New capability of Raman Spectroscopy!!

Latest Imaging
g g Applications
pp for most updated
p
Measurement
 Contents

• High Speed Imaging

• 3-D Raman Imaging NRS-5000 NRS-7000
• Sub-Micron Mapping
• V i
Various S
System
t C fi
Configuration
ti (L(Low wavenumberb
region/High wavenumber resolution measurement)
• Multiple Wavelengths Excitation（Fluorescence
avoidance/Resonance Raman）
g
• Various kinds of Program Supporting
pp g Measurement and
Analysis
 NRS-5000/7000 Specifications and Features

NRS-5000 feature NRS-7000 feature

Standard：532 nm Option：244, 266, 325, 355, 442, 488, 514.5, 633, 785, 1064 nm etc.
Laser
Total: Max. 8 lasers, 9 wavelengths, Automatic switching system
Resolution Standard: 1 cm-1 Standard: 0.7cm-1
Wavenumber 50 - 8000 cm-1 50 - 8000 cm-1
-1 -1
range 10 - 8000 cm (with low wavenumber rmeasurement 5 - 8000 cm (with low wavenumber measurement
(Raman shift) attachment) attachment)

Max. No. of
3 4
mountable grating

Standard detector CCD detector (Option: Max. 2 detectors can be mounted)

Standard function Auto-alignment, Laser light-path auto-alignment, RI, SGI, Wavenumber correction, sensitivity correction

Micro spectral measurement program (Wide spectral

spectral-band
band measurement,
measurement User help function,
function Auto
Auto-fluorescence-correction,
fluorescence correction
Standard software
cosmic-ray removal）, Curve fitting, Validation, Search（Sadtler KnowItAll）

High speed imaging system (SPRIntS), Polarization observation, Differential interference Observation, Simple macro
Option
measurement attachment, Heating-cooling stage, Multi well plate holder, Polarization measurement unit, Fiber optic probe

The routine analysis to the research study in a laboratory can be

implemented by using a NRS-5000/7000.
 High speed imaging(SPRIntS) measurement for
pharmaceutical tablet
<Measurement conditions> excitation wavelength 532 nm measurement time 15 min

Wide area imaging of pharmaceutical tablet (10 mm diam diam.))

• Left: Visual image of tablet,
• Right: Raman spatial distribution of active ingredient in analgesic drug
Measurement screen of High speed imaging
Since the laser always irradiates the sample vertically by using the
recently developed Vertiscan, the Raman image can be obtained without
distortion and losing confocality. Accurate image information can be also
obtained
b i d ffrom XYZ 3 3-D
D iimaging
i d data.

Chase pattern on Si substrate

 Submicron mapping measurement of Si wafer
Raman imaging at submicron scale can be obtained.

Siの応力測定
Si stress measurement
compression
圧縮 tensile
引っ張り

1.5 µm
1 5 m
1.5 Tensile
Compression stress ストレスフリー Tensile stress
Stress free 引っ張り応力
Stress high
圧縮応力

Peak shift
ピークシフト Peak shift
ピークシフト

Compression
521 520.5 519 Stress
Raman shift （cm-1）
1 cm-1-1のピークシフト
1cm Peak shift Equivalent
⇒ 250 of 250 MPa stress
MPaの応力に相当 high

Residual stress measurement at micro region

（Left : topographic image, Right : Raman image for stress
distribution measured at 40 nm increment）
The hole formed on Si wafer was measured at 40 nm interval. In Si Raman
imaging(right), it was found that tensile stress on one side and compression
stress on the other side were remaining.
remaining
Raman imaging of cross-section of mechanical pencil lead

5
Graphite

4 Diamond

Carbon fiber C60

3
Carbon Acethylene black
Int nanotube
2

DLC film Observation image

1

0
1800 1600 1400 1200 1000
Raman Shift [cm-1]

Raman spectra of various carbon material

G band/D band ratio color distribution

 Raman imaging of coral

Observation image

1090cm-1
155cm-11 Enlarged view
285cm-1
1300

1000

calcite
カルサイト

Int.
peak height color distribution
500 210cm-1 (red : calcite, green : aragonite)
aragonite
アラゴナイト

0
3700 3000 2000 1000 50 Raman imaging measurement of the coral gave the
visualization of distribution of calcite and aragonite, which are
Raman Shift [cm-1]

Difference of spectra depends on

crystal polymorphism. crystal polymorphism of calcium carbonate.
 Spectra
p Manager
g II screen for NRS-5000/7000

spectrum

Measurement
conditions
diti setting
tti

Real time
Observation imaging
conditions setting

Microscope image
 3-D mapping

4D image
spectrum

Microscope
Stack display
i
image ffor sample
l
 3-D
3 D imaging for the liquid crystal panel

polarizer
TAC film

Color filter
3-D imaging for the liquid crystal panel was
measured without the destruction and the
structure for each layer
y and depthp p position
information were studied.
 3-D
3 D mapping of film

3 layers
y film Particle in film
 Measurement with low wavenumber
measurement attachment
with low wavenumber measurement attachment
（上）低波数測定ユニット使用時

without low （下）低波数測定ユニット未使用時

wavenumber measurement attachment

1000 800 600 400 200 30

Raman Shift [cm-1]

Raman spectrum
p of trehalose

Low wavenumber region can be clearly measured using low wavenumber

measurement attachment.
attachment
 Crystal polymorph of pharmacological product

crystal structure amorphous

amorphous
crystal structure

Amorphous material can be evaluated with Raman spectroscopy while it is

difficult to evaluate with X-ray Diffraction.
 Raman spectrum of hydrogen gas
H H High wavenumber resolution
vibration-rotation spectrum
Hydrogen
y g molecule: Raman active
(infrared inactive)

Gas cell

4400 4000 Vibration spectrum

rotation spectrum

Anti-stockes

Installation of gas cell

4000cm-1 1000cm-1 0cm-1

Raman spectrum of hydrogen gas

Estimation of temperature
Calculation of atomic distance
Evaluation of ortho・para
hydrogen ratio
 Compatibility of measurement with high wavenumber resolution
and wide spectral-band measurement (1)
=stress measurement and alien substance measurement=
compression tensile

Compression stress Stress free Tensile stress

Peak shift Peak shift

alien substance on Si wafer

521 520.5 519
Raman shift (cm-1)
1 cm-1 Peak shift → Equivalent of 250 MPa stress
Nitriding
g film
Si substrate

Acquisition of Raman
spectrum
Library search -> alien substance
is identified as cellulose

Identification for alien substance by

Observation of imperceptible Raman
wide spectral-band measurement
shift by high resolution measurement
 Compatibility of measurement with high wavenumber resolution
and wide spectral-band measurement (2)
=qualitative analysis and crystallinity measurement=
Crystallinity measurement for PET bottle
A crystallinity high
B crystallinity low
C crystallinity medium
A B
PET (polyethylene terephthalate)
benzene ring

C=O

C
C-H

wide spectral-band measurement high wavenumber resolution spectrum

C=O peak width of PET is related to crystallinity.

lateral side--- crystallinity: high

Upper side--- crystallinity: low
 Effectiveness of Nd: YAG excitation
- 1064 nm laser and InGaAs NIR detector
1064nm laser for fluorescence removal is available
available. Fluorescence-free
Fluorescence free Measurement is
useful for samples which generate fluorescence even excited by 785 nm and also for
microscopic measurement which cannot be implemented by FT-Raman system.

(nm)
UV 785 nm
244, 266 rubber

Intensity ((a.u.)
325, 355, 441
488, 514.5
Vis.
532
1064 nm
632.8

785
IR
1064
3500 3000 2000 1000 200
Raman Shift (cm-1)

Raman spectrum of rubber

Resonance Raman (1) Raman spectrum of each part in
boiled egg（532 nm excitation）
130000

殻（カルサイト）
Shell(calcite)
100000

殻と卵白の間の皮（タンパク質）
Skin between Shell and egg albumen (protein)

Boiled egg
Int.

50000 卵白（タンパク質＋水）
egg albumen (protein + H2O)

yolk (carotenoid)
卵黄（カロテノイド）
0
3700 3000 2000 1000 100
Raman Shift [cm-1]

Spectral shape of only yolk is

distinguished from others.
Resonance Raman (2) Raman spectrum for yolk of boiled
egg CH bending
80000 C=C Amide III C-C
carotenoid + protein amide I
785 nm excitation
CH stretching
60000
633 nm excitation

Int.40000
carotenoid + protein

20000
carotenoid
532 nm excitation
it ti

0
3700 3000 2000 1000 200
Raman Shift [[cm-1]

Raman spectra of yolk excited by 3-wavelength lasers

 Resonance Raman (3) Vegetable juice
100000 C=C C-C

80000
532nm

60000

Int. 633nm
40000

785nm
20000
1064nm

0
3700 3000 2000 1000 200
Raman Shift [cm-1]
Raman spectrum of vegetable juice
 Various kinds of software

Before fluorescence
蛍光除去前
removal

After蛍光除去後
fluorescence
removal

[Auto[自動蛍光補正機能]
fluorescence correction function]:
Help function
fluorescence removal with one click
ワンクリックで蛍光除去 ヘルプ機能

[ユーザアドバイス機能]
[User advice function]:
ライブラリ検索ソフト
Libraryy search software
最適な測定条件をアドバイス
Advising proper measurement conditions
 Summary

The routine analysis to the research study in a laboratory

can be implemented by using a NRS
NRS-5000/7000.
5000/7000

• High Speed Imaging, 3-D

3 D Raman Imaging, Sub-Micron
Sub Micron Mapping
• Low wavenumber region measurement, High wavenumber resolution
• Resonance Raman to fluorescence avoidance,, Max. 8 lasers(from
( UV to NIR))
• Various kinds of program supporting the measurement and analysis

NRS-5000
NRS 5000 NRS-7000
NRS 7000