NanoComplexNanoComplex Materials GroupMaterials Group

Laboratory of Emergent Functional States Laboratory of Emergent Functional States in in NanocomplexNanocomplex MatterMatter

AlexandrosAlexandros LappasLappas

ObjectivesObjectivesTo develop multiTo develop multi--functional inorganic/organic materials functional inorganic/organic materials and their hybrid and their hybrid nanostructurednanostructured derivativesderivatives

To understand how structure, dynamics determine To understand how structure, dynamics determine functionalityfunctionality

Design & Syntheses-Optimization

Structure – Reactivityin Atomic Scale

Physical Properties-Functionality

Materials for new Technologies

Who is Who in the GroupWho is Who in the GroupInorganic MatterInorganic Matter A. A. LappasLappas Chemical Chemical

PhysicsPhysics Structure & MagnetismStructure & Magnetism

Soft MatterSoft Matter

C. Panagopoulos C. Panagopoulos Solid State Solid State PhysicsPhysics SuperconductivitySuperconductivity

I. I. AndroulakisAndroulakis Materials Materials ChemistryChemistry ThermoelectricityThermoelectricity

S.H. S.H. AnastasiadisAnastasiadis Chemical Chemical EngineeringEngineering Surfaces & InterfacesSurfaces & Interfaces

K. K. ChrissopoulouChrissopoulou Polymer Polymer PhysicsPhysics Structure & DynamicsStructure & Dynamics

M. M. VamvakakiVamvakaki ChemistryChemistry Organic SynthesesOrganic Syntheses

I.A. I.A. BitsanisBitsanis Chemical Chemical EngineeringEngineering TheoryTheory

International Collaborators:Cornell Univ., UCL, IRC Cambridge, Kyoto Univ., Institute Josef-Stefan, NNL-Lécce, CEMES-Toulouse

Funding - Major Sources:GSRT, NATO SfP, EC

What does it Involve

Organic MaterialOrganic Material

Inorganic SolidInorganic Solid

Hybrid nanophase material,novel properties

Functional molecular designAmphilicity & self-assemblyResponsivenessProcessability & mechanical properties

Low-dimensional phenomena Confinement effects Interface dominated behavior

Magneto-electronic activityOpto-electronic behaviorSuperconductivityCatalytic properties

Actuators, Sensors & BiosensorsEnergy Storage & TransferInformation StorageAir/Space TransportationEnvironmental SecurityControlled Drug DeliveryLabelling for Biomedical Imaging

Soft MatterSoft Matter

Polymer Surfaces Polymer Surfaces –– Interfaces and Thin FilmsInterfaces and Thin Films

Responsive MaterialsResponsive Materials and Material Surfacesand Material Surfaces

Functional Crystals for Polymer Functional Crystals for Polymer

NanocompositesNanocomposites

Inorganic MatterInorganic Matter

Ceramics for Extreme ConditionsCeramics for Extreme Conditions

Exploit UltraExploit Ultra--fast Dynamical Phenomenafast Dynamical Phenomena

Tailored Hybrid Tailored Hybrid NanocrystalsNanocrystals

Tune Tune ee-- Correlations via Bonding & StructureCorrelations via Bonding & Structure

Other Research TopicsOther Research TopicsOrganic DominatedOrganic Dominated

–– Polymer Surfaces Polymer Surfaces –– Interfaces and Thin FilmsInterfaces and Thin Films–– Block Copolymers and Block Copolymers and HomopolymerHomopolymer / Copolymer Blends/ Copolymer Blends–– Responsive MaterialsResponsive Materials and Material Surfacesand Material Surfaces–– Configuration and Responsiveness of Adsorbed and Anchored ChainsConfiguration and Responsiveness of Adsorbed and Anchored Chains–– AmphiphilicAmphiphilic Block Copolymers and Block Copolymers and PolyampholytesPolyampholytes–– Dynamics of Dynamics of NanoNano--Confined FluidsConfined Fluids–– Novel Sensors and BiosensorsNovel Sensors and Biosensors

Inorganic DominatedInorganic Dominated–– LowLow--dimensional Materialsdimensional Materials–– Functional Crystals in Polymer Functional Crystals in Polymer NanocompositesNanocomposites–– Magnetic Phase Control by Molecular EntitiesMagnetic Phase Control by Molecular Entities–– External Stimuli and MixedExternal Stimuli and Mixed--valentvalent NanostructuredNanostructured FrameworksFrameworks–– Directed Assembly of MagnetoDirected Assembly of Magneto--optical optical NanocrystalsNanocrystals

Interface DominatedInterface Dominated–– Influencing the Miscibility in Polymer / Layered Silicate Influencing the Miscibility in Polymer / Layered Silicate NanocompositesNanocomposites–– Synthesis of Metallic and Magnetic Synthesis of Metallic and Magnetic NanoparticlesNanoparticles within Polymer Matriceswithin Polymer Matrices–– Light Amplification and Random Lasing in Hybrid NanostructuresLight Amplification and Random Lasing in Hybrid Nanostructures

TheoryTheory–– Hierarchical Modeling of Complex Hierarchical Modeling of Complex SupramolecularSupramolecular StructuresStructures

Facilities and Methods in the GroupFacilities and Methods in the GroupIESLIESL InstrumentationInstrumentation

–– XX--ray ray diffractometer/reflectometerdiffractometer/reflectometer–– SmallSmall--angle Xangle X--ray scatteringray scattering–– Interfacial Interfacial TensiometerTensiometer–– Differential Scanning CalorimeterDifferential Scanning Calorimeter–– FluorimeterFluorimeter–– RheometerRheometer–– Dynamic Light ScatteringDynamic Light Scattering–– ThermogravimetricThermogravimetric AnalyzerAnalyzer–– HighHigh--Pressure, variable T platformPressure, variable T platform–– Magnetometer (T=2Magnetometer (T=2--320 K)320 K)–– ((Magneto)transportMagneto)transport (T=2(T=2--320 K)320 K)–– FTIRFTIR–– Glove box (anaerobic techniques)Glove box (anaerobic techniques)–– HighHigh--T furnacesT furnaces–– Laser facility

UoCUoC InstrumentationInstrumentation–– AFM (Physics)AFM (Physics)–– High resolution XRD (Physics)High resolution XRD (Physics)–– NMR (Chemistry)NMR (Chemistry)–– ConfocalConfocal Microscopy (Chemistry)Microscopy (Chemistry)–– TEM, SEM (Biology)TEM, SEM (Biology)–– Mechanical properties (Materials)Mechanical properties (Materials)–– UV/UV/VisVis, , SECSEC (Materials)(Materials)

AccessAccess to Facilitiesto Facilities–– SANS & Neutron ReflectivitySANS & Neutron Reflectivity–– Neutron DiffractionNeutron Diffraction–– MuonMuon Spin Relaxation/ResonanceSpin Relaxation/Resonance–– Synchrotron XSynchrotron X--ray Diffractionray Diffraction–– QuasiQuasi--elastic Neutron Scatteringelastic Neutron Scattering–– Electron Spin ResonanceElectron Spin Resonance–– SQUID MagnetometerSQUID Magnetometer

Laser facility

Responsive Polymer SurfacesResponsive Polymer Surfaces

Air Water

Air Water

Exposure to Water Vapor

Smart Polymer SurfacesSmart Polymer Surfaces [Anastasiadis, et al., [Anastasiadis, et al., NatureNature 36, 1994 (2003)]36, 1994 (2003)]““Responsive SurfacesResponsive Surfaces””, Research News, , Research News, Nature MaterialsNature Materials 22, 206 (2003), 206 (2003)

Air

Air

Polymer Polymer NanocompositesNanocomposites

Clusters(0-D)

Layers(2-D)

Rods(1-D)

Network(3-D)

NanocompositesNanocomposites vs.vs. CompositesComposites

Length ScaleLength Scale–– NanometerNanometer--size particles/phasessize particles/phases–– ……as opposed to much larger reinforcing as opposed to much larger reinforcing

elements/phaseselements/phases

Interfacial Interfacial ““VolumeVolume””–– Materials dominated by interfacial behaviorMaterials dominated by interfacial behavior–– ……as opposed to weighted average of bulk as opposed to weighted average of bulk

propertiesproperties

InteractionsInteractions–– Molecular InteractionsMolecular Interactions–– …… as opposed to physical reinforcementas opposed to physical reinforcement

CERAMIC THERMAL BARRIER COATINGSCERAMIC THERMAL BARRIER COATINGSLaser Materials (Laser Materials (PLDPLD) Processing) Processing

Opportunities in air and space transportation(Launchers, Human Space Flight, Satellite Protection)

Beam

DYNAMICAL ASPECTS OF SPINDYNAMICAL ASPECTS OF SPIN--LATTICE LATTICE COUPLINGCOUPLING

TimeTime--Resolved Studies Resolved Studies byby UltraUltra--fast Laser Lightfast Laser LightH Applied Field

Ferromagnet

Antiferromagnet

Opportunities in fast photo-responsive electronics. (e.g. exchange bias devices)

Probe the magnetisationdynamics (fs t-scale)

Beam

Shell (Co/Ru, Co/Cr, Fe/Cr)

Core, RP orpyrochlore

a) Growth of core/shell bi-magnetic nanocrystals

1

2

Formation of dimer by annealing

Core (CdSe, CdTe, ZnSe)

Asymmetric Shell (CdS, CdSe, ZnO)

Growth of metal or metal oxide tip (Au, FePt3, Fe2O3..)

Starting nanocrystal

Au shell growth

1

b) Growth of nanocrystal dimers

2

HYBRID NANOCRYSTALSHYBRID NANOCRYSTALSTuning Properties Tuning Properties viavia Architecture Architecture

Opportunities in opto- magneto- electronic applications(Colossal Magnetoresistance, Exchange-bias, Photoluminescence)

‘Low-temperature’intercalation of

non-oxidicmaterials

SuperconductorsSuperconductorsSuperconductors

a

cb Li+ @

1-D vacant channels

3.

Mo2SbS2

‘High-temperature’ solid-state reactions

Reduced Reduced Reduced Dimensionality Dimensionality Dimensionality ---FrustrationFrustrationFrustration

1.

SrCu2(BO3)2

Tuning Bonding & Structure in Tuning Bonding & Structure in Correlated Electronic SystemsCorrelated Electronic Systems

TT –– [[xx] ] –– PP

Tailor quantum mechanical ground statesTailor quantum mechanical ground states

‘Soft’ syntheses routes to

molecular solids

MII[N(CN)2]2

MagnetsMagnetsMagnets

2.

Response of unpaired Response of unpaired ee-- assembliesassemblies

Magnetic phase control Magnetic phase control by molecular entitiesby molecular entities

[1] A. Lappas et al, PRB 2002, 66, 14428-8 [2] A. Lappas et al, PRB 2003, 67, 144406-8