Laser Raman Spectrometer

Seminar of JASCO ProductJune 26 -- 30, 2017

(Application and Measurement)

Theory of FT/IR and Raman, Difference, Feature of RamanFeature of Raman spectrometerFeature of JASCO Raman spectrometer

What is Raman?

Excitation light（ν0）

Sample Absorption

Reflection light

Fluorescence

Interaction of Light with Matter

Transmitted light

Scattering light

Fluorescence

RamanRaman Scattering light

Fluorescence FP

Rayleigh scattering light

Raman scattering light UV/Vis/NIRFT/IR

Transmitted lightReflection light

Absorption

Reflection light

Theory of FT/IR

detect transmitted or reflection light after irradiating IR

Transmitted light

IR

IR

Excited state

ground state

Excitation light

Ener

gy

FT/IRThe absorbed energy corresponds in the molecular vibration energy

FT/IR can analyze the molecular vibration

FT/IR

Laser (ν0)(UV~NIR)

Absorption

Fluorescence

Rayleigh scatteringlight（ν0）

Raman scattering light ν0+ v : Anti- stokeν0 – ν : stoke

Scattering light

h(ν0- ν)

FT/IR

h ν

Raman detect Raman scattered light that after irradiating Laser

This energy difference (hv) correspond in the molecular vibration energy.

Raman also can analyze the molecular vibration

Theory of Raman

h(ν0+ ν)

StokeRamanscattering

Anti-StokeRamanscattering

IR

Laserhν0

Rayleighscattering

hν0

0

100

20

40

60

80

1800 15050010001500

Int.

Wavenumber [cm-1]

-S-S-

IR

Raman

-C=O

FT/IR and Raman complement each other.

L‐Cystine

The comparison of FT/IR and Laser Raman spectrum

In general,the strong bands in the FT/IR spectrum corresponds to weak bands in the Raman and vice versa.It is said that,

mannitol

starch

cellulose

saccharose

glucoseNaylon 6

PET

polyethylene

polyethyleneglycol 

polystyrene

Teflon

Spectrum pattern depends on molecular structure → qualitative analysis

Raman spectrum organic compounds and polymer

Library search program

Unknown spectrum

PET

Functional group analysis program

JASCO library : about 1300Organic compounds : about 2000Inorganic compounds : about 1600

standard

Analysis support software ~Know It All TM ~

option

Raman IR (mid-IR）Spatial resolution 〜1μm 5〜10μmNondestructive measurement ◎ ○

Pre-sampling ◎ ○Database About 5000 More than 200,000

Low wavenumbermeasurement range ~ 5 cm-1 ~400 cm-1

SamplesAmorphous

Inorganic and organic material, carbon materials

Organic material

Disadvantage Obstacle due to fluorescenceSample damage due to laser

Require handling

Comparison between Raman & IR

Confocal‐Pin hole

Imaging‐lens

Objective‐lens

Transparent sample

Spatial Resolution @532nm laser

NRS-7000/5000 seriesX,Y : < 0.7 μmZ : < 1.0 μm

Impurity

High Spatial Resolution(Confocal Optics)

Focus Point

Only the focused light can pass through Confocal pin hole.

Therefore conforcal microscopeRaman can measure in the Z

direction for transparent sample.Focused light Non target light (background) 

NRS-4500X,Y : < 1.0 μmZ : < 1.5 μm

glass

ITO

2~3 μm

Raman can measure impurity inside the transparent substance

Buried impurity in the ITO(Indium Tin Oxide)

Top view

Side view

impurity

Raman Shift[cm-1]3600 100100020003000

Int.-C-C-

-CH3 Impurity is polyethylene

For external sample measurement or in situ monitoring.

Non-destructive depth measurement of Multi-layer film

(blue：base layer, green：adhesive layer)

Observation probe (via optical fiber)

Raman IR (mid-IR）Spatial resolution 〜1μm 5〜10μmNondestructive measurement ◎ ○

Pre-sampling ◎ ○Database About 5000 More than 200,000

Low wavenumbermeasurement range ~ 5 cm-1 ~400 cm-1

SamplesAmorphous

Inorganic and organic material, carbon materials

Organic material

Disadvantage Obstacle due to fluorescenceSample damage due to laser

Require handling

Comparison between Raman & IR

It is possible to distinguish Calcite from Aragonite by the difference of the low wavenumber spectrum.

Calcite

Chalk etc.

Aragonite

Coral,pearl

Calcite

Aragonite

Lattice vibration

Analyzing polymorph of Inorganic crystal (CaCO3)

CO32-

Calcium carbonate have two types of polymorph (Calcite and Aragonite)

Distribution of CBZ Form Ⅲ800 10200400600

Int.

Raman Shift [cm-1]

Low wavenumber imaging of pharmaceutical tablet

Tablet imageFormⅡtype

Amorphous

Form Ⅲ type

Carbamazepine (CBZ) Medication for the treatment ofepilepsy and neuropathic pain.

It is possible to visualize the distribution of CBZ form Ⅲ.

0

5

1

2

3

4

1800 1000120014001600

Int

Raman Shift [cm-1]

DLC film

Diamond

graphite

C60

Carbon fiber

Amorphous carbonCNT

A variety of Carbon structure

Raman spectra of Various Carbon material

Raman can sensitively detect Carbone material

Raman IR (mid-IR）Spatial resolution 〜1μm 5〜10μmNondestructive measurement ◎ ○

Pre-sampling ◎ ○Database About 5000 More than 200,000

Low wavenumbermeasurement range ~ 5 cm-1 ~400 cm-1

SamplesAmorphous

Inorganic and organic material, carbon materials

Organic material

Disadvantage Obstacle due to fluorescenceSample damage due to laser

Require handling

Comparison between Raman & IR

Disadvantage of Raman

obstacle due to fluorescenceCause :Fluorescence arising from sample itself and matrix.

Solution1. change to long wavelength laser excitation

2. Purification of sample : Remove the impurity

3. Improving of spatial resolution (X,Y,Z direction)Usage of high power objective lens

4. longer irradiation time of excitation laser.

5. Software : Auto-fluorescence reduction (Patented)

Solution : turn laser intensity down

3100 15010002000

Int.

1064 nm

785 nm

633 nm

532 nm

Raman spectra of red pigment

damage due to laser2500 20010002000

Int.

Raman Shift [cm-1]

Auto-fluorescence reduction

Beam splitter Excitation Laser

Rejection filter

mirror

Objective lens

Sample stage

sample

monochromator

Detector

GratingSlit

Feature of JASCO Raman Spectrometer

Automatic 4 gratings switching mechanism

・ Multi-wavelength excitation・ Broadband ~ Short range

measurement

High-accuracy direct drivetype (with rotary encoder)Wavenumber scanning mechanism

532nm

457nm

785nm

NRS-5000/7000 :244,266,325,355,405,442,457,488,514.5,532,633,660,785,1064nm

NRS-4500 : 405,442,457,488,514.5,532,633,785,1064nmNumber of mountable laser

NRS-5000/7000 : MAX 8 (2 internal, 6 external)NRS-4500 : MAX 3 (2 internal, 1 external)

Automatic excitation laser switching mechanismAutomatic Rejection filter switching mechanism

pinholeaperture

Disadvantage of Raman

obstacle due to fluorescenceCause :Fluorescence arising from sample itself and matrix.

Solution1. change to long wavelength laser excitation

2. Purification of sample : Remove the impurity

3. Improving of spatial resolution (X,Y,Z direction)Usage of high power objective lens

4. longer irradiation time of excitation laser.

5. Software : Auto-fluorescence reduction (Patented)

Solution : turn laser intensity down

3100 15010002000

Int.

1064 nm

785 nm

633 nm

532 nm

Raman spectra of red pigment

damage due to laser2500 20010002000

Int.

Raman Shift [cm-1]

Auto-fluorescence reduction

Application of Laser Raman Spectrometer

Semiconductor Stress, Impurity, Study of super lattice structure, Heterostructure, Doping effect, Superconductor, photoluminescence, etc.

Polymer Identification of polymorphic form, Distribution condition of blend polymer, Analysis of monomer and isomer, Crystallinity, Orientation, Multi-layer construction, Monitoring of polymerization reaction, Composite material analysis, Purity and fault, etc

Carbon material DLC(Diamond Like Carbon), Characterization of fullerene and nanotube,Diamond,Graphite, Quality analysis of carbon film, HDD coating, etc

Pharmaceuticals Crystal polymorphism, Imaging of medicinal ingredient, etc.

GeologyMineralogy

Included gas/liquid in mineral, Temperature behaviour in extreme condition, crystal structure, etc.

impurity

Inorganic compound

polymer・organic material

semiconductor (Si)

Carbon material（DLC,CNT）

gase

complexfood・biological

impurity

Carbon material(graphene,Lithium ion battery matterial)Semiconductor

(SiC)

inorganic compound(Lithium ion mattery material)

Food・biological

complexgase

now〜5 years ago

polymer・organic material

Raman Application trend in JAPAN

1990~

1980～

1995～

Over 30 years of JASCO Raman history

NRS‐2100 (f=400mm) triple monochrometerCCD detecter

NR‐1100 (f=1m) double monochrometer

NR‐1800 (f=575 mm) triple monochrometerCCD detecter 2009 ～

2000~

2005 ～

2013 ～NRS‐1000 (f=300mm) High sensitive using Single monochrometer

NRS‐3000 (f=300mm)Automated system

fast‐imaging,3D imaging

NRS‐5000 (f=300mm)

NRS‐7000 (f=500mm)

NRS‐4100 (f=200mm)Compact, high performance

NRS‐4500 NRS‐5500/5600 NRS‐7500/7600

New Raman Spectroscopy (2016~)

High speed Raman Imaging function・Stage moving type : QRI (Quick Raman Imaging) (All series model)・Beam scanning type: SPRIntS (NRS-5000/7000 series)・Improvements of Imaging quality by Digital Filtration

Usability, User support function・Auto switching mechanism（Laser, Grating, Rejection Filter）・Auto arraignment (Laser path ,Raman optical)・Assist function for measurement

NRS-4500

Instruments : NRS-4500Sample : titanium dioxide fibersEx Laser : 532 nm Range of measurement : 30μm squareMeasurement Point : 151 x 151 = 22,801Measurement interval : 0.2 μmExposure time : 2 msecDetector : EMCCDMeasuring time : 5 min

QRI high speed imaging in narrow area

Raman imageOptical imageQRI

Focal length : 200 mmMonochromator : 2cm-1/PixelResolution 0.7m-1/Pixel opGrating : 4Confocal resolution (XY) : 1.0 μmConfocal resolution (z) : 1.5 μmImaging : QRI

Purpose of use of NRS-4500Identification of foreign matterComposition analysis

NRS-5500/5600

Objective view

Blue: Water Green: Oil

5 μm

SPRIntS

Imaging view

Imaging analysis of Emulsion sample by SPRIntS (Beam scanning type)

Focal length : 300 mmMonochromator : 1cm-1/PixelResolution 0.4m-1/Pixel opGrating : 4Confocal resolution (XY) : 0.7 μmConfocal resolution (z) : 1.0 μmImaging : QRI, SPRIntS

Water immersion objective may have a peak relatedwith Water sometimes, but itʼs easy to subtract because the peak shape of water is broad. On the other hand, Oil immersion lens is not good for analysis due to multiple peak of oil.

NRS-5000/7000 have two type Imaging and can analyze various sample type.

NRS-7500/7600Stress evaluation by QRI

‐0.2 cm‐1

(Tensile stress50MPa)

+0.2 cm‐1

(Compressive stress50MPa)

X100 Objective view Color diagram of peak shit

Nitride film

Si Substrate

Compressive stress

Tensile stress5 μm 5 μm

Compressive stress

Tensile stress

Focal length : 500 mmMonochromator : 0.7cm-1/PixelResolution 0.3m-1/Pixel opGrating : 4Confocal resolution (XY) : 0.7 μmConfocal resolution (z) : 1.0 μmImaging : QRI, SPRIntS

Purpose of use of NRS-5000/7000Physical property evaluation-Stress measurement-Low wave number measurement-Liquidity sample

Finally...

JASCO design all components from microscope to monochromatorand combine performance with usability

RMP500 seriesNRS-4500NRS-5500/5600NRS-7500/7600

JASCO laser Raman Spectrometers are “Real Standard”