New Mass Spectrometers University of Hawaii 2005 Partnership Project

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New Mass SpectrometersUniversity of
Hawaii2005Partnership Project
UNCLASSIFIED
3/2007 NCMR Technology Review
F. Scott Anderson
This presentation is classified UNCLASSIFIED
UNCLASSIFIED
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Project Information

• New Mass Spectrometers for NBC Environmental
  Characterization
• University of Hawaii/HIGP
• Lead F. Scott Anderson (50)
• UH Personnel
• Eric Pilger Physicist (50)
• Keith Nowicki Physicist (100)
• Sarah Sherman Geochemist (100)
• Jeffrey Bosel Physicist (100)
• Gary McMurtry - Spectroscopist (10)
• Karen Stockstill (Postdoc 50, but leveraged from
  NASA NAI)
• Sophie Fung (Fiscal Officer 50)
• Malie Smith - Clerical (50)
• Partners
• Southwest Research Institute MB-TOF Dave Young
  (10), Greg Miller (50)
• Atom Sciences LA-RI-MS Tom Whitaker (20)
• Sandia Shock Design Testing Tony Mittias
  (15)
• Jet Propulsion Laboratory ESI-RFMS Advising
  Steven Smith (20)

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Program Details

• Date of award 3/2005
• Date of receipt of funds 11/2005
• Date work actually started 11/2005
• Percent of funds spent to date 90
• SwRI (50)
• Atom Sciences (100)
• Sandia (100)
• JPL (50)
• Percent of year 1 work completed to date 100
• SI not undertaken per MASINT ESI - RFMS rescoped

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Plan Status
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Objectives

• EI/ESI RFMS
• RFMS New mass filtering method
• EI Atmospheric chemistry
• ESI Applied under simpler in-situ relevant
  conditions, I.e. vacuum
• Leverages NASA MIDP
• LA-RI-MS
• RI-MS to in-situ ultra-sensitive isotope
  detection
• New MBTOF MS
• Leverages NASA PIDDP, NAI, ONR IED

• Outline
• RFMS
• Previous results
• Current progress
• Future direction
• LARIMS
• Previous results
• Current Progress
• Future direction
• Program direction

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Part 1 EI-RFMS
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RFMS Principle
Detector - FC - Imager
Mass Disperser - 4 pole - 8 pole
Ionizer - Filament - EGA
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RFMS Previous Work

• Modeled principle
• Demonstrated technique
• Simultaneous measurement of masses
• No upper mass limit
• Inherently rugged
• Ballistic emplacement potential
• Moderate resolution
• ESI less relevant
• Focus on increasing resolution in full size design

Resolution 5
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RFMS Previous Work
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Previous Status

• Improve 4 areas
• Ion source focus
• Better e- curtain
• Focus elements
• EGA ?
• Better einzel lens ?
• Smaller apertures ?
• Better mass dispersion ?
• Larger RF amplitude
• Enables larger dispersion
• Steering to measure beam beyond detector size
• More RF poles (8 vs 4)

• MCP / Imaging Detection ?
• Dramatic SNR increase
• Faster DAQ
• Higher resolution
• Better vacuum ?
• Last time Construction phase
• Now results
• 2,3,4 complete
• 1 underway

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1. Ion Source
Gas in

• Improvements
• FE modeling physical testing of electric fields
  has improved understanding
• Improved einzel lens design
• Smaller apertures
• Tested EGA
• Produces more focused e- beam
• To do
• Redesign to increase transmission efficiency
• Focus e- from EGA or filament

Ions out
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1. Ion Source

• EGA Ion signal 1000x lt filament OK with ion
  imagers
• Run away behavior above 5e-5 torr
• Power consumption 1000x lt filament

Electron Gun Array
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2. Better Mass Dispersion

• New RF electronics
• Higher amplitude RF
• 8 poles, not 4
• FE model prediction
• More dispersion
• More uniform rings

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3. Imaging Detectors

• Purchased MCP/Phosphor ion imager
• Interfaced frame grabber with existing software
• 10 frames/s (720x480x15 mm) per second
• Single ion sensitivity (50-100 mm blob)
• Pressures lt 10-6 torr
• First pass at reduction techniques for spectral
  cube

2.7 cm
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4. Vacuum System

• New vacuum chamber is an enabling test bed
• Vacuum getter
• Solid state
• Shock tolerant
• Renewable
• Testing in UH submersible test bed
• Also considering
• Creare mini-turbo's
• Pre-pumping scenarios

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Results 1 Pixel RFMS

• FC43 air
• Mass peaks from 50-600
• Single pixel faraday cup
• 3 Minute acquisition
• Low resolution
• Noisy
• Low sensitivity
• Physically robust
• Proof of principle

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Result FC43 Imaging RFMS
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RFMS 2006 M10-300, R5, SNR10

• First results
• Highly linear
• Single radial
• Better SNR available
• 1 pixel detector
• Scanned over 3 minutes
• R 3-5
• Can't separate O,N2
• SNR 10
• M 10-300

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RFMS 2007 M0.1-600, R10, SNR1000

• Imaging detector
• R8-10
• SNR 1000
• M 0.1-600
• Air
• FC43
• Pump oil

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Sandia Shock Testing
Filament
Ceramic

• Passed 5000-g shock test
• RFMS Ceramics
• Filament
• Failed
• Vacuum chamber
• CF Cu gaskets
• Fix with welded flanges

5000-g shock table
Vac Chamber CF KF
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RFMS vs SOA
1
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Future Work

• Redesign ion source
• Better focus
• Higher throughput
• Pursue CMOS ion imager
• Each pixel DNR 106
• Independently adjustable
• Small, shock tolerant
• Seeking funds
• Larger RF amplitude mod to electronics
• Greater dispersion
• Steering Off axis dispersion

Courtesy Bonner Denton, Univ. AZ
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Part 2 LA-RI-MS
UNCLASSIFIED
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High Precision Isotopic Ratios

• Useful for tracking objects, dating them
• P 5000 on 1 ppm
• Disaggregate sample
• Generate separates
• Density
• Magnetically
• Hand-pick
• Dissolve
• Condense into disks
• Measurement with large sector MS or SIMS
• Cannot be miniaturized
• Wet chemistry
• Sensitive option LA-RI-MS
• 2 Modes

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LA-RI-MS vs SOA
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How LD-MS Mode Works
Laser Desorption Mass Spec

• Laser desorption
• Technically laser ablation (gt1GW/cm2)
• 99.9 Neutrals
• 0.1 Prompt Ions
• Measure ions
• Neutrals not detected
• Detect with MS
• Bad significant fractionation

UV Laser gt 1GW/cm2
Mass Spec
Sample
Prompt Ion Trap
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How LD-RI-MS Mode Works
Laser Desorption Resonance Ionization Mass Spec

• Laser desorption
• 99.9 Neutrals
• 0.1 Prompt Ions
• Remove prompt ions
• RI remaining neutrals
• Only selected element (Sr or Rb) ionized
• Detect with isotopes with MS

Tuned only for Sr or Rb
Resonance Ions
Sample
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Resonance Ionization

• All elements possess unique energy levels
• Unique energy (l) to raise e- to each level
• Use set of tuned lasers to stimulate 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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LA-RI-MS Previous Work

• System Overview

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LA-RI-MS Previous Work
1 mm
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LA-RI-MS Previous Work

• Celestite LARIMS (note scale 0.12V)

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Findings

• 460, 554 at 2-5 mJ
• 2 photon ionization from power in 554
• 1064 not required, may reduce lasers from 3 -gt 2
• 1st light precision
• 87Sr/86Sr 0.7347 /- 0.08
• Sought /- 0.0002
• Fixes
• Ablation
• Smaller ablation spot size ?
• Lower power ?
• Jitter

• Mass Spectrometer
• Better TOF Tuning ?
• New MCP's on TOF ?
• 4 GS/sec 10 bit DAQ board ?
• Removing prompt ions (LAMS) from RI ?
• Resonance ionization
• Implementing laser attenuation ?
• Power fluctuations from ablation jitter

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1. Ablation

• Aligned optics to 50 mm
• Attenuated beam to control ion production

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1. Ablation - 3 targets
Basalt Glass 100 ppm
Celestite 2e5 ppm
Basalt 1000 ppm
Ablation rate much lower in basalts
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2. Mass Spec Improvements

• Better TOF Tuning
• 4 GS/sec 10 bit DAQ board
• New MCP's on TOF
• Removing prompt ions (LAMS) from RI
• Required higher voltage than expected
• LA ions had more energy than anticipated

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3. RI Attenuation
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Better Quality of Measurements
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Better Average Results
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Basalt Glass (100 ppm Sr)
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Quality of RI vs Ablation
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Ablation Power Variation
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Spectra Quality vs Quantity
StdDev of Mean
Fewer Spectra
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Experiments for 3 Samples
20X better than previous result
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Assessing Performance
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Measured vs Goals
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Desired Precision
Achievable!
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Remaining Issues
UV Laser gt 1GW/cm2

• Degradation of RI signal at high LA power
• High LA power desirable to reduce overall of
  shots, but
• Not all LA ions removed
• Off axis ablation generates high charge region
  that adversely deflects RI ions
• RI ion creation 1 cm from sample
• Intersects minimal part of ablation gas ejecta
• LA jitter causing adverse RI power variation

Off axis
Sample
RI Lasers
Non-ideal separation intercepts less of gas
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12. MS Transmission Efficiency

• Off-axis LA reduces efficiency
• New optics being installed to target axis
• Increase ion generation hence precision
• Rental RTOF cannot handle ion energy distribution
• MB-TOF energy focusing mirrors
• Designed for LA energy distribution
• Delayed until September, but, get miniaturization
  and initial NASA flight qualification free!
• Position of RI beams
• New optics currently being installed

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3. LA Jitter

• Custom 206 nm laser
• lt 1 ns pulse
• High peak power
• 25 W in, TW out
• Built in attenuator
• Size 16 x 18 cm!
• No poison gas
• 1 ns jitter

206nm Ablation Laser Schematic
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3. LA Jitter
YbYAG Breadboard Fundamental Output _at_ 1030 nm _at_
0.3 mJ
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3. LA Jitter
High Doped 6 mm 10 YbYAG Crystal
Passive Q-switch Output Coupler
25 Watt 940 nm Pump
25 Watt 940 nm Fiber Pump Source for 206 nm Laser
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Future Work

• Due to reduced funds, we will delay
• A low risk but shoebox sized tunable RI laser
  system (YAG OPO)
• Higher risk flashlight sized tunable RI laser
  system (solid state)
• Smaller redesign for MB-TOF called ZZ-TOF
• ESI with MB-TOF
• However, may leverage other funds in Sept 07

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Side-by-side summary
Tasks as defined by contract
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Progress

• Publications (7 conference presentations)
• Stockstill, K., Anderson, F.S. , E Pilger, G
  McMurtry, L French, A Rugged Miniature
  Mass-Spectrometer for Aqueous Geochemistry on
  Mars, American Geophysical Union, Fall Meeting,
  2005.
• M M Osterloo, F S Anderson, T Whitaker, G Miller,
  D Young, J Mahoney, M Norman, A LASER RIMS
  Instrument to Date Igneous Rocks using Rb-Sr and
  Measure Elemental Chemistry, American Geophysical
  Union, Fall Meeting, 2005.
• F. S. Anderson, T. Whitaker, G. Miller, D. Young,
  J. Mahoney, and M. Norman, L. French, A LASER
  RIMS INSTRUMENT TO DATE IGNEOUS ROCKS USING RB-SR
  AND MEASURE ELEMENTAL CHEMISTRY, abstract no.
  1843, LPSC XXXVI, 2005.
• L. C. French, F. S. Anderson, G. McMurtry, E.
  Pilger, J. Stopar, A RUGGED MINIATURE
  MASS-SPECTROMETER FOR MEASURING AQUEOUS
  GEOCHEMISTRY ON MARS, abstract no. 2138, LPSC
  XXXVI, 2005.
• Anderson, F.S., New Mass Spectrometer Designs for
  Astrobiology Applications, Invited Talk at NASA
  Astrobiology Institute Executive Council meeting,
  2005.
• Anderson, F.S., Ruggedized Nanospray RF Mass
  Spectrometer for Environmental Characterization
  and Biomolecule Detection, Bioastronomy
  Conference, 2004.
• Anderson, F.S., et al., A LASER RIMS Instrument
  to Date Igneous Rocks, Measure Geochemistry,
  Characterize Alteration in-situ on Mars, American
  Geophysical Union, Fall Meeting, 2002.
• Patents (0, two planned)
• 2 Manuscripts in preparation

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Experiments

• RFMS last 6 months
• 30 tests of ion transmission and detection
• 20 imaging tests
• 20 imaging DAQ's for spectral characterization
• LARIMS last 6 months
• 20 LAMS tests
• 50 LA-RI MS tests
• Of these, the following DAQ tests completed
• 8 Celestite tests
• 3 Basalt tests
• 7 Basalt glass tests

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Summary Assessment

• RFMS
• Basic physics well understood (year 1)
• Initial testing of optimized components underway
  (year 2)
• Ion imager
• 8 pole disperser
• Vacuum subsystems
• DNR/SNR 100x better
• R 2x better
• Mass range improved
• Components to 5000-g
• LARIMS
• Many experiments
• Optimized power
• 20x better precision
• 200K, 1K, 100 ppm samples

• Issues
• Reduced funding slows year 2 development of key
  components for breadboard delivery
• CMOS ion imager
• Sandia shock testing
• Miniature pumps
• Miniature RI lasers
• ESI ZZ-TOF
• Cannot meet original plan
• Not all bad More time to optimize!
• Other Progress
• Contracting complete
• Hiring complete