Laser Raman Spectrometer

Transcription

1 Laser Raman Spectrometer (Application and Measurement) Seminar of JASCO Product June , 2017

2 What is Raman? Theory of FT/IR and Raman, Difference, Feature of Raman Feature of Raman spectrometer Feature of JASCO Raman spectrometer

3 Interaction of Light with Matter Rayleigh scattering light Raman scattering light Scattering light Transmitted light UV/Vis/NIR Reflection light FT/IR Reflection light Excitation light(ν 0 ) Fluorescence FP Fluorescence Raman Scattering light Raman Sample Absorption Fluorescence Transmitted light

4 Theory of FT/IR FT/IR detect transmitted or reflection light after irradiating IR Reflection light Excitation light IR Excited state Absorption Energy IR ground state Transmitted light The absorbed energy corresponds in the molecular vibration energy FT/IR FT/IR can analyze the molecular vibration

5 Theory of Raman Raman detect Raman scattered light that after irradiating Laser Scattering light Rayleigh scattering Raman scattering light light(ν 0 ) ν 0 + v : Anti- stoke ν 0 ν : stoke Laser hν 0 hν 0 h(ν 0 -ν) h(ν 0 + ν) Laser (ν 0 ) Fluorescence (UV~NIR) IR h ν Absorption Rayleigh scattering Stoke Raman scattering Anti-Stoke Raman scattering FT/IR This energy difference (hv) correspond in the molecular vibration energy. Raman also can analyze the molecular vibration

6 The comparison of FT/IR and Laser Raman spectrum C=O IR Int S-S- L Cystine 20 Raman Wavenumber [cm-1] In general,the strong bands in the FT/IR spectrum corresponds to weak bands in the Raman and vice versa. It is said that, FT/IR and Raman complement each other.

7 Raman spectrum organic compounds and polymer glucose saccharose cellulose starch mannitol Naylon 6 PET polyethylene polyethyleneglycol polystyrene Teflon Spectrum pattern depends on molecular structure qualitative analysis

8 Analysis support software ~Know It All TM ~ PET Unknown spectrum JASCO library : about 1300 Organic compounds : about 2000 Inorganic compounds : about 1600 standard option Library search program Functional group analysis program

9 Comparison between Raman & IR Raman IR (mid-ir) Spatial resolution 1μm 5 10μm Nondestructive measurement Pre-sampling Database About 5000 More than 200,000 Low wavenumber measurement range ~ 5 cm -1 ~400 cm -1 Samples Amorphous Inorganic and organic material, carbon materials Organic material Disadvantage Obstacle due to fluorescence Sample damage due to laser Require handling

10 High Spatial Resolution(Confocal Optics) Confocal Pin hole Imaginglens Focus Point Focused light Only the focused light can pass through Confocal pin hole. Therefore conforcal microscope Raman can measure in the Z direction for transparent sample. Non target light (background) Objectivelens Transparent sample Impurity Spatial laser NRS-7000/5000 series X,Y : < 0.7 μm Z : < 1.0 μm NRS-4500 X,Y : < 1.0 μm Z : < 1.5 μm

11 Buried impurity in the ITO (Indium Tin Oxide) Observation probe (via optical fiber) 2~3 μm Top view Side view ITO glass For external sample measurement or in situ monitoring. impurity -CH 3 Impurity is polyethylene Non-destructive depth measurement of Multi-layer film Int. -C-C Raman Shift[cm-1] Raman can measure impurity inside the transparent substance (blue:base layer, green:adhesive layer)

12 Comparison between Raman & IR Raman IR (mid-ir) Spatial resolution 1μm 5 10μm Nondestructive measurement Pre-sampling Database About 5000 More than 200,000 Low wavenumber measurement range ~ 5 cm -1 ~400 cm -1 Samples Amorphous Inorganic and organic material, carbon materials Organic material Disadvantage Obstacle due to fluorescence Sample damage due to laser Require handling

13 Analyzing polymorph of Inorganic crystal (CaCO 3 ) Calcium carbonate have two types of polymorph (Calcite and Aragonite) CO 3 2- Calcite Chalk etc. Calcite Aragonite Aragonite Lattice vibration Coral,pearl It is possible to distinguish Calcite from Aragonite by the difference of the low wavenumber spectrum.

14 Low wavenumber imaging of pharmaceutical tablet Carbamazepine (CBZ) Medication for the treatment of epilepsy and neuropathic pain. FormⅡtype Tablet image Int. Form Ⅲ type Amorphous Raman Shift [cm-1] Distribution of CBZ Form Ⅲ It is possible to visualize the distribution of CBZ form Ⅲ.

15 Raman spectra of Various Carbon material 5 graphite 4 3 Carbon fiber C60 Diamond Int 2 CNT Amorphous carbon DLC film Raman Shift [cm-1] A variety of Carbon structure Raman can sensitively detect Carbone material

16 Comparison between Raman & IR Raman IR (mid-ir) Spatial resolution 1μm 5 10μm Nondestructive measurement Pre-sampling Database About 5000 More than 200,000 Low wavenumber measurement range ~ 5 cm -1 ~400 cm -1 Samples Amorphous Inorganic and organic material, carbon materials Organic material Disadvantage Obstacle due to fluorescence Sample damage due to laser Require handling

17 Disadvantage of Raman obstacle due to fluorescence 532 nm Cause :Fluorescence arising from sample itself and matrix. Int. 633 nm Solution 1. 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 1064 nm 785 nm Raman spectra of red pigment 4. longer irradiation time of excitation laser. 5. Software : Auto-fluorescence reduction (Patented) Int. damage due to laser Solution : turn laser intensity down Raman Shift [cm-1] Auto-fluorescence reduction

18 Feature of JASCO Raman Spectrometer Detector mirror pinhole aperture Rejection filter Slit Grating Automatic 4 gratings switching mechanism Multi-wavelength excitation Broadband ~ Short range measurement High-accuracy direct drive type (with rotary encoder) monochromator Wavenumber scanning Beam splitter 785nm Excitation Laser mechanism sample 532nm 457nm Objective lens Sample stage NRS-5000/7000 :244,266,325,355,405,442,457,488, 514.5,532,633,660,785,1064nm NRS-4500 : 405,442,457,488,514.5,532,633,785,1064nm Number of mountable laser NRS-5000/7000 : MAX 8 (2 internal, 6 external) NRS-4500 : MAX 3 (2 internal, 1 external) Automatic excitation laser switching mechanism Automatic Rejection filter switching mechanism

19 Disadvantage of Raman obstacle due to fluorescence 532 nm Cause :Fluorescence arising from sample itself and matrix. Int. 633 nm Solution 1. 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 1064 nm 785 nm Raman spectra of red pigment 4. longer irradiation time of excitation laser. 5. Software : Auto-fluorescence reduction (Patented) Int. damage due to laser Solution : turn laser intensity down Raman Shift [cm-1] Auto-fluorescence reduction

20 Application of Laser Raman Spectrometer Semiconductor Stress, Impurity, Study of super lattice structure, Heterostructure, Doping effect, Superconductor, photoluminescence, etc. Polymer Carbon material 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 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. Geology Mineralogy Included gas/liquid in mineral, Temperature behaviour in extreme condition, crystal structure, etc.

21 Raman Application trend in JAPAN food biological complex gase Food biological complex gase Inorganic compound inorganic compound (Lithium ion mattery material) impurity semiconductor (Si) polymer organic material impurity Semiconductor (SiC) Carbon material (graphene, Lithium ion battery matterial) Carbon material (DLC,CNT) 5 years ago polymer organic material now

22 Over 30 years of JASCO Raman history 1980~ NR 1100 (f=1m) double monochrometer 2005 ~ NRS 3000 (f=300mm) Automated system 1990~ NR 1800 (f=575 mm) triple monochrometer CCD detecter 2009 ~ NRS 5000 (f=300mm) 1995~ NRS 2100 (f=400mm) triple monochrometer CCD detecter NRS 7000 (f=500mm) fast imaging, 3D imaging 2000~ NRS 1000 (f=300mm) High sensitive using Single monochrometer 2013 ~ NRS 4100 (f=200mm) Compact, high performance

23 New Raman Spectroscopy (2016~) NRS 4500 NRS 5500/5600 NRS 7500/7600 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

24 NRS-4500 QRI high speed imaging in narrow area QRI Focal length : 200 mm Monochromator : 2cm -1 /Pixel Resolution 0.7m -1 /Pixel op Grating : 4 Confocal resolution (XY) : 1.0 μm Confocal resolution (z) : 1.5 μm Imaging : QRI Purpose of use of NRS-4500 Identification of foreign matter Composition analysis Optical image Raman image Instruments : NRS-4500 Sample : titanium dioxide fibers Ex Laser : 532 nm Range of measurement : 30μm square Measurement Point : 151 x 151 = 22,801 Measurement interval : 0.2 μm Exposure time : 2 msec Detector : EMCCD Measuring time : 5 min

25 NRS-5500/5600 Imaging analysis of Emulsion sample by SPRIntS (Beam scanning type) SPRIntS Focal length : 300 mm Monochromator : 1cm -1 /Pixel Resolution 0.4m -1 /Pixel op Grating : 4 Confocal resolution (XY) : 0.7 μm Confocal resolution (z) : 1.0 μm Imaging : QRI, SPRIntS Objective view Imaging view 5 μm Blue: Water Green: Oil Water immersion objective may have a peak related with 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.

26 NRS-7500/7600 Stress evaluation by QRI Nitride film Compressive stress +0.2 cm 1 (Compressive stress 50MPa) Focal length : 500 mm Monochromator : 0.7cm -1 /Pixel Resolution 0.3m -1 /Pixel op Grating : 4 Confocal resolution (XY) : 0.7 μm Confocal resolution (z) : 1.0 μm Imaging : QRI, SPRIntS Si Substrate X100 Objective view 5 μm Tensile stress 5 μm Color diagram of peak shit 0.2 cm 1 (Tensile stress 50MPa) Compressive stress Tensile stress Purpose of use of NRS-5000/7000 Physical property evaluation -Stress measurement -Low wave number measurement -Liquidity sample

27 Finally... JASCO design all components from microscope to monochromator and combine performance with usability JASCO laser Raman Spectrometers are Real Standard NRS-7500/7600 NRS-5500/5600 NRS-4500 RMP500 series