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Raman Characterization of Carbon Nanotubes and Carbon Materials: Obtaining Representative Measurements

Presenter: Mark Wall Product Specialist Raman Spectroscopy E-mail: mark.wall@thermofisher.com

Presentation Overview
What is Raman spectroscopy? What can Raman tell you about Carbon? What is involved in a collecting a Raman measurement?

Questions and Answers

Brief Description of Raman Spectroscopy


Raman spectroscopy is a laser light scattering technique
A form of Vibrational Spectroscopy Records vibrations of covalent bonds Provides detailed molecular information Most sensitive to symmetric bonds A good tool for characterizing molecular backbones Sensitive to even slight changes in bond angle or strength Highly sensitive to geometric structure Highly sensitive to stresses in molecules or modifications which impact bond properties

R H
3

H
R

What Can Raman Tell You About Carbon?


First, Raman can identify it and distinguish it from other materials

The Diamond spectrum is very similar to that of crystalline Silicon and Germanium except that the lighter weight Carbon bonds vibrate at higher frequency.

What Can Raman Tell You About Carbon?


Raman easily differentiates different allotropes
D band may represent sp3 bonds (tetrahedral configurations) or it may represent disorder in hybridized sp2 bonds (graphene edge configurations) G band represents sp2 bonds (planar configurations) These two bands form the core of Raman carbon spectrum
G band known as the graphite or tangential band D band known as the disorder, defect, or diamond band.

Silicon

Other Forms of Carbon Nanocrystalline Diamond


Raman is very sensitive to morphology differences
Nanocrystalline diamond has a slightly different structure to bulk diamond due to the increased surface area on the nanocrystals The effect on the Raman spectrum is dramatic

Other Forms of Carbon Diamond like Carbon (DLC)


The band position shows us that this Diamond like Carbon film probably has both sp2 and sp3 carbon

Other Forms of Carbon Fullerenes

Raman tells us that C60 bonds are much more uniform than C70
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Other Forms of Carbon Graphene


Graphene consists of the single layer units that make up graphite

G'

Other Forms of Carbon Graphene


Graphene Graphite Graphene

Graphite

Examination of G' band is revealing


Graphene has one primary mode Multilayer Graphite exhibits multiple modes

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Other Forms of Carbon Graphene Layer Thickness

1587.94

Double Layer Single Layer

1581.72

1584.16

Graphite

OMNIC

Raman Spectroscopy Software

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1590 1580 Raman shift (cm-1)

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Wang,Hui; Cao,Xuewei; Feng,Min; and Lan,Guoxian

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Other Forms of Carbon Graphene Layer Thickness


Triple Layer

Double Layer Single Layer

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Other Forms of Carbon Graphene Layer Thickness

750 700 650 600 550 500 450

In t

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Multi Layer

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Three Layer

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Two Layer
In t

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Single Layer

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Other Forms of Carbon Graphene Layer Thickness


2D

I2D/IG= 2

Single Layer Graphene

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Other Forms of Carbon Carbon Nanotubes (CNT)


Single-wall Carbon Nanotubes (SWCNT)
Represent a rolled up sheet of graphene in the form of a tube

Graphene

SWCNT

Multi-wall Carbon Nanotubes (MWCNT)


Consist of concentric nanotubes

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Other Forms of Carbon Carbon Nanotubes (CNT)

2D

G D

RBM

Single-Walled Carbon Nanotubes (SWCNT) introduce a new mode


Radial Breathing Modes (RBM) Characteristic of SWCNT
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Other Forms of Carbon SWCNTs

RBM Frequency correlates to tube diameter


Theoretical calculation is diameter (nm) = 248/(RBM frequency cm -1) In practice, exact RBM frequency can be shifted by other factors so it is better used for relative comparisons
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Other Forms of Carbon SWCNTs


Red Semiconducting and Metallic Mix Blue Semiconducting only

iTOLA

Metallic and Semiconducting properties


SWCNTs can have either semiconducting or metallic properties depending on the chirality of the tube. Differences are less pronounced, but relative comparisons can be made
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Other Forms of Carbon Carbon Nanotubes (CNT)


MWCNTs
Do not exhibit RBM modes Typically have a higher D/G ratio than SWCNTs

G D

RBM

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Other Forms of Carbon MWCNTs


Collection of MWCNTs ranging in diameter from <8 nm to >50 nm

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Raman Measurements Sample Preparation


Raman samples materials neat under atmosphere
This means there is relatively little sample preparation

Samples typically run under a microscope


Loose powders can be compressed between two slides CNTs are often cast onto slides in a surfactant matrix Films are run in their native state

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CNT Sample Preparation for Raman Characterization


Raw CNTs light and fluffy consistency poses a challenge
Excitation laser is focused to a spot Analytical or Scattering Volume Fluffy nature means very few CNTs in the analytical volume

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CNT Sample Preparation for Raman Characterization


Light compression of raw CNT
Compacts sample to increase the density of CNTs

Take small sample from bag

Transfer sample to slide

Place second slide over sample

Apply pressure to top slide

Remove top slide

CNT ready for measurement

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Raman Measurements Laser Sensitivity


Many Carbon materials are sensitive to laser power at sample
Spectral changes may represent different excited modes at different laser power

1.0 mW 2.0 mW 3.0 mW

with increasing laser power

with increasing laser power

MWCNTs excited at 3 different laser powers peak height normalized


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Raman Measurements Laser Sensitivity


Many Carbon materials are sensitive to laser power at sample
Spectral changes may represent different excited modes at different laser power

G band of SWCNTs excited at different laser powers peak height normalized


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Raman Measurements Laser Sensitivity


Many Carbon materials are sensitive to laser power at sample
In some cases spectral changes may indicate damage to the material

Decomposition products

Thermal baseline

C60 excited over a range of laser power peak height not normalized
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Laser Power Regulation


Precise and fine laser power control at sample!

Legend: Zone A: The Laser Power Regulator controls the laser power reaching the sample to ensure reproducible results. Zone B: As the laser power declines over its lifetime, measurements become non-reproducible on instruments lacking a Laser Power Regulator. Zone C: Beyond the expected laser lifetime. The Raman instrument can still be used reproducibly at lower power levels.

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Raman Measurements Selection of Excitation Laser


Many CNT bands are subject to resonance enhancement
RBM bands and G band in particular are highly resonant

2D

D
Blowup of RBM bands

RBM

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Raman Measurements Types of Measurements


Microscope measurements
Single point collection Mapping

Bulk measurements
Only applicable if sample is densely packed Sometimes this applicable to liquid suspensions Even investigation of single CNTs

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Single Point Raman measurements - Spectrum Variability

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Multipoint Measurements - Raman Mapping

532nm Excitation contour map is based upon G band intensity


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Multipoint Measurements - Raman Mapping

260 cm-1
P os i ti on (m i c rom eters )=-321 m ;-206 m Num b er: 473

150 cm-1
Pos ition (mic rometers )=-71 m ;-176 m Numbe r: 753

Diameter (nm) = 248/RBM(cm-1)

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Raman s h ift (c m-1)

1nm SWCNT
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1.7nm SWCNT

Calculating a Representative Raman Spectrum Chemical Map

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Ram an s h i ft (c m -1)

Average Spectrum = RamanSpectra / total number of spectra


417 s pec t ra: A verage 417 s pec t ra: V ari anc e

Average Variance

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Ram an s h i ft (c m -1)

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Rapid Representative Raman Measurements


Alternative method for obtaining a representative Raman spectrum
Based upon rastering the laser rapidly across sample (100 hz) Collect Raman scatter continuously during multiple passes of the laser across the sample Raman spectrum indicative of the area traversed by the laser

Variable Dynamic Point Sampling (VDPS)

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Comparison of Average Map Spectrum to VDPS

VDPS Map

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Raman s h ift (c m-1)

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How Raman is Applied Industrial Applications


Measurements of consistency of product
DLC films Purity of CNTs Incoming QC Outgoing QC
SWCNT with a peak near 313 cm -1

Sm

Sometimes the range of variation is important


Distribution mapping

SWCNT with a peak near 276 cm -1

Diameter

Verifying that processing is not altering the material


Functionalization steps

SWCNT with a peak near 247 cm-1

Lg
SWCNT with a peak near 239 cm-1

Distribution of SWCNTs within MWCNT matrix


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How Raman is Applied Research Applications


Quick characterization of materials before utilization
Formation of CNTs pretty well established as this time Still useful for quick checking of formation process before moving on Current research focuses on purification, separation, and integration within end commercial materials and devices.

G'

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Conclusions
Raman is an extremely powerful tool for characterizing Carbon nanomaterials Raman sampling is easy and faster than many other techniques Raman has a role to play in both research and QC The limits to the information that Raman can provide on Carbon materials are still unfolding
As this field continues to develop, the role of Raman is most likely going to increase

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Suggestions for Further Learning


Additional reading on interpretation of Raman spectra of CNTs:
Raman spectroscopy of carbon nanotubes M.S. Dresselhaus, G. Dresselhaus, R. Saito, A. Jorio 10.1016/j.physrep.2004.10.0006

Additional reading on sorting CNTs:


Sorting carbon nanotubes by electronic structure using density differentiation M.S. Arnold, A.A. Green, J.F. Hulvat, S.I. Stupp, M.C. Hersam nature nanotechnology, vol 1, October 2006, pages 60-65

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Questions?
Thank You For Your Time! Email survey Your feedback is important Presentation slides and recording will be available on the Materials Today website Additional Thermo Fisher Scientific Raman webinars
www.thermoscientific.com/ramanwebinars

Any additional questions?


E-mail: mark.wall@thermofisher.com Please include subject line: Raman CNT Webinar Request

For product information please see:


http://www.thermoscientific.com/dxr
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Mark Wall