Raman Spectroscopy Technology

Enwave Optronics, Inc.

ANIMEGH MANDAL
SINSIL INTERNATIONAL
KOLKATA
09331043269
2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
1
Optronics, Inc.

Wavelength Shifted Light Scattering

from
Matter
The Raman effect
was
theoretically predicted by
Smekal in 1923

The first experimental

observation was made by Sir
C. V. Raman in 1928
C. V. Raman won the Nobel
Prize in Physics in 1930 for
Less than one in a
this discovery
millions of photons
scattered off matter
will experience color
(wavelength) changes
reflecting the

Outline
1. The Science & Technology of Raman
Spectroscopy
2. Applications of Raman spectroscopy
3. Enwaves Raman Instrument
Products

2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
3
Optronics, Inc.

The Science and

technology of Raman
Spectroscopy

2012 This document may not be reproduced or distributed in any form without the written permission of Enwave 4
Optronics, Inc.

Overview: Raman Spectroscopy

Ramanspectroscopyisavibrationalspectroscopyformolecularanalysis
RamanandIRarethemostcommonvibrationalspectroscopiesfor
assessingmolecularspeciesandsymmetryinformation
Ramanspectroscopyisbasedoninelastic(energychanging)scatteringof
amonochromaticexcitationsource
Usualspectralrangeofinterest:2004000cm 1
RamanhascomplementaryselectionrulestoIRspectroscopy
SomevibrationalmodesarebothIRandRamanactive
Greatformanyrealworldsampleanalysis
Minimalsamplepreparation(gas,liquid,solid)
Compatiblewithwetsamplesandnormalambientcondition
Theworstchallenge(interference)usuallycomesfromsamplefluorescence

Raman Technology Today

Raman spectroscopy is becoming one of the most
attractive techniques and a standard equipment in
laboratories
Raman provide information for easy fingerprinting
identification of substances and is a valuable
qualitative/quantitative tool in many areas:
Pharmaceutical industry
Petrochemical, industrial chemical, polymers
Material science
Semiconductors, photovoltaic materials
Life science (human, animal and plants : biology,
biochemistry, biophysics,
virus, tumor...)
Geology and mineralogy, gemology
Forensics sciences
Art, archeology, paints, pigment, stained-glass windows,
earthenware, potteries, inks...
The technique has become friendly of use and the costs

Light-Matter Interaction and

Optical Spectroscopy as Analytical
ToolsLight can
When Light Meets Matter,

Transmission
experience:
Part or whole energy pass through the substance
Reflection
Bounce back from the surface of the substance
Absorption
Part or the whole energy can be absorbed into the substance
system
(NIR, Mid IR, UV/Visible spectroscopy). Energy can be
released from
substances after absorption as re-emitted lights
(Fluorescence/Emission spectroscopy)
Scattering
Light can be scattered off matter in all directions with or without
energy
changes (Raman spectroscopy)

and gain useful information about matter

7

Components of Raman Spectroscopy

Instrument

A modern Raman instrument is made up of 4 basic

components:
1.Excitation source: An intense monochromatic
light source is ideal for Raman spectroscopy. A
frequency stabilized narrow line width laser is the
best choice
2.Sampling probe with Rayleigh rejection filter
3.Spectrograph separates the light with different
frequencies and detector that measures the
energy, or intensity, of each component
frequency.
4.Computer System with software for instrument
control, data acquisition, data processing and
analysis.

Components in a Dispersive Raman

Instrumentation

Information from Raman Spectroscopy

Peak intensity yields sample

concentration
Peak positions yields sample composition
Calibration set of sample components
used for chemical analysis for real-time
Chemometrics modeling and predictions

10

Fluorescence as a Raman Interference

Choose appropriate laser excitation to decrease fluorescence
interference

2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
Optronics, Inc.

Important factors for Raman Spectra

Sufficient spectral resolution and coverage (Spatial
resolution)
Spectral coverage for the interested range
Separate spectral peaks narrower than the narrowest anticipated
spectral features of sample

Signal to Noise ratio (S/N)

Adequate S/N to provide high quality of Raman spectrum for analysis

Repeatability

Comparison of Vibrational Spectroscopy

Techniques
Raman
Mid IR
Near IR
Phenomenon

Scattering

Absorption

Absorption

Information

Fundamental
Vibrations
(Fingerprint Detail)
Sharp, well-defined
peaks

Fundamental
Vibrations
(Fingerprint Detail)
Sharp, well-defined
peaks

Overtone/combinat
ion
Broader,
overlapping
More difficult to
interpret

Regions

100-4000 cm-1

4000 to 200 cm-1

12800 ~ 4000 cm-1

Type of Sample
Analyzed

Organics and
Inorganics

Organics and
Inorganics

Organics mainly
Containing C-H, NH, O-H

Sample
Preparation

None, no need

Often KBr Pellet or

ATR
(compression)

None

Sample State

Solid, Liquid,
slurry, paste, gel,
suspension, etc.

Solid, Liquid,
slurry, paste, gel,
suspension, etc.

Gases..very
limited

Solids and liquids

requiring varying
degrees of samples
preparation.
Gasesvery
good

Minimal problem

Interference from

Minimal problem

Sampling Issues

Glass Vials

Gases..very
limited

The Applications of
Raman Spectroscopy

14

Targeted Markets
Pharmaceuticals Forensic
Raman
Surface Enhanced
Raman Spectroscopy
(SERS)

Microwave
Assisted
Synthesis

Homeland
Security

Enwaves Core
Technologies

R & D Labs
Academic
Institutions

Semiconductor
Analyses

Fake & Imitation

Consumer Product
Identification
(China)

Polymer
Industrial
Production
Process Control
control

Enwave Optronics, Inc. (Confidential)

15

Examples of Raman Applications

Art and museum
---- Pigment analysis ; Art Authentication; Archaeometric analysis
of ancient pottery; Art restoration
Biology & Biomedical
----- Dermatological Research; Human skin; SERS analysis of
single living lymphocytes; wheat grain kernels; Teeth; Studies of
transdermal drug transfer; Cancer identification (oral, skin,
breast, cervical, colorectal); Studies of bone (composition,
mechanics, and disease state); Soft dental tissue; Intravascular
atherosclerosis; Studies of the eye (lens, fluids)..
BioTech
---- Analysis of a Batch Fermentation Process
Carbon materials
------ Carbon nanotube; Diamond; DLC; Graphite; Graphene;
Study the effect of boron on the mechanical properties of
diamond
Enwave Optronics, Inc. (Confidential)

16

Raman Applications (Cont.)

Catalysis
---- In Situ Characterisation of Heterogeneous Catalytic
Reactions; Investigation of Surface-Catalyzed NO
Decomposition
Chemical
-----The Formation of Phosphorus Trichloride from
Phosphorus and Chlorine; The Production of Methyl
Chlorosilanes ; Monitoring the Rutile/Anatase Ratio in TiO2
Production ; Headspace Gas Analysis ; Monitoring CaCO3
Polymorph Formation in the Presence of Polymeric Additives
Environmental and Agrochemical
---- Fertilizers; Peticides; Water Contamination

Enwave Optronics, Inc. (Confidential)

17

Raman Applications (Cont.)

Forensic
----- Ink; Forged document investigation; Identification of
controlled drugs and narcotics; Explosive materials; Paint chip
sample; Identifying Drugs of Abuse ; Pigment analysis; Plastics
or textiles to commercial products
Food/ Nutrition Product
----- Oils and Fats; Sugars; Sweeteners; Vitamins and Minerals;
Beverages; Alcohol
Geosciences / Gemology / Mineralogy
---- Geological materials analysis; Jade; Heavy mineral sands;
Sandstone; Chemical Treatment Detection; Gem / Pearl / Coral
Authentication & Identification; ..
Polymer
----- Plastic recycling; Polymorph..
Enwave Optronics, Inc. (Confidential)

18

Raman Applications (Cont.)

Pharmaceuticals
----- Polymorph in Pharmaceuticals; Incoming raw material ID;
active pharmaceutical ingredients and excipients in a tablet; Final
Product Testing..
Petrochemical
Reaction monitoring and process control
---- Microwave Assisted Synthesis; Polymorph Characterization .
Recycling
----- Plastic
Semiconductor
----- Solar cell; Integrated Circuits; silicon stress in microelectronics
SERS
Enwave Optronics, Inc. (Confidential)

19

Mixture in PFA Yube

Enwave Optronics, Inc. (Confidential)

H2O2

Low Concentration Sulfate in Water

I

Y=274.38X, R=0.99986

Peak Area

2.5ppm
5ppm
10ppm
25ppm
50ppm
100ppm

20

40

60

80

100

Concentration (ppm)

960

SO4

980

1000

1020

1040

Water OH
bending
mode

Food:

Alcohol & Liquor

Enwave Optronics, Inc. (Confidential)

Forensic -- Ink

Enwave Optronics, Inc. (Confidential)

Forensic --- Ink

Solar (Silicon)

Excitation
532nm

Enwave Optronics, Inc. (Confidential)

c= 0.43

26

Semiconductor -- Silicon

Silicon Thin Film Measured

with ProRaman-L
1-Second Integration Time
Averaged 30 times

Carbon materials: SWCNT & Graphene

Powder

Enwave Optronics, Inc. (Confidential)

28

Low cost EZRaman-M-785

Models

EZRaman-M

MiniRam

MiniRam III

i-Raman

Manufacture

Enwave

B&W Tek

B&W Tek

B&W Tek

Laser output

~300-400mW

<300mW

Spectral range

A2: 250-2350
A1: 100-2200
B: 100-3300

175-3150

175-3150

H: 175-2700
S: 175-3200

Resolution (cm-1)

A2&A1:
B:

10 @ 912nm

10

H: 3.5 @912nm
S: 4.5 @ 912nm

TE Cooled Linear
Array

TE Cooled Linear
Array

TE Cooled Linear
Array

Pixel number

2048

2048

2048

Pixel size

14200m

14200m

14200m

TE cooling
temperature

14oC

14oC

10oC

Dynamic Range

300:1 (typical)

300:1 (typical)

300:1 (typical)

Readout speed

500KHZ

250KHZ

500KHZ

Integration time

5ms-65535ms

9ms-65,535ms

5ms-65535ms

4.5
6.5

<300mW

Detector
Detector type

Software

TE cooled CCD

BWIQ:
Chemometric
software

Low cost EZRaman-M-785

Models

EZRaman-M

Desktop LPeakseeker

Manufacture

Enwave

RamanSystems

Laser output

~300-400mW

5 to 300

Spectral range

A2: 250-2350
A1: 100-2200
B: 100-3300

200-3000

Resolution (cm-1)

A2&A1:
B:

12

Signal to Noise ratio

250:1

250:1 (at full signal)

Photometric stability

<4% in 12 hours

<4% in 12 hours

Optics

Better

NA=0.22, sample spot

size=0.1 0.3mm

4.5
6.5

Enwave Optronics, Inc. (Confidential)

Low cost EZRaman-N-785

Models

EZRaman-N

PRO-785

innoRam

Manufacture

Enwave

RamanSystems

B&W TEK

Laser output

~300mW

~ 300

<300

Spectral range

A2: 250-2350 / A1:

100-2200
B: 150-3200 / C: 1003100

200-2000
E: 200-3900

H: 65-2500
S: 65-3000

Resolution (cm-1)

A2&A1:
B & C:

6
E: 10

H: 3.5 @912nm
S: 4.0 @912nm

6
7

Signal to Noise
ratio

1000:1 (at full signal)

Photometric
stability

<1% in 12 hours

Wavelength
stability

<1cm-1 in 12 hours

Optics

F/1.6 CCD

NA=0.22, spot size=0.1

0.3mm

Detector
Detector type

TE Cooled, Back-thinned, 2D
Binning CCD

TE cooled CCD

Pixel number

2048

Pixel size

1212m

TE cooling
temperature
Dynamic Range

-20oC

-20oC
30,000:1(min)

Low cost EZRaman-N-785

Models

EZRaman-N

PRAM-1-785

Advantage 785

Manufacture

Enwave

BaySpec

DeltaNu

Laser output

~300mW

100-500mW

120mW

0.2nm typ/0.3nm
max

Laser Bandwidth

Spectral range

A2: 250-2350 / A1: 1002200

B: 150-3200 / C: 1003100

200-3200

200-2000
100-2000

Resolution (cm-1)

A2&A1:
B & C:

5-7cm-1

6
7

Stray light rejection

Optics

0.05%
F/1.6 CCD

Detector
Detector type

TE cooled CCD

TE cooled CCD

Pixel number

2048

Pixel size

14m

TE cooling
temperature

-20oC

Dynamic Range

3000:1 typ

Readout speed

250KHZ

Integration time

0-300sec

Material library

Enwave Optronics, Inc. (Confidential)

>1000 (organic &

Advantages of ENWAVEs Low Cost Raman

Instruments

Enwaves Advantages
v.s.

1.Better laser technology provides higher system

Competitors
Disadvantage

stability and reliability

1.Optics throughput

2.High throughput optics design for higher

2.Linear CCD or backthinned

sensitivity

3.Utilized low noise 2-D CCDs resulting in very low

noise and can take up to 300 second integration time

without increasing much noise. Excellent low pattern
noise performance and eliminate the need to
subtract dark signal and shorten the measurement
time by 2 times

CCD

3.Long measurement time

4.Expensive for performance

4.Smooth spectral response profile result in better

spectral characterization capability and system to
system transferability

5.Accurate

calibration results in better accuracy of

identification and quantification and better spectral
database instrument to instrument transferability

33

Enwaves Raman
Products

34

Introduction to Routine Raman Analyzer

Routine Raman Analyzers are
designed with no moving parts to
ensure the accuracy and reliability
of the analytical results every
time.
Routine Raman Analyzers are
designed for industrial chemical
analysis
requiring
consistent
results instead of the requirement
of academic research laboratories
for one time discovery and
constant changing
needs of
instrument configurations.

Available Excitation
wavelength
532nm/785nm/687nm/
905nm

35

Enwaves Routine Raman Product Lines

Laboratory Raman

Process Raman

EZRaman-N --- Low cost

LabRaman
ProRaman-L --- High Sensitivity

Field Portable Raman

EZRaman-H -- Handheld
EZRaman-I --- High Sensitivity

Affordable Process Raman

--- ProRaman-L Series
High Performance Process
Raman
---ProRaman-I
---ProRaman-W

Sense Microscope

Sense-N --- Low cost

Sense-I/L ---- Cost effective, High
Performance

36
2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
Optronics, Inc.

Laboratory Portable Raman Instruments

EZRaman-N Low cost Raman instrument

ProRaman-L High performance Raman instrument

37
2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
Optronics, Inc.

EZRaman-N-785/532
Feature
Frequency Stabilized narrow
Linewidth laser
F/1.6 CCD spectrograph
CCD Cooled to 25 C from ambient
temperature
High Throughput high Rayleigh
rejection Fiber Probe
Measure 50ppm Nitrate in
15seconds for S/N>3

38
2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
Optronics, Inc.

EZRaman-N Series
Raman Spectrum of CNT powder

EZRaman-N-532
39
2012 This document may not be reproduced or distributed in any form without the written permission of Enwave
Optronics, Inc.

Pro Raman Analyzer

SYSTEM FEATURES
High Sensitivity Raman System for
Laboratory & Industrial Process
Monitoring
High Power, NIR, Frequency
Stabilized, Narrow Linewidth
Excitation Source
CCD Cooled to 60 C

Available Excitation
wavelength
532nm/ 785nm

Averaged Optical Resolution ~6

cm-1, Spectral Coverage: ~250 to
2,350 cm-1
HRP-8 High Throughput Laboratory
Probe (O.D. > 8)
Enwave Optronics, Inc. (Confidential)

Best Performance / Cost

40

Raman
Low Cost Raman Microscope

Sense-N

Sense

High Performance Raman Microscope

Sense-I/L

Industrial research and

development labs
Contaminant identification and
cleaning verification.

Industrial research and

development labs
Contaminant identification and
cleaning verification

Enwave Optronics, Inc.

(Confidential)

41

GasRaman-NOCH1/2 Series

532nm DPSS laser with ~100 mW output power

High Sensitivity CCD spectrograph
Spectral range 250-4200 cm-1
RamanReader-G gas analysis software

Enwave Optronics, Inc.

(Confidential)

42

OEM Raman
Frequency Stabilized Diode
Lasers

OEM Raman Modules; Specialty Raman Products

Enwave Optronics, Inc. (Confidential)

43

Accessories

Microviewer

Precision XYZ Stage

Sample Holder Chamber

Lens Tube

Safety goggles
Fiber Probe
Remote Measurement Lens and Tripod
..

Enwave Optronics, Inc. (Confidential)

44

Thank You for Your

Attention!
Question?

45