WIRMS5, Banff, Canada, September 2009VACUUM 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 2 R&D Vacuum Optics Product line VERTEX 70v (2008) IFS 125HR (2003) VERTEX 80v (2006) 3 Significant price advantage compared to VERTEX 80v • • • 4 . In general identical: mirrors.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. etc. sources. electronics. detectors. spectral resolution and range. automation and software Design of the vacuum housing is identical to VERTEX 80v: windows and window flanges. etc. Rapid. solid state far IR).g. automatic sample compartment shutters.and Step-Scan options. Bolometer connectors. vacuum pump. 110 Kg IFS125HR >50. 600 Kg Analog Digital Converter (ADC) Weight 5 .0007cm-1 Cube Corner interferom.5/4 nsec with TRB 14bit 24bit. Interleaved TRS. real dual channel ca. real dual channel ca.06 cm-1 UltraScan >110 Spectra/Sec@16 cm-1 6 µsec internal ADC 2.5/4 nsec.16 cm-1 RockSolid >58 Spectra/Sec@ 16 cm-1 6 µsec internal ADC 2. TRB 14bit 24bit.000-10 cm-1 (opt.Vacuum Series in Comparison VERTEX 70v Spectral range Spectral resolution Interferometer Rapid Scan StepScan TRS 28.) down to <0.5/4 nsec with TRB 14bit 24bit. real dual channel ca.000-5 cm-1 (opt.) down to <0. 100 Kg VERTEX 80v 50.000-5 cm-1 (opt.) down to <0. down to 2. 2 Single channel 0.1 0.5 min 140 mbar. ~1 min 35 mbar. ~3 min ~0.1 mbar.4 0.6 0.Benefits of a vacuum optics 0.0 0. ~5 min 7000 6000 5000 4000 3000 Wavenumber cm-1 2000 1000 0 6 .3 0. ~0.5 1030 mbar 396 mbar. ~1.5 min 3 mbar. g.Vacuum Optics: For Demanding Applications Significant vacuum advantages for following applications • Measurements of very small band intensities e. Ellipsometry.g. CVD and ALD nano-science • Coupling to IR beam lines @ Synchrotron sources e. farest IR/terahertz spectroscopy down to 5cm-1 • External UHV-chamber adaptation e. Ultra High resolution. 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. microscopy 7 .g. 001 customer sample: SAM mercapto alkane acid reference: deuterated alkanethiol 3500 3000 2500 2000 1500 1000 4000 Wavenumber cm-1 8 .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 0.002 80° reflection unit sample spot size <9mm measurement time 2min 0.003 Absorbance Units 0.001 0.000 -0. 0008 CH2/CH3 (sample) 3000 2500 Carboxylic acid (sample) deuterated (reference) 2000 Wavenumber cm-1 1500 1000 9 .Benefits of a vacuum optics 0.0004 0.0010 VERTEX 70 VERTEX 70 automatic water vapor & CO2 compensation VERTEX 70v 2 x 10-4 AU (0.0002 Absorbance Units 0.0002 0.0004 -0.02%T) -0.0006 0.0000 0. &filter wheel 2 internal detec. Exits left and front 2 internal sources Exits right and front 10 .Outstanding Optics Beam Path Flexibility VERTEX series internal apt.&filter wheel Inputs at rear and right side Input beam passing apt. 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 11 . g. for: • pellets and foils. especially in Far IR • compact accessories and small gas cell • temperature controlled liquid cells maximum space 12 .Optional Sample Compartment Telescope minimum space suited e. 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 13 .External Measurement Modules A large number of accessories/modules are available • • • • • • • XSA external sample chamber on the right. 217 14 .309.001° deviation=1cm over 1km only! Wear-free bearings based on crossed steel springs.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. like a clockwork US Patent No 5. 000:1 • Rapid Scan with more than 110 spectra/sec • Step Scan temporal resolution down to 2.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 300.5/4 nsec 15 . 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 16 . 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 17 . 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) 18 . 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 19 . 5 0.1 0.0 45000 0.VERTEX 80v: Er doped LiYF4 UV/VIS/NIR range and CaF2-BMS 0. Tungsten lamp Si diode. Tungsten lamp MCT D316.2 0.3 GaP.4 Absorbance Units 0. Deuterium lamp GaP. Tungsten lamp 40000 35000 30000 25000 Wavenumber cm-1 20000 15000 10000 5000 20 . 31 625.4 0.2 0.62 391.0 1.86 144. Internal Source.61 464.6 Absorbance Units 8 mg Paracetamol in 220 mg PE (500 mg in 650 mg formulation) 0.38 604.95 1.8 1.VERTEX 70v: FIR/THz Measurement Solid State BMS.59 362.35 413.70 98.4 1.62 169.85 68.88 217.45 339.2 600 500 400 Wavenumber cm-1 300 200 100 30 21 .00 503. RT Detector 649.0 0.28 519.6 0.30 118. 06 R-branch P-branch 0.SPECTRAL PEAK RESOLUTION:CO VERTEX 80-80v: High Resolution in the MIR CO vapor: C≡O stretching vibration rotational R.04 -0.05 Line width at half height Absorbance Units 0.03 0.1%.01 0.01 Proof of High Resolution Performance <0.00 2250 2200 2150 Wavenumber cm-1 2100 2050 2000 0.2% 2125 2124 2123 2122 Wavenumber cm-1 2121 2120 2119 -0.02 0.01 isotope splitting! 22 .00 0.and P-branch transitions 0.01 Absorbance Units 0.06 cm-1 C12O16 -0.060 cm-1 C13O16 C12O18 Natural abundance: C13 1.05 2200 cm-1 2000 ∆ν < 0.03 0. O18 0.02 0.04 0. 08 0.14 18.06 cm-1 18.000:1 0.137 cm-1 18341.8 0.7 18340.11 0.200 18200 18000 0.10 0.06 0.07 Si ngle channel 0.4 18341.09 <0.2 18 1.8 18340.6 183 41.13 19200 19.SPECTRAL PEAK RESOLVING POWER: IODINE VERTEX 80-80v: Resolving Power ν/∆ν Iodine Vapor: Rotation vibrational electronic B ßàX transitions in the visible spectral range Proof of Resolving Power ν/∆ν >300.6 23 .200 cm-1 19000 18800 18600 Wavenumber cm-1 18400 18.340.05 0.04 18341 .0 34 W avenum cm ber -1 18.12 0.342 cm-1 18341.341. 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. 24 .93 sec ~115spectra/sec • Scanner VEL=320 kHz • 16 cm-1 spectral res. … Results in • an instrument line shape close to the theoretical limits • IUPAG high resolution vapor phase reference spectra are acquired on the IFS 120HR ! 25 .The IFS 125HR: Ultra High Resolution Major features • Very high spectral resolution: <0.000 cm-1 • High flexibility due to modular design (separate vacuum cabinets) • State of the art electronics: dual-channel 24bit ADC. relative wavenumber precision <10-7 • Very broad spectral range: 5–50.00068 cm-1 (OPD up to 1170 cm!) • Resolving power of >106:1. Ethernet. 01 -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.8 Wavenumber [cm -1 2605.6 2605.0 2605.01 0.4 0.00 -0.0 0.02 0.02 2606.7 2605.8 Transmittance 0.0 Residual Resolution: 0.2 0. forward Obs Calc -1 (OPD: 257 cm) 0. 15x expanded in T%-scale 0. A-side.9 ] 26 .IFS125 HR: Vacuum Spectrometer Lineshape 1.0035 cm bef DTC. 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 27 . IFS 125HR: Semiconductor Research Impurities in single crystal GaAs at low temperatures Carbon Boron 28 . Melbourne.Microscopy and IR beam lines VERTEX 80v with HYPERION 3000 IR beamline e-Synchrotron. Australia 29 . Saskatchewan 30 .Ultra High Resolution and IR beam lines IFS 125HR at Canadian Light Source (CLS). Switzerland Optical Path Difference (OPD): 1170 cm (11 chambers) Spectral resolution: 0.Ultra High Resolution and IR beam lines IFS 125HR at Paul Scherrer Institute.00063 cm-1 31 . Villigen. Synchrotron THz and NIR in Parallel BessyII & Berlin Germany Frascati Rom Italy See recent publication in the Journal Phys. Chem. Vol.34. Nr. August 2009 32 . 13. brukeroptics.com 33 .www.