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First detection of thermal ions and ion swarm imaging in a
  DT-IMS by means of a high spatial-resolution IonCCD™
                        Omar Hadjar1, Stephen Davila2, Gary Eiceman2
      1OI Analytical, CMS field product, Mass Spectrometry and Ion Imaging, Pelham, AL
            2 NMSU, Department of Chemistry and Biochemistry, Las Cruces, NM
Motivations
• To explore the capabilities of the IonCCD as a detector for IMS
• To extend detectability from keV down to thermal ions
• To provide real time, high density imaging of the ion swarm at
  ambient pressures.
• To determine the diffusion of ion swarms in the drift region
• To characterize optics for ions
• To obtain sufficient experimental data on ion motion under electric
  fields and form theoretical modeling and calculations
Introduction to the
IonCCD
Ring 1                                    Setup Schematics
                                                                                                         Ring 2                    of the DT-IMS
                                                                                                                           Ring 3

                                                                                                                               Ring 4

                                                                                                                                    Ring 5

                                                                                                                                        Ring 6

                                                                                                                                             Ring 7

                                                                                                                                                   Ring 8

                                                                                                                                                      Ring 9
                                                   9




                                                                                             IonCCD Housing
               Potential                       8
                                                                                                              1 2              3 4 5 6       7 8      9
                                           7




                                                                                                              Slit-Plate
                                       6
                                                         Detector board


                                   5
                                                                          Cold foot
       Slit-plate                                                                     Chip
                               4                       Femto-Amp
IonCCD housing
                           3
 IonCCD chip         2
                 1
                                           Distance
Experimental
                                                                     Setup


                                                          Ring stack of the DT-IMS



                                                           IonCCD in SS enclosure


                                                                            Camera box


                                                          IonCCD base lined signal




Picture shot while Stephen was changing the DT-IMS rings arrangement with
  the IonCCD ON and recording no ion signal but an unperturbed base line
IonCCD housing voltage bias effect
                         1000                                                                                             450
                                   3 kV DT-IMS                              IonCCD
                                                                            encosure
                                                                                                                                    3 kV
                                                                            bias:
                          800                                                     70V                                               2 kV
                                                                                  50V                                     400
                                                                                  30V
IonCCD signal (dN)


                                                                                  25V
                          600                                                     20V
                                                                                  14V                                     350
                                                                                  10V
                                                                                  6V
                          400
                                                                                  4V
                                                                                  1.6V
                                                                                                                          300




                                                                                         IonCCD integrated signal (kdN)
                                                                                  0.8V
                          200                                                     0.2V
                                                                                  0.1V
                                                                                  0V
                                                                                                                          250
                            0
                             -10         -5      0       5      10    15   20

                          500                                               IonCCD
                                   2 kV DT-IMS                                                                            200
                                                                            encosure
                                                                            bias:
                                                                                  70V
                          400                                                     50V
                                                                                  30V                                     150
    IonCCD signal (dN)




                                                                                  25V
                                                                                  20V
                          300
                                                                                  14V
                                                                                  10V                                     100
                                                                                  6V
                          200                                                     4V
                                                                                  1.6V
                                                                                  0.8V
                                                                                  0.2V                                     50
                          100
                                                                                 0V

                            0                                                                                               0
                             -10         -5      0       5      10    15   20                                                   0    20        40        60     80
                                                 IonCCD X axis (mm)                                                                 IonCCD enclosure Bias (V)

                                                     6 rings DT-IMS (pre-ring lens & slit disc)
Detection Efficiency
                     800                                                                                         400                                        80
                             IMS voltage (V)
                                  3000
                     700          2500
                                  2000
                                  1500
                                  1000                                                                           300                                        60
                     600
                                  500




                                                                                IonCCD integrated signal (kdN)




                                                                                                                                                                 FemtoAmplifier (pA)
                     500
IonCCD signal (dN)




                                                                                                                 200                                        40
                     400



                     300


                                                                                                                 100                                        20
                     200



                     100


                                                                                                                  0                                         0
                      0

                           -25 -20 -15 -10     -5   0   5   10   15   20   25                                          0   500   1000 1500 2000 2500 3000
                                    IonCCD coordinates (mm)                                                                      IMS voltage (V)
IonCCD vs. FemtoAmp response to the IMS ion throughput
                                                           350
                                                                     Equation     y = a + b*
                                                                     Adj. R-Squar   0.99793
                                                           300                                 Value       Standard Erro
                                                                     E            Intercept    -22913.3526   5498.23184
                                                                     E            Slope          5263.6508     119.6966
                                                           250




                                            IonCCD (kdN)
                                                           200

                                                           150

                                                           100

                                                           50

                                                            0
                                                                 0       5   10 15 20 25 30 35 40 45 50 55 60 65 70
                                                                                     FemtoAmplifier (pA)
    The integrated profiles are plotted here
  against the Femto-Amplifier response when
 operated at 1011 gain. This comparative study
     was conducted at same experimental
    condition with a 16x1mm2 slit plate and
     grounded IonCCD plate to expose both
 detection surfaces to the same ion beam cross
   section hence the same total ion current.
10000
                                                                             IonCCD detection efficiency at
                                                                             different IMS high voltage bias
IonCCD responce (ion/dN)


                                            noise floor (12 dN)
                           1000
                                                                            We observed a slight decrease of the IonCCD detection
                                                                            efficiency at lower IMS HV. This can be due to experiment-
                            100                                             to-experiment variation, or witnessing the effect of the
                                                                            floating pixels, during charge integration time, on the ion
                                                                            collection (retarding field effect).
                             10


                                                                                                  10000
                              1
                                  1000   1500     2000        2500   3000
                                           IMS voltage (V)




                                                                               IonCCD response (ion/dN)
                                                                                                          1000                               5
                                                                                                                   Broad band detection>10
                           Using the averaged value obtained we show
                            clearly that not only the IonCCD not detects                                  100
                        thermal ions but equally important maintain its
                      detection efficiency from ~keV down to ~meV ion
                       energies. By analogy to optical CCDs, the IonCCD
                                                                                                           10
                                       has a broad band detection > 105

                                   Ion energy range of maintained
                                                                                                            1
                                       IonCCD detection efficiency                                          0.01   0.1   1      10    100   1000   10000

                                                                                                                         Ion energy (eV)
B&N gate Imaging
                                                                16 mm                      B&N Gate
                                     1000
                                                                                             nd
                                                                                           2 ring
                                                                                           transversal

                                     800
IonCCD signal (dN) Offset Y values




                                     600                                                         740V
                                                                                                 720V
                                                                                                 700V
                                                                                                 680V
                                     400                                                         660V
                                                                                                 650V
                                                                                                 640V
                                                                                                 630V
                                     200
                                                                                                664V


                                       0
                                            -10 -8   -6   -4   -2   0   2   4   6   8   10 12 14 16 18
                                                               IonCCD coordinates (mm)
16 mm                      B&N Gate
                                                                                            th
                                                                                          6 ring
                                     800                                                  transversal
IonCCD signal (dN) Offset Y values




                                     600


                                                                                              2070V
                                                                                              2050V
                                     400                                                      2030V
                                                                                              2010V
                                                                                              2000V
                                                                                              1990V
                                     200
                                                                                              1980V
                                                                                              1970V
                                                                                              1989V

                                      0
                                           -10 -8   -6   -4   -2   0   2   4   6   8   10 12 14 16 18
                                                              IonCCD coordinates (mm)
3.5
                                             B&N Gate                                                                                                           Gate location             8th ring
                                     800         8th ring +5V                                                              3.0                                                            6th ring




                                                                                              Structure FWHM (mm)
                                                 6th ring -9V                                                                                                                             2nd ring
                                                 2nd ring -24V                                                             2.5
                                     700
                                                                                                                           2.0
                                                                                                                                                                                           truncated
                                                                                                                           1.5
IonCCD signal (dN) Offset Y values




                                     600
                                                                                                                           1.0

                                                                                                                           0.5
                                     500
                                                                                                                           0.0
                                                                                                                              -8         -6      -4          -2       0       2       4      6         8
                                     400
                                                                                                                                          Structure centroid location (mm)
                                                                                                                           4.0
                                                                                                                                                    y = Intercept + B1*x^1
                                                                                                                                     Equation




                                                                                                 average peak width (mm)
                                                                                                                           3.5       Weight       Instrumental
                                     300                                                                                             Residual            0.02831
                                                                                                                                     Sum of
                                                                                                                                     Squares
                                                                                                                           3.0       Adj. R-Squar        0.99857
                                                                                                                                                                      Value Standard
                                                                                                                                                                             Error
                                     200
                                                                                                                           2.5       C
                                                                                                                                                    Intercept         0.9567    0.02184
                                                                                                                                                    B1                0.1940    0.00518

                                                                                                                           2.0
                                     100
                                                                                                                           1.5
                                                                                                                                                                          ring-to-ring=10 mm
                                      0                                                                                    1.0
                                           -25 -20 -15 -10   -5   0   5   10   15   20   25                                      0       1      2        3        4       5       6   7       8        9
                                                    IonCCD coordinates (mm)                                                                          Gate position(ring #)
The slope suggests that diffusion in those conditions
           (3000V/8 rings=80mm, and Please check the total distance)
             result in ~0.2 mm radial expansion for every 10mm axial
                                  motion (~2%)


                             3000V/80mm

0.194 mm
                                 10 mm



                               300 ml/min
Opening and closing settings of the B&N gate
                                                                            B&N gate
                                 100000
IonCCD integrated singnal (dN)




                                 10000




                                  1000       B&N 2nd transversal
                                             B&N 6th transversal




                                   100
                                      -100   -50             0         50          100
                                                     wire-set V (V)
Tyndall gate Imaging
                                                              16 mm                       Tyndall Gate
                                                                                           nd
                                                                                          2 ring
                                     600                                                  collinear
IonCCD signal (dN) Offset Y values




                                                                                           740V front
                                     400                                                   720V front
                                                                                           700V front
                                                                                           660V front
                                                                                           664V back

                                     200




                                      0
                                           -10 -8   -6   -4    -2   0   2   4   6   8   10 12 14 16 18
                                                              IonCCD coordinates (mm)
Front set scan                                                                                                     Back set scan
                                     1400                                                                                                      1000
                                                                                           Tyndall Gate                                                                  16 mm
                                                               16 mm                                                                                                                                  Tyndall Gate
                                                                                             nd                                                                                                         nd
                                                                                           2 ring                                                                                                     2 ring
                                     1200                                                  transversal                                                                                                transversal
                                                                                                                                               800
IonCCD signal (dN) Offset Y values




                                                                                                          IonCCD signal (dN) Offset Y values
                                     1000


                                                                                                                                               600
                                     800
                                                                                                                                                                                                       720V back
                                                                                            740V front                                                                                                 700V back
                                     600                                                    720V front                                                                                                 690V back
                                                                                            700V front                                         400                                                     680V back
                                                                                            680V front                                                                                                 660V back
                                     400                                                    670V front                                                                                                 640V back
                                                                                            660V front                                                                                                 620V back
                                                                                                                                               200
                                                                                            664V back                                                                                                  664V front
                                     200



                                       0                                                                                                         0
                                            -10 -8   -6   -4    -2   0   2   4   6   8   10 12 14 16 18                                               -10 -8   -6   -4    -2   0    2   4   6   8   10 12 14 16 18
                                                               IonCCD coordinates (mm)                                                                                   IonCCD coordinates (mm)
16 mm                     Tyndall Gate
                                                                                         th
                                     500                                                6 ring
                                                                                        collinear
IonCCD signal (dN) Offset Y values




                                     400

                                                                                         2070V front
                                                                                         2060V front
                                     300                                                 2040V front
                                                                                         2020V front
                                                                                         2010V front
                                                                                         2000V front
                                     200
                                                                                         1989V front

                                                                                         1989V back

                                     100




                                      0
                                           -10 -8   -6   -4   -2   0   2   4   6   8   10 12 14 16 18
                                                              IonCCD coordinates (mm)
Front set scan                                                                                            Back set scan
                                                                                                                                               800
                                     1000                                                 Tyndall Gate                                                                  16 mm                     Tyndall Gate
                                                               16 mm                      6th ring                                                                                                6th ring
                                                                                          transversal                                                                                             transversal

                                     800
                                                                                                                                               600
IonCCD signal (dN) Offset Y values




                                                                                                          IonCCD signal (dN) Offset Y values
                                     600

                                                                                                                                               400
                                                                                           2120V front                                                                                             2060V back
                                                                                           2100V front                                                                                             2040V back
                                     400
                                                                                           2080V front                                                                                             2020V back
                                                                                           2060V front                                                                                             2000V back
                                                                                           2040V front                                                                                             1980 back
                                                                                                                                               200                                                 1960V back
                                                                                           2020V front
                                     200
                                                                                           2000V front                                                                                             1989V front
                                                                                           1980V front
                                                                                           1989V back
                                       0                                                                                                        0
                                            -10 -8   -6   -4    -2   0   2   4   6   8   10 12 14 16 18                                              -10 -8   -6   -4   -2   0   2   4   6   8   10 12 14 16 18
                                                               IonCCD coordinates (mm)                                                                                  IonCCD coordinates (mm)
•   1117 V, 2 ring
Dynamic Images with IMS   •   Ion source in-and-out
                          •   10 pixels avg., 10 frames avg.
     Parameters           •   95 MB file
                                          IonCCD signal (dN)
• Zoom window, 35 sec, 19 mm
Dynamic Images with IMS   • No pixel and frame avg.
                          • 24 µm x 100 ms Resolution
     Parameters
                                      IonCCD signal (dN)
Increasing vs. decreasing E-field effects
                          4000


                          3000
     Ring potential (V)




                          2000


                          1000
                                       Increasing
                            0          Decreasing

                                 0           2           4                  6         8       10
                                                            ring # source-to-IonCCD

                          1000         Increasing E-field
                                       Decreasing E-field
IonCCD signal (dN)




                          800
                                                                           345 kdN
                          600


                          400


                          200                                     170 kdN
                            0
                                 -10                -5                 0                  5        10
                                                              IonCCD X axis (mm)
Conclusions
• IonCCD showed linear response and detection of ions in the thermal
  energy regime, extending the detection band with from thermal to
  medium energy regime (10 meV – 10 keV)
• The first high resolution imaging of ion diffusion determined
  experimentally with better than 0.1 mm resolution in one direction.
• Shadowing of the ions observed from shutter wires throughout the
  drift region of the IMS.
• Gathered experimental data for improved ion modeling.



                       Acknowledgements
           OI Analytical, for funding the collaborative work
Questions

I

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High-resolution ion swarm imaging and detection of thermal ions in a drift tube ion mobility spectrometer using an IonCCD detector

  • 1. First detection of thermal ions and ion swarm imaging in a DT-IMS by means of a high spatial-resolution IonCCD™ Omar Hadjar1, Stephen Davila2, Gary Eiceman2 1OI Analytical, CMS field product, Mass Spectrometry and Ion Imaging, Pelham, AL 2 NMSU, Department of Chemistry and Biochemistry, Las Cruces, NM
  • 2. Motivations • To explore the capabilities of the IonCCD as a detector for IMS • To extend detectability from keV down to thermal ions • To provide real time, high density imaging of the ion swarm at ambient pressures. • To determine the diffusion of ion swarms in the drift region • To characterize optics for ions • To obtain sufficient experimental data on ion motion under electric fields and form theoretical modeling and calculations
  • 4. Ring 1 Setup Schematics Ring 2 of the DT-IMS Ring 3 Ring 4 Ring 5 Ring 6 Ring 7 Ring 8 Ring 9 9 IonCCD Housing Potential 8 1 2 3 4 5 6 7 8 9 7 Slit-Plate 6 Detector board 5 Cold foot Slit-plate Chip 4 Femto-Amp IonCCD housing 3 IonCCD chip 2 1 Distance
  • 5. Experimental Setup Ring stack of the DT-IMS IonCCD in SS enclosure Camera box IonCCD base lined signal Picture shot while Stephen was changing the DT-IMS rings arrangement with the IonCCD ON and recording no ion signal but an unperturbed base line
  • 6. IonCCD housing voltage bias effect 1000 450 3 kV DT-IMS IonCCD encosure 3 kV bias: 800 70V 2 kV 50V 400 30V IonCCD signal (dN) 25V 600 20V 14V 350 10V 6V 400 4V 1.6V 300 IonCCD integrated signal (kdN) 0.8V 200 0.2V 0.1V 0V 250 0 -10 -5 0 5 10 15 20 500 IonCCD 2 kV DT-IMS 200 encosure bias: 70V 400 50V 30V 150 IonCCD signal (dN) 25V 20V 300 14V 10V 100 6V 200 4V 1.6V 0.8V 0.2V 50 100 0V 0 0 -10 -5 0 5 10 15 20 0 20 40 60 80 IonCCD X axis (mm) IonCCD enclosure Bias (V) 6 rings DT-IMS (pre-ring lens & slit disc)
  • 7. Detection Efficiency 800 400 80 IMS voltage (V) 3000 700 2500 2000 1500 1000 300 60 600 500 IonCCD integrated signal (kdN) FemtoAmplifier (pA) 500 IonCCD signal (dN) 200 40 400 300 100 20 200 100 0 0 0 -25 -20 -15 -10 -5 0 5 10 15 20 25 0 500 1000 1500 2000 2500 3000 IonCCD coordinates (mm) IMS voltage (V)
  • 8. IonCCD vs. FemtoAmp response to the IMS ion throughput 350 Equation y = a + b* Adj. R-Squar 0.99793 300 Value Standard Erro E Intercept -22913.3526 5498.23184 E Slope 5263.6508 119.6966 250 IonCCD (kdN) 200 150 100 50 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 FemtoAmplifier (pA) The integrated profiles are plotted here against the Femto-Amplifier response when operated at 1011 gain. This comparative study was conducted at same experimental condition with a 16x1mm2 slit plate and grounded IonCCD plate to expose both detection surfaces to the same ion beam cross section hence the same total ion current.
  • 9. 10000 IonCCD detection efficiency at different IMS high voltage bias IonCCD responce (ion/dN) noise floor (12 dN) 1000 We observed a slight decrease of the IonCCD detection efficiency at lower IMS HV. This can be due to experiment- 100 to-experiment variation, or witnessing the effect of the floating pixels, during charge integration time, on the ion collection (retarding field effect). 10 10000 1 1000 1500 2000 2500 3000 IMS voltage (V) IonCCD response (ion/dN) 1000 5 Broad band detection>10 Using the averaged value obtained we show clearly that not only the IonCCD not detects 100 thermal ions but equally important maintain its detection efficiency from ~keV down to ~meV ion energies. By analogy to optical CCDs, the IonCCD 10 has a broad band detection > 105 Ion energy range of maintained 1 IonCCD detection efficiency 0.01 0.1 1 10 100 1000 10000 Ion energy (eV)
  • 10. B&N gate Imaging 16 mm B&N Gate 1000 nd 2 ring transversal 800 IonCCD signal (dN) Offset Y values 600 740V 720V 700V 680V 400 660V 650V 640V 630V 200 664V 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm)
  • 11. 16 mm B&N Gate th 6 ring 800 transversal IonCCD signal (dN) Offset Y values 600 2070V 2050V 400 2030V 2010V 2000V 1990V 200 1980V 1970V 1989V 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm)
  • 12. 3.5 B&N Gate Gate location 8th ring 800 8th ring +5V 3.0 6th ring Structure FWHM (mm) 6th ring -9V 2nd ring 2nd ring -24V 2.5 700 2.0 truncated 1.5 IonCCD signal (dN) Offset Y values 600 1.0 0.5 500 0.0 -8 -6 -4 -2 0 2 4 6 8 400 Structure centroid location (mm) 4.0 y = Intercept + B1*x^1 Equation average peak width (mm) 3.5 Weight Instrumental 300 Residual 0.02831 Sum of Squares 3.0 Adj. R-Squar 0.99857 Value Standard Error 200 2.5 C Intercept 0.9567 0.02184 B1 0.1940 0.00518 2.0 100 1.5 ring-to-ring=10 mm 0 1.0 -25 -20 -15 -10 -5 0 5 10 15 20 25 0 1 2 3 4 5 6 7 8 9 IonCCD coordinates (mm) Gate position(ring #)
  • 13. The slope suggests that diffusion in those conditions (3000V/8 rings=80mm, and Please check the total distance) result in ~0.2 mm radial expansion for every 10mm axial motion (~2%) 3000V/80mm 0.194 mm 10 mm 300 ml/min
  • 14. Opening and closing settings of the B&N gate B&N gate 100000 IonCCD integrated singnal (dN) 10000 1000 B&N 2nd transversal B&N 6th transversal 100 -100 -50 0 50 100 wire-set V (V)
  • 15. Tyndall gate Imaging 16 mm Tyndall Gate nd 2 ring 600 collinear IonCCD signal (dN) Offset Y values 740V front 400 720V front 700V front 660V front 664V back 200 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm)
  • 16. Front set scan Back set scan 1400 1000 Tyndall Gate 16 mm 16 mm Tyndall Gate nd nd 2 ring 2 ring 1200 transversal transversal 800 IonCCD signal (dN) Offset Y values IonCCD signal (dN) Offset Y values 1000 600 800 720V back 740V front 700V back 600 720V front 690V back 700V front 400 680V back 680V front 660V back 400 670V front 640V back 660V front 620V back 200 664V back 664V front 200 0 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm) IonCCD coordinates (mm)
  • 17. 16 mm Tyndall Gate th 500 6 ring collinear IonCCD signal (dN) Offset Y values 400 2070V front 2060V front 300 2040V front 2020V front 2010V front 2000V front 200 1989V front 1989V back 100 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm)
  • 18. Front set scan Back set scan 800 1000 Tyndall Gate 16 mm Tyndall Gate 16 mm 6th ring 6th ring transversal transversal 800 600 IonCCD signal (dN) Offset Y values IonCCD signal (dN) Offset Y values 600 400 2120V front 2060V back 2100V front 2040V back 400 2080V front 2020V back 2060V front 2000V back 2040V front 1980 back 200 1960V back 2020V front 200 2000V front 1989V front 1980V front 1989V back 0 0 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 IonCCD coordinates (mm) IonCCD coordinates (mm)
  • 19. 1117 V, 2 ring Dynamic Images with IMS • Ion source in-and-out • 10 pixels avg., 10 frames avg. Parameters • 95 MB file IonCCD signal (dN)
  • 20. • Zoom window, 35 sec, 19 mm Dynamic Images with IMS • No pixel and frame avg. • 24 µm x 100 ms Resolution Parameters IonCCD signal (dN)
  • 21. Increasing vs. decreasing E-field effects 4000 3000 Ring potential (V) 2000 1000 Increasing 0 Decreasing 0 2 4 6 8 10 ring # source-to-IonCCD 1000 Increasing E-field Decreasing E-field IonCCD signal (dN) 800 345 kdN 600 400 200 170 kdN 0 -10 -5 0 5 10 IonCCD X axis (mm)
  • 22. Conclusions • IonCCD showed linear response and detection of ions in the thermal energy regime, extending the detection band with from thermal to medium energy regime (10 meV – 10 keV) • The first high resolution imaging of ion diffusion determined experimentally with better than 0.1 mm resolution in one direction. • Shadowing of the ions observed from shutter wires throughout the drift region of the IMS. • Gathered experimental data for improved ion modeling. Acknowledgements OI Analytical, for funding the collaborative work