WIRMS5, Banff, Canada, September 2009

VACUUM FT-IR SPECTROMETERS FOR SYNCHROTRON APPLICATION

Guenter Zachmann R&D Product & Application Manager Bruker Optics, Germany

Motivation and Outline

FT-IR vacuum product line Vacuum benefits Optics bench features and accessories Design of the dedicated interferometers Performance demonstration by spectra IR beam line installation examples

R&D Vacuum Optics Product line

VERTEX 70v (2008)

IFS 125HR (2003)

VERTEX 80v (2006)

VERTEX 70v: Advantages by Synergy

Mechanical and optical components are compatible to VERTEX 70 purge version and VERTEX 80v:

Interferometer specific (RockSolidTM) components and specifications are identical to VERTEX 70 purge version: beamsplitter (e.g. solid state far IR), spectral resolution and range, Rapid- and Step-Scan options, etc. In general identical: mirrors, sources, detectors, electronics, automation and software Design of the vacuum housing is identical to VERTEX 80v: windows and window flanges, automatic sample compartment shutters, Bolometer connectors, vacuum pump, etc. Significant price advantage compared to VERTEX 80v

Vacuum Series in Comparison

VERTEX 70v
Spectral range Spectral resolution Interferometer Rapid Scan StepScan TRS 28.000-10 cm-1 (opt.) down to <0.16 cm-1 RockSolid >58 Spectra/Sec@ 16 cm-1 6 sec internal ADC 2.5/4 nsec with TRB 14bit 24bit, real dual channel ca. 100 Kg

VERTEX 80v
50.000-5 cm-1 (opt.) down to <0.06 cm-1 UltraScan >110 Spectra/Sec@16 cm-1 6 sec internal ADC 2.5/4 nsec, TRB 14bit 24bit, real dual channel ca. 110 Kg

IFS125HR
>50.000-5 cm-1 (opt.) down to <0.0007cm-1 Cube Corner interferom.

Interleaved TRS, down to 2.5/4 nsec with TRB 14bit 24bit, real dual channel ca. 600 Kg

Analog Digital Converter (ADC) Weight

Benefits of a vacuum optics

0.6 0.0 0.1 0.2 Single channel 0.3 0.4 0.5

1030 mbar 396 mbar, ~0.5 min 140 mbar, ~1 min 35 mbar, ~1.5 min 3 mbar, ~3 min ~0.1 mbar, ~5 min

7000

6000

5000

4000 3000 Wavenumber cm-1

2000

1000

Vacuum Optics: For Demanding Applications

Significant vacuum advantages for following applications Measurements of very small band intensities e.g. mono-layers Rapid and Step Scan application slow (hours) to very fast (nanosec) reaction processes High resolution measurements vapor phase and impurities in semiconductors at LT Far-infrared analysis e.g. farest IR/terahertz spectroscopy down to 5cm-1 External UHV-chamber adaptation e.g. CVD and ALD nano-science Coupling to IR beam lines @ Synchrotron sources e.g. Ellipsometry, Ultra High resolution, microscopy

Benefits of a vacuum optics

0.004

VERTEX 70 weak bands are masked by water vapor & CO 2 VERTEX 70 automatic water vapor & CO 2 compensation VERTEX 70v no water vapor & CO 2 artifacts

0.003

Absorbance Units 0.001 0.002

80 reflection unit sample spot size <9mm measurement time 2min

0.000 -0.001

customer sample: SAM mercapto alkane acid reference: deuterated alkanethiol

3500 3000 2500 2000 1500 1000

4000

Wavenumber cm-1

Benefits of a vacuum optics

0.0010

VERTEX 70 VERTEX 70 automatic water vapor & CO2 compensation VERTEX 70v 2 x 10-4 AU (0.02%T)

-0.0004 -0.0002

Absorbance Units 0.0000 0.0002 0.0004 0.0006

0.0008

CH2/CH3 (sample)
3000 2500

Carboxylic acid (sample) deuterated (reference)

2000 Wavenumber cm-1 1500 1000

Outstanding Optics Beam Path Flexibility

VERTEX series internal apt.&filter wheel Inputs at rear and right side Input beam passing apt. &filter wheel

2 internal detec. Exits left and front

2 internal sources

Exits right and front

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VERTEX Vacuum Optics

QUICKLOCK SAMPLE COMPARTMENT Vacuum O-rings (EMV compatible)

AAR

Automatic sample compartment shutters and/or windows Removable front cover VERTEX compatible flanges and threads

QuickLock

QuickLock release button

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Optional Sample Compartment Telescope

minimum space
suited e.g. for: pellets and foils, especially in Far IR compact accessories and small gas cell temperature controlled liquid cells

maximum space

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External Measurement Modules

A large number of accessories/modules are available

XSA external sample chamber on the right- or left side As well in vacuum version HYPERION 2000/3000 for IR microscopy and FPA imaging RAMII FT-Raman and RamanScopeIII FT-Raman microscope HTS-XT module for high sample throughput Photoluminescence (PL) module PLII Polarization Modulation module PMA50

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VERTEX 70-70v: RockSolidTM Interferometer

State-of-the-art technology: Same type of retro-mirrors like in the IFS125HR

Cube Corner mirrors: permanently aligned Angle accuracy: better than 0,001 deviation=1cm over 1km only! Wear-free bearings based on crossed steel springs, like a clockwork

US Patent No 5.309.217

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VERTEX 80-80v: UltraScanTM Interferometer

21 - design providing higher throughput and efficiency actively aligned friction free linear air bearing automatic BMS alignment Resolving power better than 300,000:1 Rapid Scan with more than 110 spectra/sec Step Scan temporal resolution down to 2.5/4 nsec

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VERTEX 80-80v: UltraScanTM Interferometer

Additional mirror inside the moving mirror interferometer arm is used to actively correct possible tilt errors: Interferogram is fixed on the detector No additional signal modulations are created

The Right Way of Active Alignment

No side band artifacts No additional noise

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Ultra High Resolution and Beam Path Flexibility

IFS 125HR Hybrid scanner Modular scanner chamber design up to 4 internal 2 sample and 2 external compartments detectors Modified Michelson interferometer using permanent aligned cube corner mirrors Up to 3 internal watercooled sources and 1 external input

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IFS 125HR: Interferometer

Scanner Drive Device

Hybrid Scanner Moving mirror is translated on a hybrid bearing Allows for a beam integrity over extremely long OPD (>11m)

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Detector Technologies
Patented DigiTectTM MCT-detector

True 24-bit dynamic range

16.777.216:1 (!)

Parallel dual-channel technology Integrated detector electronics Reproducible exchange due to dove tail mount Automatic recognition and check

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VERTEX 80v: Er doped LiYF4 UV/VIS/NIR range and CaF2-BMS

0.5 0.4 Absorbance Units 0.0 45000 0.1 0.2 0.3

GaP, Deuterium lamp GaP, Tungsten lamp Si diode, Tungsten lamp MCT D316, Tungsten lamp

40000

35000

30000

25000 Wavenumber cm-1

20000

15000

10000

5000

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VERTEX 70v: FIR/THz Measurement Solid State BMS, Internal Source, RT Detector
649.31 625.38 604.28 519.00 503.61 464.35 413.62 391.59 362.45 339.88 217.62 169.86 144.30 118.70 98.85 68.95

1.4

1.6

Absorbance Units

8 mg Paracetamol in 220 mg PE (500 mg in 650 mg formulation)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

600

500

400 Wavenumber cm-1

300

200

100

30

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SPECTRAL PEAK RESOLUTION:CO

VERTEX 80-80v: High Resolution in the MIR

CO vapor: CO stretching vibration rotational R- and P-branch transitions
0.06

R-branch

P-branch

0.04

-0.01

Proof of High Resolution Performance <0.06 cm-1 C12O16

-0.00 2250 2200 2150 Wavenumber cm-1 2100 2050 2000

0.05

Line width at half height

Absorbance Units 0.02 0.03

0.01

Absorbance Units 0.02 0.03

0.04

0.05

2200

cm-1

2000

< 0.060 cm-1

C13O16 C12O18
Natural abundance: C13 1.1%; O18 0.2%
2125 2124 2123 2122 Wavenumber cm-1 2121 2120 2119

-0.01

0.00

0.01

isotope splitting!

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SPECTRAL PEAK RESOLVING POWER: IODINE

VERTEX 80-80v: Resolving Power /

Iodine Vapor: Rotation vibrational electronic B X transitions in the visible spectral range Proof of Resolving Power / >300.000:1
0.11 0.10 0.12 0.13

19200

19.200 cm-1

19000

18800

18600 Wavenumber cm-1

18400

18.200

18200

18000

0.05

0.06

0.07

Si ngle channel 0.08 0.09

<0.06 cm-1

18.341,137 cm-1
18341.14

18.342 cm-1
18341.8

0.04

18341 .6

183 41.4

18341.2

18 1.0 34

W avenum cm ber -1

18.340,7

18340.8

18340.6

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VERTEX 80-80v: Fastest Rapid Scan TRS

Combustion of Butane
Required Options Rapid Scan LN2 cooled MCT Optical filter @3900cm-1 OPUS 3D

Proof of Highest Scan Speed! 800spectra@6.93 sec ~115spectra/sec Scanner VEL=320 kHz 16 cm-1 spectral res.
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The IFS 125HR: Ultra High Resolution

Major features Very high spectral resolution: <0.00068 cm-1 (OPD up to 1170 cm!) Resolving power of >106:1, relative wavenumber precision <10-7 Very broad spectral range: 550,000 cm-1 High flexibility due to modular design (separate vacuum cabinets) State of the art electronics: dual-channel 24bit ADC, Ethernet, Results in an instrument line shape close to the theoretical limits IUPAG high resolution vapor phase reference spectra are acquired on the IFS 120HR !

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IFS125 HR: Vacuum Spectrometer Lineshape

1.0

0.8 Transmittance

0.6

HBr absorption line measured at 0.0035cm-1 resolution: 08/10/02 H276SHBR Very close agreement with the calculation (red) Difference spectrum (blue) ca. 15x expanded in T%-scale
0.02 0.01 0.00 -0.01 -0.02 2606.0 Residual Resolution: 0.0035 cm bef DTC, A-side, forward Obs Calc
-1

(OPD: 257 cm)

0.4

0.2

0.0

2605.6

2605.7

2605.8 Wavenumber [cm

-1

2605.9 ]

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Applications of HR Spectroscopy
Atmospheric Research Stratospheric trace gases Absolute line strength of atmospheric gases Radiative transfer through the atmosphere Physical Chemistry Ro-vibrational spectroscopy Determination of molecular dynamics Spectroscopy of molecular crystals at low temperatures Hollow cathode molecular emission Semiconductor and physical Applications Impurities at low temperature Magneto optical splitting
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IFS 125HR: Semiconductor Research

Impurities in single crystal GaAs at low temperatures Carbon

Boron

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Microscopy and IR beam lines

VERTEX 80v with HYPERION 3000 IR beamline e-Synchrotron, Melbourne, Australia

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Ultra High Resolution and IR beam lines

IFS 125HR at Canadian Light Source (CLS), Saskatchewan

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Ultra High Resolution and IR beam lines

IFS 125HR at Paul Scherrer Institute, Villigen, Switzerland

Optical Path Difference (OPD): 1170 cm (11 chambers)

Spectral resolution: 0.00063 cm-1

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Synchrotron THz and NIR in Parallel

BessyII & Berlin Germany Frascati Rom Italy

See recent publication in the Journal Phys. Chem. Vol. 13, Nr.34, August 2009

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www.brukeroptics.com

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