Diagnostic and analytical techniques for advanced materials and nanostructures

Michele Muccini Istitute for Nanostructure Materials

CNR Research Area Roma 1, Montelibretti

michele.muccini@cnr.it

2

q  GlimpseonCNRResearchArea-Roma1researchinfrastructure

Outline

q  Exsitucharacteriza<on&diagnos<ctechniquesØ  SEM-EDSØ  Auger&X-rayPhotoelectronSpectroscopyØ  CombineduseofSEM,EDS,XPSØ  RamanandIRSpectroscopyØ  SPMØ  LaserScanningSpectroscopy

q  Poten<alandperspec<ves

3

4

www.mlib.cnr.it

700employees37,000sqmtechnologicalinfrastructure’sarea.

Duetoitswideversa<lity,SEMislargelyusedtoinves<gatethemicroandnano-morphological-structural-chemicalfeaturesandbehaviourofawidepanoramaofmaterialswithalargeindustrialuseorhightechnologicalinterest.

Morphological investigation of organic nanostructured

materials: lipid nanoparticles for drug delivery (Bondì)

ScanningElectronMicroscopy(SEM)

Processevalua>onofmicroelectroniccomponentsproduc>on

Structural and morphological study of thin films multi-layered structures for electronic devices

Micro-patterning: study of ablation defects

Investigation of the deposition processes of TiN protective films

TiN 240 nm

SiO2

Si

Optimisation of the ITO deposition

parameters

Produc>onandanalysisofepoxyresinsforthepackagingofavionicsystemcomponents

Dispersion of graphene platelets

The morphological investigation has guided the synthesis and the dispersion procedures of nanostructures improving: •  the electrical conductivity of 1100 %; •  the thermal conductivity of 470 %.

Dispersion of CNTs e AuNPs

Dispersion of CNTs

Cross sections of Ni-based superalloys (Nimonic 80 A, MM002).

SEM images and EDS spectra describe the protective oxide

multilayered structure.

FailureanalysisofjetengineturbinebladesDegrada<onmechanismsiden<fied

SEM-EDSmorphologicalandchemicalanalysis

Auger & X-ray Photoelectron Spectroscopy

B.E. Ef K.E. E3 E2 E1

hν

e-

BE = hν – KE – φspec

e-

KE123 = KE1 – KE2 – KE*3

VB SPECTRUM

CORE LEVEL SPECTRUM (XPS)

AUGER SPECTRUM (AES) Ø  SURFACE CHEMICAL COMPOSITION (1-10 nm)

Ø  CHEMICAL IMAGING

Ø  SURFACE CHEMICAL COMPOSITION (1-10 nm)

Ø  CHEMICAL IMAGING

Ag MNN image

Au NOO image

Ar+ Ø  ION SPUTTERING

Electron-gun

C 1s GRAPH.

C 1s CARB.

Si 2p

TBC deposited on a jet engine turbine blade (25.5 wt% CeO2–2.5 Y2O3 – ZrO2) after a thermal cycling test. The coating fracture has been caused by impurities (Si, Al, Na) segregation phenomena inducing also a columnar growth.

Combined XPS and SEM analysis allows: •  to optimise the production processes; •  to evaluate the durability and reliability •  to prevent catastrophic failure

Si 2p

70 80 90 100 110 120 1300

1x105

TBC 1 TBC 2 TBC 3 TBC 4

Phot

oem

issi

on in

tens

ity (a

u)

Binding energy (BE)

2

4

3

1

XPSspectraofTBCsproducedbyadop>ngdifferentdeposi>onparameters(energyregionAl2p,Si2p,Fe3s,Ce4d)

Al2p

Fe3sSi2p

Ce4d

Coa>ngsofturbinebladesandcombus>onchamberinjetengines

Renishaw2000µ-Ramanwith a Pel<er cooledCCD camera inconjunc<onwithaLeicaop>calmicroscopeandlaserexcita<on

Raman spectroscopy is a scaTering technique based on theinelas<cscaTeringofincidentradia<onthroughitsinterac<onwithvibra<ngmolecules(Ramaneffect).

The vibra<on modes of a substancedependon:Ø massoftheatomsØ bondingforcesØ symmetriesofthemoleculesTherefore, the Raman spectrum of amolecule corresponds to a "fingerprint"withwhichtoiden<fyit.

µ-Ramanspectroscopy

500 1000 1500

100 120 140 160 180 200

R

aman

Inte

nsity

(a.u

.)

Raman Shift (cm-1)

0 1 2 3 4 5151.1

151.2

151.3

151.4

151.5

151.6

151.7

151.8

% Eu

FWHM

Eg p

ositio

n (c

m-1)

Eg FWHM

23

24

25

26

27

28

R

aman

Inte

nsity

(a.u

.)

Raman Shift (cm-1)

TiO2 0.5% Eu 1.0% Eu 2.0% Eu 3.0% Eu 5.0% Eu

G/DandG-/G+ra<osareindicatorsofsamplequalityandconduc<vityofthesample

RadialBreathingMode(RBM)isdirectlyrelatedtothediameterofnanotubes

1800 1600 1400 1200 300 200 1000

5000

10000

15000

20000

25000

D

G-

ChT60 ChT90 ChT99

Ram

an In

tens

ity

Wavenumber/cm-1

G+

RBM

stretching mode in the graphite plane

disorder band

⎟⎟⎠

⎞⎜⎜⎝

⎛ Δ⋅⎟⎠

⎞⎜⎝

⎛−

+=

0112

ωω

υυ

σ G

Molecular self assembly

diamondlikecarbonDLC

Evalua<onofinternalstressofaDLCfilmonaSisubstrate:

Eu-TiO2NCsfunc:onalizedco<on

carbonnanotubes

ATR-FTIRspectroscopyforCulturalHeritage

Inves<ga<onofthecomposi<onofdegrada<onproductsoncopper-basedworksofart.

Analysisofpa<nacomposi<on:ü  Iden<fica<on of degrada<on products on

c o p p e r - b a s e d a l l o y s , a s c o p p e rhydroxyclhoridesandhydroxysulphates

ü  D i s<ngu i s h d eg r ada<on p r odu c t spolymorphs with different chemicalreac<vity(asclinoatacamiteandatacamite)

3600 3400 3200 3000 1000 900 800 700 600

0,00

0,05

0,10

0,15

0,20

+

C uprite+

C linoa tacamite

*

°**

*

*

*

P A -C lig htg reena reaP A -C g reena reaP A -C reda rea

Abs

orba

nce(a.u.)

W avenumber(cm -1)

*

°

°

*A tacamite

° **

*

* °

*

*

3600 3400 3200 3000 1200 1000 800 600

P A -D g reen-blue a reaP A -D reda rea

Abs

orba

nce(a.u.)

W avenumber(cm -1)

Copperhydroxyclhoridedegrada>onproducts

Copperhydroxysulphatedegrada>onproducts

G. Di Carlo et al., Applied Surface Science 421 (2017) 120–127

Adolfo Wildt

SPM

Surface potential

Mechanical properties

Mechanical properties

Electrical properties

Electrical properties

Magnetic properties

Single molecules properties

Topography

Surface Friction

Mechanical properties of soft matter

Time-resolved micro-spectroscopy laboratory

Confocal laser scanning microscope image

PL spectrum PL temporal decay

q  Spatially resolved (<300 nm) q  Energy resolved q  Time resolved (2 ps) q  Temperature 450 – 4,2 K

20 µm

500 525 550 575 600 625 650 675 700

PL in

tens

ity [a

.u.]

Wavelength [nm]

Molecular orientation

Correlation morphology-structure-function in composite systems AFM CLSM Localized PL spectrum

Nature Materials, 4 (2005) 81

18

q SEM, XPS, XRD, SPM, RAMAN, FTIR, DTA-TG-DSC, LASERSPECTROSCOPYandOM,allowsthethorough

•  inves<ga<onofdegrada<onphenomena(failureanalysis)ofstructuresandcomponents•  op<miza<onofproduc<onprocesses•  tailoringofthematerialsfinalproper<es

In summaryq The combina<on of different analysis techniques is

essen<alforthedevelopmentofALMTechnology

Aimatin-situprocessmonitoringandmetrology

19

AcknowledgmentsElectron&Op>calMiscroscopyLabIngoRiccucciMessinaPascucci

RamanSpectrocopyLabDeCaroRuani

FTIRSpectrocopyLabDiCarloGiulianiIngo

SPMLabLeoCerriPadele`ValleBrucaleAlbone`

LaserScanningMicro-SpectrocopyLabToffaninBolognesi

SurfaceAnalysisLabKaciulisMezzi

Thankyou!

PECVD–MOCVDLabCascheraToroFederici

XRDLabVeroli

Someoftheprojects@ISMNMlibMIUR-PONPANREXEU-NANORESTARTEU-HERACLESEU-MOSTOPHOSMinDifesa–FABRICSAFEEU-INNOVACONCRETE