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Introduction to the CMSE Shared Experimental Facilities. Anthony J. Garratt-Reed, SEF Staff Thu Jan 11, 02-05:00pm, 13-2137, Refreshments provided No enrollment limit, no advance sign up , Single session event - PowerPoint PPT Presentation
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IAP 2007
Introduction to the CMSE Shared Experimental
FacilitiesAnthony J. Garratt-Reed, SEF Staff
Thu Jan 11, 02-05:00pm, 13-2137, Refreshments provided
No enrollment limit, no advance sign up , Single session event
The Shared Experimental Facilities in the Center for Materials Science and Engineering provide a wide range of Materials Characterization instrumentation openly available to
researchers. This includes electron microscopes, X-ray diffraction systems, surface analysis, spectroscopy techniques, thermal analysis and crystal growth furnaces. Come and find out more details about what we have, what it can do for you, and who runs it! Each staff member will give a short introduction to the instruments in their care. Most staff will be offering a more detailed presentation about their equipment later during
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Contact: Anthony J. Garratt-Reed, 13-1027, x3-4622, [email protected] Sponsor: Center for Materials Science and Engineering
Latest update: 27-Nov-2006
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Tim McClureAnalysis Shared Experimental Facility
Project TechnicianOffice: 13-4149
Phone: (617) 258-6470Email: [email protected]
http://mit.edu/mtim/wwwMIT Center for Material Science and Engineering
77 Massachusetts Avenue, Cambridge, Massachusetts 02139
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AnalysisShared Experimental Facility
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Analysis SEF
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Analysis SEF Staff
Dr. Shaoyan Chu [email protected] X3-0054Tim McClure [email protected] X8-6470Elisabeth Shaw [email protected] X3-5045
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Analysis SEF
13-4111 13-4139 13-4147
13-4137 13-4149
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Analysis SEF
Thermal Analysis 13-4111Dr. Shaoyan Chu [email protected]
Surface Analysis 13-4137Libby Shaw [email protected]
Spectroscopy 13-4139Tim McClure [email protected]
AFM/Thin Film 13-4147Libby Shaw [email protected]
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13 - 4139
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Instrumentation in 13-4139Spectroscopy
Microscopy
Thin Film
Support
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Instrumentation in 13-4139Spectroscopy
FTIR, Raman, UV/VIS/NIR, Fluorimeter
Microscopy
Thin Film
Support
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Instrumentation in 13-4139Spectroscopy
FTIR, Raman, UV/VIS/NIR, Fluorimeter
MicroscopyOptical, Thermal, FTIR, Raman
Thin Film
Support
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Instrumentation in 13-4139Spectroscopy
FTIR, Raman, UV/VIS/NIR, Fluorimeter
MicroscopyOptical, Thermal, FTIR, Raman
Thin FilmProfilometer, Flexus, Thermal Co-Evaporator, Plasma Cleaner
Support
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Instrumentation in 13-4139Spectroscopy
FTIR, Raman, UV/VIS/NIR, Fluorimeter
MicroscopyOptical, Thermal, FTIR, Raman
Thin FilmProfilometer, Flexus, Thermal Co-Evaporator, Plasma Cleaner
SupportTemperature Controlled Microscope Stages, Cryostat, Lasers, Exhaust Hood, Oven
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Spectroscopy
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SpectroscopyThere are many types of spectroscopic
analysis techniques
XRAYXPSICPEtc.
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Optical Spectroscopy Methods
Absorption
Emisson
Luminescence
Scattering
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Absorption Spectroscopy
Absorbance or the ratio of transmitted to incident radiant power
•Atomic absorption•UV/VIS molecular absorption•IR absorption
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Emission Spectroscopy
Radiant power of emission
•ICP•Spark•Flame•DC Arc
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Luminescence Spectroscopy
Radiant power of luminescence
•Molecular Fluorescence•Phosphorescence•Chemical and Bioluminescence•Atomic Fluorescence
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Scattering Spectroscopy
Radiant power of scattering
•Raman Scattering•Mie scattering•turbidity
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Optical SpectroscopyInteraction of optical electromagnetic
radiation with matter
Vibrational
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Spectra
Intramolecular Vibrations
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Stretching Vibrations
•In a simple diatomic molecule A-B the only vibration which can occur is a periodic stretching along the A-B bond.
•Stretching vibrations resemble the oscillations of two bodies connected by a spring.
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Hooke’s Law
For stretching of the bond A-B,the vibrational frequency v (cm-1) is
given by the equation:
v = (1/2c) (f/)1/2
c = Velocity of lightf = Force constant of the bond = reduced mass of the system
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Reduced Mass Equation
= (mA.mB)/(mA+mB)
= reduced mass of the systemmA and mB are the individual masses of A and B
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Spectrochemical Analysis
•Water we drink•Food we eat•Status of human health•Quality of the environment
Is used to monitor
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Spectroscopic Intruments
•Fourier Transform Infrared (FTIR) -Thermo Nicolet–Magna 860 Bench–Nic Plan Microscope
•Raman Microprobe -Kaiser–Hololab 5000R Modular Research System–Argon Ion (514.5nm), Titanium Sapphire (785nm) CW Lasers, Diode (785nm)
•UV/Vis Spectrometers -Cary•5e•500i
•Fluorimeter -PTI•QM6/2006
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FTIR Bench and Microscope
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Infrared Spectra
The absorption or emission spectrum arising from the rotational and vibrational motions of a molecule which is not electronically excited is
mostly in the infrared region.
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IR Active Vibration
Selection RuleThere must be a net change in permanent dipole
moment during the vibration
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Vibrational Energies
The energy of a vibrational mode depends onmolecular structureand environment.Atomic massbond ordermolecular substituentsmolecular geometryhydrogen bonding
all effect the vibrational force constant
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IR Spectroscopy Studies
Identification of a SubstanceDetermination of Molecular structure
Determination of PurityReaction Kinetic Studies
Fundamental Studies of Molecules
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Spectra
•A unique physical property and is characteristic of the molecule
•The infrared spectrum can be used as a fingerprint for identification
•Compare with previously recorded reference spectra
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Nicolet Magna 860 FTIR Spectrometer
Beam splitter, Detector, Source combinations allow extended range measurement in the Mid, Near and Far IR ranges.
AccessoriesEmission ExperimentsHorizontal Attenuated Total ReflectanceVariable Angle ReflectanceOptical CryostatSolid, Liquid, Gas Sampling Accessories
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Spectra Tech Nic Plan FTIR Microscope
This Microscope works with the Nicolet Magna 860 Spectrometer.
Spot sizes as small as 10 microns can be sampled.
It has a motorized stage with Sample Mapping and Video Capture capabilities.
AccessoriesATR Objective15X, 32X IR ObjectivesMicro Compression CellView Thru Aperture
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FTIR Spectrum of Cyclohexane
542.47
861.08
903.50
1241.21
1449.50
2659.19
2799.93
2852.53
2926.76
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
Absorbance
1000 1500 2000 2500 3000 3500 Wavenumbers (cm-1)
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FTIR Sensitivity to Carbon Hydrogen BondsCyclohexane_C6_H12
0.2
0.4
0.6
0.8
1.0
Abs
Methylcyclohexane_C7_H14
0.2
0.4
0.6
0.8
1.0
Abs
Decahydronaphthalene_C10_H18
0.2
0.4
0.6
0.8
1.0
Abs
1000 1500 2000 2500 3000 3500 Wavenumbers (cm-1)
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FTIR Detector Comparison
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Raman Microprobe
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Raman Effect
ClassicalPerturbation of the molecule’s electric field
Quantum mechanicalscattering is an excitation to a virtual statelower in energy than a real electronic transition with
nearly coincident de-excitation and a change in vibrational energy
The scattering event occurs in 10-14 seconds or less
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Raman Spectroscopy
The Raman effect arises when a photon is incident on a molecule and interacts with the
electric dipole of the molecule.
It is a form of electronic spectroscopyVibronic is more accurate
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Raman Spectrum
The difference in energy between the incident photon and the Raman scattered photon is equal
to the energy of a vibration of the scattering molecule.
A plot of intensity of scattered light versus energy difference is a Raman spectrum
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Weak Raman Scatterers
Highly polar moiety vibrationsO-H bond
An external electric field can not induce a large change in the dipole moment
Stretching or bending the bond does not change this
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Strong Raman Scatterers
Moieties with distributed electron clouds
carbon-carbon double bonds
The electron cloud of the double bond is easily distorted in an external electric field
Bending or stretching the bond changes the distribution of electron density substantially, and causes a large change in induced dipole moment
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IR & Raman Molecular Frequencies
Infrared absorption frequencies frequently agree with the frequency shifts found in the Raman effect
Not always trueDepends on the symmetry of the molecule
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Raman Uses
Vibrational Raman spectroscopy is not limited to intramolecular vibrations
Crystal lattice vibrations and other motions of extended solids are Raman-active
PolymersSemiconductors
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Vibration/Rotation Spectra
Gas phaserotational structure is resolvable on vibrational
transitionsThe resulting vibration/rotation spectra are widely used to study combustion and gas phase reactions
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Vibrations in Solids
Spectra of crystals are almost always sharper than those of melts or solutions.
Spectra of solids when compared to those of the solute in solution or their melts are invariably much more complex.
The frequencies of the bands in the solid are shifted from those of itself in the liquid phase. Some bands can move considerably (30cm-1 is not unusual). (IJVS)
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Raman Microprobe
Kaiser Optical SystemsModular 5000R Research Grade Raman
Leica MicroscopePrior Motorized Stage
514.5nm or 785nm Excitation LasersHolographic Grating Spectrometer
Andor Deep Depletion CCD 1024 X 512Small or Large Fibers
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Raman Spectrum of Cyclohexane
387.10
432.25
595.09
802.52
1028.85
1267.34
1444.90
2665.01
2853.49
2938.90
10
20
30
40
50
60
70
80
90
100
110
120
130
140
Int
500 1000 1500 2000 2500 3000 3500 Raman shift (cm-1)
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Raman & FTIR Spectrum of Cyclohexane
861.08
903.50
1037.53
1257.38
1449.50
2659.19
2793.24
2852.53
2926.76
Cyclohexane FTIR
0.2
0.4
0.6
0.8
1.0
1.2
Abs
802.52
1028.85
1158.74
1267.34
1347.99
1444.90
2633.092
665.01
2695.952
853.49
2924.33
2938.90
Cyclohexane Raman
-0
20
40
60
80
100
120
140
Int
1000 1500 2000 2500 3000 Wavenumbers (cm-1)
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Cary 500i UV/Vis/NIRDual-Beam Spectrophotometer
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Cary 5E UV/Vis/NIRDual-Beam Spectrophotometer
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UV/VIS/NIR spectroscopy
UV/VIS/NIR spectroscopy is the measurement of the wavelength and intensity of absorption of near-ultraviolet
and visible light by a sample
Ultraviolet and visible light are energetic enough to promote outer electrons to higher energy levels
UV/VIS/NIR spectroscopy is usually applied to molecules and inorganic ions or complexes in solution
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UV/VIS/NIR Spectra
The UV/VIS/NIR spectra have broad features that are of limited use for sample identification but are very useful for
quantitative measurements.
The concentration of an analyte in solution can be determined by measuring the absorbance at some wavelength and applying the Beer-Lambert Law
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Cary 5E UV/Vis/NIRDual-Beam Spectrophotometer
Wavelength Range:175 to 3300 nm
Sources:UV: Deuterium arc lamp
Vis/NIR: Tungsten halogen lampDetectors:
UV/Vis:R928 Photo Multiplying Tube (PMT)
NIR:Thermoelectrically cooled lead sulfide photocell
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Cary 500i UV/Vis/NIRDual-Beam Spectrophotometer
Wavelength Range:175 to 1750 nm
Sources:UV: Deuterium arc lamp
Vis/NIR: Tungsten halogen lamp
Detectors:UV/Vis: R928 photomultiplier tube
NIR: Thermoelectrically cooled InGaAs PIN photodiode
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Dual-Beam Spectrophotometer
Measures the transmittance of the sample and solvent simultaneously
Easier to identify small changes between sample and reference
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UV/Vis Spectrophotometer Accessories
Solid Sample & Cuvette Holders
Multicell HolderAutomated measurement of multiple liquid samples
Temperature Controlled
Optical CryostatsLiquid NitrogenLiquid Helium
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UV/Vis Spectrophotometer Accessories
Specular Reflectance (SRA)Fixed 7°
Variable Angle Specular Reflectance (VASRA)
20 to 70°
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UV/Vis Spectrophotometer Accessories
Diffuse Reflectance (DRA)114mm Integrating Sphere
Internal Detectors (250nm - 2500nm)PMTPbs
Praying Mantis Reflectance Accessory
Diffuse Reflectance Accessory (220nm to 3300nm)PowdersPastesLiquids
3mm Analysis Area
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Photon Technology Int. QM-6/2006 Spectrofluorimeter
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Photon Technology Int. QM-6/2006 Spectrofluorimeter
This is a solid state UV/VIS/NIR Spectrofluorimeter that is on loan from PTI.
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Fluorimetry
Light emission from atoms or molecules can be used to quantitate
the amount of the emitting substance in a sample
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Fluorimetry Applications
Yields detailed information about complex molecules and their reaction pathways.
Binding of biochemical species can be easily studied in situ.
Distances within macromolecules may be measured.
The dynamics of the folding of proteins can be studied.
Concentrations of ions can be measured inside living cells.
Membrane structure and function may be studied with fluorescence probes.
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Fluorimetry Applications
Minute traces of fluorescent materials can be detected and identified in mixtures.
Oil samples can be finger-printed and identified by their fluorescence.
The electronic structure and dynamics of an excited state of a molecule may be elucidated.
Drug interactions with cell receptors can be investigated.
Useful for NIR photoluminescence measurement of carbon nanotubes
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Fluorimeter Data
Show Example Data
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Optical MicroscopesZeiss Axioskop
Zeiss Ultraphot
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Zeiss Axioskop
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Zeiss AxioskopZeiss Axioskop
T & RPolarizer'sDIC35mm CameraDigital CameraImage Analysis Software
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Zeiss Ultraphot
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Zeiss Ultraphot1930s Analytical Metalographic Microscope
Stable TransmissionReflectionDepth of Field Flatness of Field
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Temperature Controlled Microscope Stages
Linkum FTIR600(-190C) to 600C
MettlerR.T. to 350C
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Linkum Freeze Stage
For use under any of the laboratories microscopes
(Raman, FTIR, Optical)
Temperature Range -190°C to 600°CTransmission or Reflection
ProgramableControlled Sample Atmosphere
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Plasma Cleaner
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Plasma Cleaner
Harrick Plasma Model 32-GPyrex Chamber 3” X 7” deep
Input Power: 100WRF Frequency: 8 to 12 MHz
RF Coil Power: L-6.8W, M-10.5W, H-18W
PlasmafloDual Process Gas Flow Meters
Thermocouple Gauge (Varian 801)
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Plasma Cleaner
Principle of Operation
When a gas under sufficiently low pressure is subjected to a high frequency oscillating
electromagnetic field, the accelerated ions in the gas collide with the gas molecules ionizing them
and forming plasma.
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Plasma Cleaner
Principle of Operation (Cont)The ionized gas particles in the plasma interact with
solid surfaces placed in the same environment by:Removing organic contamination from surfaces.
The high energy plasma particles combine with the contaminant to form carbon dioxide (CO2) or methane (CH4)
Modifying or enhancing the physical and chemical characteristics of surfaces.
A chemical reaction occurs between the plasma gas molecules and the surface undergoing treatment.
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Plasma Cleaner
The type of interaction between the plasma and the surface depends on:
RF PowerFrequencyIntensity
GasPressureFlow Rate
TimeSample
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Thermal Co-evaporator
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Thermal Co-evaporator
This evaporator has three filament positions. The deposition can be controlled from two separate
crystal monitor controllers allowing for CO-Evaporation from two sources (2 KVA and 4 KVA)
simultaneously. The substrate stage is water cooled and temperature
monitored.It has a cryo-pumped vacuum system with an
interlocked Ion gauge controller and automatic valve sequencing controls.
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KLA Tencor P10 Profilometer
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KLA Tencor P10 Profilometer
Provides high precision surface topography measurements on a wide variety of substrates using a diamond tipped stylus.
This system features a motorized stage.Dual view optics (side view: 95-410X, top view: 115-465X and
185-750X with user interchangeable lenses).The maximum sample size is 355 X 355 mm (14" X 14") and a
maximum scan length of 60 mm (2.3").3d Mapping2.5um Styli
Used for Features 100Angstrom to 327micorns
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KLA Tencor P10 Profilometer
Show Example Data
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Tencor Flexus 2320Thin Film Stress Measurement System
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Tencor Flexus 2320Thin Film Stress Measurement System
This instrument measures the changes in the radius of curvature of a substrate caused by deposition of a stressed thin film.
The change in radius of curvature can be measured over time and as a function of temperature.
This system has been modified to extend the normal operating temperature of the hotstage. -150°C to 500°C
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MIT LinksCenter for Materials Science & Engineering web.mit.edu/cmse/
CMSE SEFs prism.mit.edu
Materials@MIT materials.mit.edu
Tims Web mit.edu/mtim/www/
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Informational LinksInternet Journal of Vibrational Spectroscopy
www.ijvs.com
Optical Microscopy Primer
micro.magnet.fsu.edu/primer/
FTIR & Raman Search
ftirsearch.com
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Instrument Manufacturers Links
Kaiser Optical www.kosi.com
Photon Technology International www.pti-nj.com
Varian www.varianinc.com
Thermo Scientific www.thermo.com
KLA Tencor www.kla-tencor.com
Carl Zeiss www.zeiss.com/micro
Harrick Plasma www.harrickplasma.com/
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References•Fourier Transform Infrared Spectrometry
Peter R. Griffiths, James A. de HasethISBN: 0-471-09902-3
•Molecular VibrationsThe Theory of Infrared and Raman Vibrational SpectraE. Bright Wilson, Jr., J.C. Decius and Paul C. CrossISBN: 0-486-63941-X
•Analytical Applications of Raman SpectroscopyMichael J. PelletierISBN: 0-632-05305-4
•Handbook of Raman SpectroscopyFrom the Research Laboratory to the Process LineIan R. Lewis, Howell G. EdwardsISBN: 0-8247-0557-2
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User Levels
AssistedNot interested in becoming a self user (1X)
TrainingWe work together on your sample until we are both comfortable with your operation of the instrument
Self24 Hour access (Undergraduates restricted)Instrument TrainingRoom Safety Orientation
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Getting Access to 13-4139
Contact meDiscuss your needsReserve the instrument together
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Spectroscopic Instrumentation at CMSE
Wed Jan 31, 10am-12:00pm, 13-2137No limit but advance sign up required (see contact below)
Signup by: 23-Jan-2006Single session event
The Center for Materials Science and Engineering's Analysis Shared Experimental Facility has an assortment of Spectroscopic instrumentation available for the use of MIT
researchers. These include FTIR, Raman, UV/VIS and Fluorimeter. There will be presentations on the instrumentation and the various measurement techniques
available.
Preregister via e-mail.Contact: Tim McClure, 13-4149, x8-6470, [email protected]
