 145-164A. Liscio, V. Palermo

and

P. Samorì, Acc. Chem. Res. 2010, 43, 541-550

AFM setup

• Metals • Semiconductors • Thin insulators

Morphology &Work Function (charge density)simultaneously

ISOF years Scanning Probe Microscopies (AFM, EFM, KPFM...)

Fully description of the SPM measurement

• Theoretical description of tip-sample interaction,

• Quantitative definition of the lateral resolution: effective area

• Quantitative analysis of the acquired image:

Artifacts

Roughnesss

Surface Potential

Charge density

Key point: The measured objects may be smaller than the size of the used probe

COFFEE TALKS @ ISOF

Transfer function representation

zrW

zrrzrr

zr

,,

lim,//

2////

0,//////

surface

meas zdzrSPzrrrdrSP0

//0//////// ,,

E electric fieldW electrostatic energy

Liscio

et

al., Adv. Funct. Mater. 16, (2006), 1407,

Liscio et al., Adv. Funct. Mater. 18,

(2008),

907,

Liscio et al., J. Phys. Chem. C 112, (2008), 173698,

Liscio et al., Acc. Chem. Res. 43, (2010), 541, Liscio et al., Small 7, (2011), 634

?Real Potential Image Measured Potential Image

COFFEE TALKS @ ISOF

COFFEE TALKS @ ISOF

Quasi 1D-systems:P3HT nanofibres on HOPG

Merlo

J.A. et

al., J. Phys. Chem. 108

(2004), 19169

Poly-3-hexylthiophene (P3HT)

200 nm 200 nm 200 nm

Topography Measured KPFM Simulated

KPFM

Z range = 10 nm Z range = 180 mV Z range = 180 mV

-1 0 1 2 3 4 5 6 7-200

-150

-100

-50

0

50

SP

(mV)

length (m)

1 m 1 m

A. Liscio, G. De Luca, F. Nolde, V. Palermo, K. Müllen, P. Samorì,

JACS 2008, 130, 780-781

Z range = 60 mV

N

O

O

N

O

O

Acceptor (PDI)

AFM KPFM (DARK)

Z range = 40 nm

S

C6H13

* *n

Donor (P3HT)

Photovoltaic activity occurring between PDI and P3HT

Z range = 60 mV

1 m

KPFM (LIGHT)

A A D

COFFEE TALKS @ ISOF

COFFEE TALKS @ ISOF

A. Liscio, G. De Luca, F. Nolde, V. Palermo, K. Müllen, P. Samorì,

JACS 2008, 130, 780-781

Photovoltaic activity occurring between PDI and P3HT

A A D

A

D

A

D

Photo-induced charges at interface = ca

103

electrons / μm2

VdQ

COFFEE TALKS @ ISOF

Present work in ISOF

Project Manager activities in an ITN project:

Technical/administrative skills:

• finance,

• time budgeting,

• reporting.

Scientific skills:

• interdisciplinary,

• intra-node coordination,

• inter-node coordination.

COFFEE TALKS @ ISOF

GENIUS will offer a top-quality environment for multidisciplinary training

and

Transfer of Knowledge (ToK)

in a very wide spectrum of techniques including:

• organic and supramolecular synthesis,

• nanofabrication techniques to self-assemble the GOHs in solution and on surfaces,

• SPM characterization of physico-chemical properties of the GOHs,

• new computational techniques to model graphenic systems,

• steady-state and time-resolved spectroscopies both in solution and solid state,

• fabrication and testing of graphene-based devices,

• development of new composites for electronics and consumer products.

Aim of the project

COFFEE TALKS @ ISOF

ISOF-CNRSelf-assembly of graphene-based materials, electrical characterization at nanoscale by SPM

UCAMNanomaterials and Spectroscopy(Raman)

UCLOptoelectronics and nano-optics

UBERSurface characterisation (STM, STS, XPS, UPS)

BASFSynthesis and electronics

MPGOrganic synthesis

UMONSMolecular mechanics/dynamics and quantum chemical calculations

UdSSelf-assembly, nanoprobes and nanofabrication of nanodevices

Partners

COFFEE TALKS @ ISOF

ISOF UCL

UMONS

UdS

UCAM

MPG

BASF

UBER

Networking

Molecular design Molecular synthesis

Devices

Physico-chemical characterization

COFFEE TALKS @ ISOF

Nanochemisty lab (ISOF)

Main activities• Graphene oxide single layer• Graphite exfoliation• Graphene-organic hybrid systems• Boron nitride exfoliation

COFFEE TALKS @ ISOF

Zhen Yuan Xia(ER)

HOPG exfoliation in solution

Sonication

in DMF Electrochemical oxidation(0.5 M H2

SO4

, 0.5 h)Chemical oxidation(H2

SO4

, KMnO4

)

Studies of the mechanismsperformed by• OM• AFM• SEM

COFFEE TALKS @ ISOF

Andrea Schlierf(ESR)

Graphite exfoliation in solution using small molecules

centrifugation + excess dye removal

Exfoliation and suspension of graphene

Mas

s co

ncen

tratio

n [m

g/m

L]

Sonication time [hrs]

CompositionRAMAN

% S

ingl

e sh

eets

Morphology AFM TEM

P S 2

PS2

1m

PS1 PS2 PS3 PS4

COFFEE TALKS @ ISOF

Konstantinos K. Agalou(ESR)

Boron nitride exfoliation

1. Powder 2. Solution in IPA 3. Centrifugation

AFM

200 nm

4. Deposition on Si substrate

profile

Multi-layer: 2 nm

Single layer: ca 0.5 nm

COFFEE TALKS @ ISOF

BOLOGNA Dr. Vincenzo PalermoDr. Emanuele Treossi

Networking & Aknowledgments

Graphene-Organic SuPramolEcular functionaL composites

www.gospel-network.eu/

www.genius-network.eu/

www.graphene-flagship.eu/

Marie Curie RTN Threadmil (2006-2010)Marie Curie IEF Hesperus (2008-2010)Marie Curie ITN Superior (2009-2012)

NanoSci-E+ project SENSORS (2009-2011)

COFFEE TALKS @ ISOF

Collaborations

S

S

S

S

HN

O

SiEtO

EtOOEt

GO +

GOT4T4

Chemical functionalization of GO

Direct visualization of polymeric nanocarriers

electrostatically

loaded with porphyrin

photosensitizers

Plasmonic: direct visualization of Rabi splitting

Casimir effect: Patches influence

AFM KPFM

Size: 1.28 x 1.28 μm2