Physical & Theoretical Chemistry

Direct absorption measurements

using fibre-loop cavity ring-down
spectroscopy

Cathy Rushworth

Supervisor: Dr. Claire Vallance

25th November 2009

Outline

 Absorption spectroscopy
– Cavity ring-down spectroscopy (CRDS)
– For gases, using mirrors
– For liquids, using fibre optics

 Results so far

 Challenges ahead
– including likely strategies for fibre-chip coupling

Page 2
 Absorption spectroscopy

I
Beer-Lambert Law:  e  αcl
I0
Usually the path length is ~ 1 cm, but in a chip it can be 1000 times smaller
… How can we make absorption measurements on sample volumes this
small?

Page 3
 CRDS – with mirrors

d

Intensity

c(1  R  cl )
No absorber
Absorber present

Time
O’Keefe and Deacon 1988
Page 4
 CRDS – with fibres
θ2

θ1
Core RI = 1.457
Cladding RI = 1.439
n1sinθ1 = n2sinθ2

d

c( L  cl )
Loock 2002
Page 5
Fiberguide Industries, Inc.
Fibre signal

 Light travels in the core and the cladding

Cladding

Core

Cladding modes
Intensity

Core modes

Time
Start recording signal
after this point

Page 6
 Sample measurements

 Direct absorption

 Evanescent wave absorption

Cladding
Cladding
Core HF etching
Core

Taper

Page 7
Optical set-up

Page 8
Sample introduction

Page 9
Fibre-loop ring-downs
50 um core diameter fibre, l = 24 um,
In t e n s it y / a r b it r a r y u n it s
0.5 pL sample volume!
Water
τ = 224 ns
200

150

100

50

0
0.00E+00 2.00E-07 4.00E-07 6.00E-07 8.00E-07 1.00E-06 1.20E-06 1.40E-06
Time / s
12
Intensity / arbitrary units

10
8 R6G 0.1125 mM
6 τ =181 ns
4
2
0
0.00E+00 2.00E-07 4.00E-07 6.00E-07 8.00E-07 1.00E-06 1.20E-06 1.40E-06
Time / s

Page 10
 End separation – in water
0.95

0.90

0.85

0.80
200 um
Transmission

0.75

0.70

0.65
105 um

0.60
50 um
0.55 100 um
0.50
0 50 100 150 200 250 300

Separation / um

Page 11
 5.00E-07
Air
SFS100 4.50E-07
4.00E-07
3.50E-07

Ring-down / s
3.00E-07
5.00E-07 2.50E-07
2.00E-07
4.50E-07
1.50E-07
4.00E-07 1.00E-07
5.00E-08
3.50E-07 0.00E+00
0 2 4 6 8 10 12 14 16 18 20
3.00E-07
Ring-down / s

Separation / um
2.50E-07

2.00E-07

1.50E-07

1.00E-07

5.00E-08 Water
0.00E+00
0 50 100 150 200 250

Separation / um

Page 12
 Finding optimum l and d – for SFS100
0
For a given αabsC,
dτ/dC (s M-1)
0 optimise l and d to
maximise sensitivity
0

0
0 50 100 150 200 250 300 350
Separation / um

Waechter 2009
Page 13
Lensing

100 um

Page 14
Preliminary results – SFS50, l = 24 um, d = 4 m
250
Ringdown / ns

230

210

190

170

150

130
2.00E-04 2.50E-04 3.00E-04 3.50E-04 4.00E-04 4.50E-04 5.00E-04
Concentration of Rhodamine 6G in water / M

Probed volume ~ 0.5 pL

50 uM R6G: Detect ~ 2 fmoles, ~ 1 billion molecules

Page 15
Improvements

 Minimize loop losses

– Optimise coupling efficiency

 Separate core and cladding modes

– Amplification

– Data analysis

Page 16
 Options for fibre – chip coupling
 Contact HF etching in situ
Uncleaved fibre
Chip
Fibre ends Chip

Channel – HF
Fibre ends flow
 Non contact
Plan view
Fibre end
Chip

Observation
Chip
windows
Fibre ends
Remembering… Fibre alignment, Limit to end separation, RI (core) = 1.457

Page 17
Important considerations

 Fibre – chip coupling parameters

 End separation tolerances

 Systems to study
– Light sources
– Detectors
– Absorption coefficient/concentration

 Data acquisition rate?

Page 18
Acknowledgements

 Thank you for listening

 Thank you to Claire, Joao, Bobby and Joanna

Questions?

Page 19