Development of Small Shock Tolerant Mass Spectrometers MidYear Review F.S. Anderson University of Ha

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Development of Small Shock Tolerant Mass
SpectrometersMid-Year ReviewF.S. Anderson
University of Hawaii
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Basics

• New Mass Spectrometers for NBC Environmental
  Characterization
• University of Hawaii/HIGP
• Lead F. Scott Anderson (50)
• UH Personnel
• Eric Pilger Physicist (50)
• Gindi French - Engineer (50)
• Lloyd French - ME (25)
• Gary McMurtry - Spectroscopist (10)
• Karen Stockstill (Postdoc 50, but leveraged from
  NASA NAI)
• Sophie Fung (Fiscal Officer 50)
• Hiring 2 Physicists clerical help (50)
• Partners
• Southwest Research Institute MB-TOF Dave Young,
  Greg Miller
• Atom Sciences LA-RI-MS Tom Whitaker
• Sandia Shock Design Testing Tony Mittias
• Jet Propulsion Laboratory ESI-RFMS Advising
  Steven Smith

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Program Details

• Date of award 3/1/2005
• Date of receipt of funds 10/26/2005
• Date work actually started 11/1/2005
• Percent of work completed to date 15
• Processing of subcontracts PO's lagging

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Summary Focus on Strengths
X
X
?
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LA-RI-MS

• Goal
• In-situ high resolution isotope measurements
• Simple sampling strategy
• Requirements
• Small size
• Low power
• Solutions
• Laser ablation
• Resonance ionization to obtain selectivity
• High resolution MS (MB-TOF)

Elements and RI schemes
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How LA-RI-MS Works

• Laser ablation gt
• 99.9 Neutrals
• 0.1 Ions
• Remove or measure ions
• RI remaining neutrals
• Detect with MS

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How LA-RI-MS Works

• All elements possess unique energy levels
• Specific energy required to raise e- to each
  level
• Use set of tuned lasers to stimulate unique
  excitation steps for a given element
• More lasers provide more selectivity
• Applied to gas phase

Example of Sr RI Bushaw Cannon, 1997
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Applications

• Technology could be applied widely
• Provide 3 examples of applications
• Geochronology
• Extremely difficult isotopic measurement
• Requires precise measurement of large of atoms
• Forensics
• Trace analysis of explosives or other materials
• Geolocation
• XXX
• Currently discussing applications with Boeing
  Cubic

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Application Rb/Sr Geochronology
l1.42x1011y1

• Requirement
• ID 87Rb-87Sr R300K
• 87Sr/86Sr .02
• 87Rb/86Sr 1

Faure, 1986
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LA-RI-MB-TOF Method
Sr RI MS test, error 0.17, but integration time
x103 low, final error x30 better

• Separation of 87Rb-87Sr
• Resonance Ionization
• Ionizes only a single element
• Removes isobaric interference
• Enables 87Sr/86Sr .02
• 87Rb/86Sr 1 Laser Ablation
• Proven to 0.6
• Using UV or fs/ps laser
• Challenging Rb-Sr measurement possible
• Can tune bench top system other isotopes

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Application Forensics
Sr87/Sr86 map of UK

• Stable isotopes
• Geolocation
• Trace analysis
• Principle Fractionation
• Geologic
• Weather
• Hydrology
• Similar to geochronology
• Ratios (0.704-0.720)
• Abundances
• Track Identify
• Organisms
• Explosives
• Water

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Application XXX
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Key Technical Advances

• Goals - Year 1
• Demonstrate method in lab
• Build miniature MS
• Key technical areas for in-situ use
• Laser ablation (LA)
• Creation of sufficient sample
• Avoiding fractionation of sample
• Tune pulse power, length, and wavelength
• Mass separation using LA
• Development of high resolution miniature TOF

• Key technical areas (cont.)
• Mass separation with RI
• RI with minimal number pulses (power)
• Pulse length (power)
• Laser development
• Laser tuning
• Detectors
• MCP dynamic range
• ADC or TDC
• All have been done before - but none with focus
  on in-situ application requiring tuning of all
  parameters

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Completed Lab for LA-RI-MS
All deliveries within next 2 weeks!
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Scope of Work

• Laser ablation
• In-situ systems available, but
• Ablation process critical
• Part of our research on optimizing ablation
• High powered lasers for resonance ionization
• Foreign in-situ systems available, but very
• Part of our research on better designs
• High resolution MS for in-situ use
• Part of our research on MS called MB-TOF
• High speed detectors for in-situ use
• Part of our research focuses on MCP and DAQ
  requirements
• Part of our research is on system integration

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Laser Ablation Fractionation

• Used for a variety of targets (silicates, oxides,
  carbonates, phosphates, metals, sulfides)
• Minimal sample preparation
• Beam diameter 0.01-0.5 mm, spatial resolution for
  analysis of sub-domains of individual grains
• Ablated layer thickness 0.1-1000s nm

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Impact of Laser Ablation Sampling

• Robust LA analysis aided by stoichiometric
  ablation
• The extent to which this can be achieved depends
  in part on
• Laser characteristics
• wavelength, photon energy, power density
• Ablation pit development
• down-hole inter-element fractionation
• Ambient gas
• Particle formation (composition, size, timing)
• Beam delivery optics
• Uniformity, divergence

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l Laser Ablation

• UV very high photon energy (e.g. ArF excimer
  6.4 eV)
• Absorbed efficiently by a diverse range of
  materials, include many wide band-gap phases
  (e.g. plagioclase, calcite, quartz,)

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Thermal vs Mechanical Ablation
Strong absorber Photothermal ablation
Poor absorber Photomechanical ablation
Photomechanical ablation _at_ 266nm
Photothermal ablation _at_ 193nm
calcite
NIST 612
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Particulate Condensates Bad

• Desired
• High fluence
• Short l
• No atmosphere
• Minimal pulsing

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Ablation Lasers Available

• European LA-TOF MS
• IR small TOF limit results
• Ablation Megachip design
• 1064 or 532 nm available
• 1 ns pulse
• 12 ?J / pulse
• 7 kHz
• Ablates microns / shot
• We are currently working on designs at other
  wavelengths and power levels
• Concepts Research Corporation
• Engineered Megachip

Rohner et al, 2004
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Microlaser Technology
Microchip Size 1 mm3
US Patent No. 5,394,413 Passively Q-Switched
Picosecond Microlaser by Zayhowski
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1-Pass 2-Stage Microchip YVO4 Amp

• Previous designs demonstrate amplification of up
  to 5-10X amplification/stage

J.J. Zayhowski and A.L. Wilson, Jr.,
Energy-scavenging amplifiers for miniature solid
state lasers, Yelena Isyanova, Kevin F. Wall,
John H. Flint, Peter F. Moulton, and John J.
Degnan, High-Power, Short-Pulse,
Compact SLR2000 Laser Transmitter,
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1-Pass 2-Stage Microchip YVO4 Amp

• Initial 2-stage prototype
• Water cooler
• Based on available parts
• Limited shot system will utilize air cooling
• Un-optimized performance
• Energy 185uJ/Pulse
• Pulse Width 720ps
• Optical Power 204mW
• Optical Gain 18.5X

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5 Pass 3-Stage Amplifier
Amplifier Stages
Microchip Laser
Phase Control Waveplates
Isolator to prevent frequency shifting due Cr4
Photo-Bleaching from re-imaged back reflected
light
Diode Bar
NdYVO4
NdYVO4
Diode Bar
Average energy use 5 x 3V x 40 A x 10 ns 6
mW Even if efficiency 10-4 60 mW
NdYVO4
Diode Bar
5
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RI High Power Lasers

• RI requires on the order of 1 mJ/pulse
• In-situ high powers lasers can be built LIBS
• NdYAG
• 85 mJ
• 10 ns pulses
• 0.1 Hz
• 1 kg
• Solar panels
• Wiens et al, 2002

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Principle of MB-TOF-MS

• Multiple bounce path
• Higher resolution in a smaller instrument
• Initial testing with EI source
• Orthogonal
• Storage

M/?M t/?t L/?t
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Each Bounce Increases Resolution
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Peak Width Maintained

• In spite of longer effective flight tube
• Peak width maintained
• RTOF principle

2 Bounces, 100 ns FWHM
16 Bounces, 100 ns FWHM
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Signal Loss Low Per Bounce

• Expect ion loss with each bounce
• Due to longer effective flight path
• Results better than expected

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6 Bounce Ar spectrum R10K

• Started R2K
• Last time R10K
• Excellent resolution, but
• Required significant tuning for each mass
• Low signal

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Original Orthogonal Source

• Ion beam burn on
• Electropusher
• Extractor plates
• Electroformed grids
• Suggests that e- beam
• Not well defined
• Sprays onto the grid surfaces
• Solution Build storage source
• More ions, better focus over all masses
• But more energy dispersion

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New Storage Source
New assembled electron impact storage ion source
is compact, has less capacitance, can be
heated,magnets are well-aligned and separated by
only 25 mm
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Layout with Storage Source
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MB-TOF Resolution Progress

• RM/dMt/2dt
• Critical minimize dt
• Orthogonal source
• Could be hand tuned to 8-10 ns for one mass
• New storage source
• Increases resolution over whole mass range
• Typically 20 ns without tuning
• Better preamplifier resulted in reduction to 8 ns
• Further tuning will be better yet
• Reduce ringing

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ZZ-TOF

• Outgrowth of MB-TOF
• Easier to measure all masses simultaneously
• Lower power
• No pulsing
• Smaller

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Detector DAQ

• Requirements for our 3 potential applications
• Large 's of ions (105)
• High precision measurement (5000 13 bits)
• Short pulses (10-1000 ns)
• Averaging 100 pulses per measurement
• Reduces precision by x10 (9 bits)
• Solutions
• Hybrid ETP discrete dynode detector
• Aqiris ADC 8 GS/s, 10 bits

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New Detector Directions

• Current plan ADC
• Traditionally good for high ion counts
• However
• High power (10W)
• Slow (500 ps)
• Moderate bit-depth
• Option TDC
• Traditionally good for low counts
• Recently demonstrated for up to 106 ions
• Advantages
• Low power (10mW)
• Fast (lt50 ps)
• High bit-depth

Note lt50 ps peak
New SWRI TDC Design
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Laboratory LARIMS Design
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In-Situ LARIMS design
Non-Linear Crystal Carriage
KTP
BBO
NdYVO4
KTP
BBO
Microchip Laser
NdYVO4
Relay Lens System/ wave-plate
NdYVO4
Ablation Red Ionized Blue Neutral
0101
Sample
High speed DAQ
Selective Ionization of Neutrals
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Multi-Bounce Time of Flight
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LARIMS Results Summary
Extensive leveraging of late NASA PIDDP funds
(arrived 11/05) Ongoing leverage from NASA NAI,
ONR IED Program Work transitioned from NSF to
Partnership Program
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Honest Assessment

• Downside
• About 3 months behind on spending profile
• Takes 1-2 months for accruals to transit UH
  subcontract system
• Spending will catch up
• Sought initial data for this review
• Upside In first 3 months
• Construction complete
• AF, MHPCC contracting substantiation complete
• All purchases and most deliveries complete
• Subcontracts almost complete
• New hiring begun
• Team meeting
• Preliminary design review
• Initial construction underway

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