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1 PImMS Collaboration Jaya John John • PIXEL2012, Inawashiro PImMS an event-triggered time-stamping sensor with storage of multiple timestamps Jaya John John, on behalf of the PImMS Collaboration 6 September 2012, PIXEL2012, Inawashiro 1

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Page 1: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

1 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS an event-triggered time-stamping sensor

with storage of multiple timestamps

Jaya John John, on behalf of the PImMS Collaboration

6 September 2012, PIXEL2012, Inawashiro

1

Page 2: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

2 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Context and requirements for PImMS sensors

PImMS1 and PImMS2 sensors

Specifications, design and operation

Project timeline and status

PImMS1 characterisation

PImMS1 application results

Summary and future work

Outline

PImMS 1

7.2 mm

Page 3: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

3 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Context: time of flight mass spectrometry

Mass spectrum for human plasma

~ 100 µs duration

Page 4: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

4 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Pixel Imaging Mass Spectrometry

Combines time-of- flight MS with 2D ion imaging.

We can image:

the velocities of the ions at their point of formation -- giving info on fragmentation dynamics, or

the positions of the ions at their point of formation – used in surface imaging or parallel acquisition of multiple mass spectra from an array of samples

Page 5: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

5 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Requirements: self-triggering

Proof of concept experiments with a fast-framing camera: multiphoton fragmentation of dimethyldisulfide (images recorded in 2008 using a Dalsa Zenith CCD camera).

Required prior knowledge of timing of mass peaks, programming the framing for the known time of arrival of each peak.

M. Brouard, E.K. Campbell, A.J. Johnsen, C. Vallance, W.H. Yuen, and A. Nomerotski, Rev. Sci. Instrum. 79, 123115, (2008)

CH3S2CH3

Page 6: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

6 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Requirements: multiple timestamps

Want a fast sensor, flexible to analyse any mass spectrum

Sparse events consider time-stamping approach

To record both early and late ions, need multiple memories. How many? Simulate:

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1

0 50000 100000 150000 200000

ion13

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1

0 50000 100000 150000 200000

ion39

p (

ion

det

ecte

d)

p (

ion

det

ecte

d)

n (ions flown)

n (ions flown)

p (

ion

det

ecte

d)

n (ions flown)

all 40 ions simulated

2 registers

4 registers

1 register

3 registers

Page 7: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

7 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Requirements: timing resolution

Time Resolution for Δm = 1

If we want Δm = 1:

m/Δm ≈ t/2Δt

Δt = t/2m

Initial spec for time resolution: 50ns

Updated spec, based on our significant progress in mass spectrometer timing, is to distinguish ions with a mass difference of 1 Dalton over a wide range of masses.

This yields a new target spec of 12.5ns (see results later)

25ns

12.5ns

6.25ns

Page 8: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

8 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS sensors: specifications Spec PImMS1 PImMS2

Array size 72 x 72 pixels 324 x 324 pixels

Active area 5mm x 5mm 22.7mm x 22.7mm

Sensor size 7mm x 7mm 25.4mm x 26.1mm

Pixel size 70µm x 70µm

Pixel threshold trim 4 trim bits + 1 masking bit per pixel

Timestamp storage Four 12-bit registers per pixel

Test pixel 1 test pixel with access to inner analogue nodes

Time resolution Initial spec: 50ns; simulation target: 25ns Updated spec: 12.5ns

Current performance 12.5ns verified (will be tested in future)

Substrate 5µm epi 5µm epi 18µm high-resistivity epi

Page 9: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

9 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS pixel

t t

t t

vD

t

vPA vS vC vO

vS1

vS2 vC2

vC1 hit

Analogue Readout

Pre-Amplifier Collection

Diodes Shaper

Digital Control

Logic

Comparator Trim Block

Comparator

Memory 1

Memory 4

Memory 2

Memory 3

- +

vTh2

vTh1

DA

C

DA

C

3

2

1

0 vTr1

vS2

vS1

vTr2 Pixel Trim Bits

vC2

vC1 vD vPA vO

Digital Readout 12 bits

Digital Timecode 12 bits

Pixel Memories 12 bits each

Page 10: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

10 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Pixel operation

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

0 0 0 0 0 6 6 6 6 6 6 6 6 6 6 6 6 6

0 0 0 0 0 0 0 0 0 0 0 0 0 14 14 14 14 14

diode

crossing => hit

preamplifier

shaper

comparator inputs

hit indicator

timecode

memory 1

memory 2

crossing => hit

10

Page 11: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

11 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Pixel layout

11

Page 12: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

12 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS sensors: overview

Timecode Distribution

Trim

an

d r

ow

co

ntr

ol

72 x 72 Pixel Array

Sense Amplifiers

Readout Circuit

Analogue Output Path

Trim

rea

db

ack

Bia

s B

lock

Test Pixel @ (3, 2)

12

PImMS1

Timecode Generation (Counter)

Trim

an

d r

ow

co

ntr

ol

324 x 324 Pixel Array

Sense Amplifiers

Readout Circuit

Analogue Output Path

Trim

rea

db

ack

+ ro

w c

on

tro

l B

ias

DA

Cs

Test Pixel @ (3, 2)

12

PImMS2

Page 13: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

13 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

New features:

• Array size increased to 324x324

• Additional digital output taps

• Additional analogue outputs

• Extra counters

• Right hand side driver circuitry for row control signals

• Internal bias generator

• Extra pixel trim bias

PImMS1 to PImMS2:

324 x 324

Page 14: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

14 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS sensors: technology

0.18µm CMOS fabrication

INMAPS process developed at the Rutherford Lab: Isolated N-well Monolithic Active Pixel Sensors

PImMS pixel: 615 transistors per pixel

over 3 million transistors in total for PImMS1

Page 15: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

15 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Readout: camera

USB control and readout

F-mount SLR lens

C-mount SLR lens also possible – delivers more light to sensor

Cooling system based on copper finger and Peltier device

Connection for nitrogen/dry air flushing

Page 16: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

16 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Project timeline and status

Milestone Date

Start of PImMS project July 2009

PImMS1 sensor received and first light December 2010

PImMS2 design start March 2011

PImMS1 first mass spectrometry results April 2011

Resolution of several PImMS1 camera (DAQ) issues January 2012

PImMS1 25ns timecodes verified April 2012

PImMS2 design submitted February 2012

PImMS1 12.5ns timecodes verified Last week

PImMS2 current status: wafers are being diced This week

Next steps: wirebonding then initial tests of PImMS2 Second half of September

Page 17: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

17 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS1 characterisation: timing resolution

50ns 100ns 25ns 12.5ns

Testing with timecodes at increasing speeds, using a low-power laser pulse generator

The edges of the laser spot have progressively lower intensity, showing the degree of timewalk, ~125ns

Page 18: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

18 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Timing resolution, continued

Timecodes present in one frame only:

• sigma 1.65

• time resolution 20.6ns

Timecodes present in all frames:

• sigma 1.68

• time resolution 21ns

Timecodes present for a single pixel:

• sigma 0.33

• time resolution 4.1ns

Page 19: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

19 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS1 characterisation: dead time

Results for firing two lasers at the same set of pixels, varying the delay between the lasers.

If the second laser occurs within the dead time, no pulse will be recorded in the second register.

Results for 4 individual pixels, showing the range of responses.

Page 20: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

20 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Application results

Page 21: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

21 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Applications: velocity map imaging

N,N-dimethylformamide (DMF) is a prototype molecule for studying peptide bond cleavage.

PImMS data on the 193 nm photolysis of DMF is shown below.

Page 22: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

22 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Applications: coincidence imaging

Here bromine gas (Br2) is dissociated. By switching the polarity of the ion optics, first the electrons are imaged, then the ions.

(a) shows the mass spectrum including 79Br+ and 81Br +

(b) shows the mass intersections for the electrons and Br ions

(c) zooms in on the two isotopes, 79Br + and 81Br +

Page 23: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

23 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Applications: spatial imaging

This is imaging the mass spectrum over a 2D surface.

Materials used: lines of Auramine O (yellow) and Rhodamine 590 (red)

The samples produced 10 mass peaks in all. 5 are highlighted here.

Data taken at 25ns time resolution

Demonstrates multi-mass imaging

Page 24: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

24 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Spatial imaging, continued

1

3

0

20

40

60

80

100

1

2

3

4

5

6

7

8

9

1…

Register

Peak

For an intense area of the image, we investigated:

• the proportion of each mass peak seen

• in which pixel register the mass peaks appeared.

Page 25: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

25 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

Summary and future work

PImMS is both a new technique in mass spectrometry and a self-triggered time-stamping sensor.

PImMS1 has been proven for mass spectrometry, operating at 12.5ns timecode rates (4x initial spec)

Multiple memories record various events within

one experimental cycle.

Taking a wider view, PImMS also suits other

applications generating step changes of signal.

PImMS2 testing will begin in the second half of

September, promising improved spatial resolution,

with its larger pixel array.

Page 26: PImMSpimms.chem.ox.ac.uk/downloads/PImMS_PIXEL2012.pdf · degree of timewalk, ~125ns . PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 18 Timing resolution, continued

26 PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro 26

The support of the STFC, ICONIC, EPSRC, ERC, RC-UK and ISIS Innovation Ltd. are gratefully acknowledged.

Thank you for your attention. Questions?

The PImMS Collaboration

Mark Brouard, Edward Halford, Alexa Lauer, Craig Slater, Benjamin Winter, Wei Hao Yuen Claire Vallance, James Bull, Cécilia Cauchy, Sara Gardiner, Jason Lee, Laura Lipciuc, Edward Wilman

Department of Chemistry, University of Oxford

Andrei Nomerotski, Richard Nickerson, Xavier Coubez, Laura Hill, Jaya John John, Robert Pisarczyk Department of Physics, University of Oxford

Renato Turchetta, Andy Clark, Jamie Crooks, Ben Marsh, Iain Sedgwick STFC Rutherford Appleton Laboratory

PImMS Collaboration • Jaya John John • PIXEL2012, Inawashiro

PImMS2 wafer: