Signal processing for chemical sensors

Martin Holmberg
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Applied Physics, Department of Physics and
Measurement Technology (IFM)
Linkping University

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Human olfactory system

a large number of olfactory cells (10 million) but only a small number of
sensitivity classes (30)
a mixture of volatile compounds results in a signal pattern to the brain via the
mitral cells (10 thousand)
the brain interprets the signal pattern as a specific odour

nasal chamber

odour

epithelium
olfactory receptor cells

odour moleclues bind to olfactory proteins

produces an electrical response

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brain
olfactory bulb

olfactory cortex

mitral cells

neurons

signal processing:
data reduction

signal processing:
pattern recognition

perception

Electronic nose concept

sensitivity to many compounds using a limited number of chemical

sensors with different and partly overlapping selectivity profiles
analyse the sensor signal pattern rather than the individual signals
gives a description of the total measurement state, i.e. the sum of all
components, which can be more important than a detailed knowledge of
each of the individual components

sensor chamber(s)

odour

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chemical sensors

computer
preprocessing

pattern
recognition

information

Solid-state gas sensor principles

adsorption/desorption or chemical reactions

on surfaces or in (thin) films

cause

which depend on

PHYSICAL CHANGES

MOLECULAR PROPERTIES

mass

polarisation

size

conductivity
temperature

affinity
reactivity

optical properties

polarity

which can be used in several types of

DEVICES
acoustic

calorimetric
fibre optic
resistive

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field effect

polarisability

Electronic nose gas flow diagram

Valve

Field-effect sensors

Air
Sample
Metal oxide sensors
FiS

Metal oxide sensors

Figaro

IR CO2 sensor

Pump
Drain

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Massflow controller

Signal processing: feature extraction

500
on integral off integral
400

sensor signal

off derivative
300

MOSFET 3
MOSFET 7
Figaro 3

response

on derivative

200
baseline

100

100
sample on off

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200

time [s]

300

400

Background; The Tongue

Based on voltammetry
Currents are measured as a
function of applied potential on
electrode surfaces
The currents are caused by:

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Redox reactions at the surface

Ionic movement in the sample

Background; Voltammetry
Potential [V]

1
0.5
0
-0.5
-1
0

Au

Rh

Ir
1

Pt
4

6
x 10

Current [mA]

0.3
0.2
0.1
0
-0.1
-0.2
0

Time [ms]

6
x 10

The currents are sampled once every [ms] 56.000 variables

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Information overflow

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An electronic nose or tongue generates large data

series
(one measurement can consist of up to 56.000
variabler Linkpings telephone book)
Impossible to get a good grip of these numbers
We need to decrease the information content
A lot of redundant information means that
compression is possible

Other possible problems

Noise
Drift
Low sensitivity
Sampling problems
Measurements system

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What is drift?

Definition:

a gradual change in any quantitative characteristic

supposed to remain constant

that is

(Websters Seventh New Collegiate Dictionary)

For chemical sensors:

Measurements made under identical chemical conditions give
different sensor responses at different times.

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Causes of drift

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Reactions on the sensor surface (poisoning)

changes in the physical properties of the
sensing material (e.g. the size of the metal
islands on a MOSFET)
adsorption of species on the sensor surface
layer formation of reaction products
Variations in the gas (composition, pressure, temperature,)
Remaining gas in the measurement system

Example of drift

Measurements made
during 60 days on nine
different mixtures of four
gases
Gradual change + jumps
Drift + noise
Drift in different directions
for the different sensors

Below are shown the responses of

three sensors as a function of time
500
450
400
response (mV)

350
300
250
200
150
0

10

20

30

40

time (days)

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50

60

70

Comparison noise and drift

Drift
low frequency
caused by changes in
the measurement system
similar for similar
sensors

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Noise
high frequency
caused by randomness
in the measurements
individual for each
sensor

What do we do?

Pre-processing to compensate for some of the

problems mentioned previously
Pattern recognition models to give the desired
information
If possible, give feedback regarding the
measurements
sensor chamber(s)

odour

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chemical sensors

computer
preprocessing

pattern
recognition

information

Geometrical interpretation
1,2,3-variables

56.000 variables

?
Easy to visualise

Abstract

Reduce the number of dimensions

Often made by choosing directions with a lot of variation
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Principal Component Analysis

Can be used for data compression, feature extraction, or visualisation

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Examples of pre-processing

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1st example uses PCA to find a direction where

irrelevant information is dominant. This direction is
then removed from the data set.
2nd example shows how wavelets are used to
compress data, and how the choice of wavelets
depends on the application.

Component correction

Uses a reference gas

Calculates the direction of drift by PCA for the reference
gas
Removes this direction(s) from all other measurements

Example: Artursson et al. J. of Chemometr. 14, 5/6 (2000) 711-724

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Component correction

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1st (or several) component in a PCA analysis of the

reference gas will describe the drift direction, p
Project the samples, X, on the first loading, p from
the PCA on the reference gas,
t=Xp
Subtract the bilinear expression, tpT, from X
T
X
corrected=X- tp

Component correction
before

component correction

400

300
300

200

200

100

PC 2 (24%)

PC 2 (24%)

100
0
-100
-200

-100

-300

-200

-400

-300

-500
-500

-400

-300

-200

-100

100

200

300

400

500

PC 1 (63%)

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Also used for quantification

-500

-400

-300

-200

-100

100

PC 1 (71%)

200

300

400

500

Wavelets

Data is described
using wavelet base
functions with
different scales
The number of
wavelets = the
number of original
variables

Scale 1

LPF

HPF

A1

D1

Scale 2

LPF

HPF

A2

.......

D2

A2

D2

wavelet coefficients

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D1

Wavelet selection

By selecting only the most relevant wavelets, a data

reduction is obtained
Different criteria for selection in different applications
(e.g. variance or discrimination)
Here approximately 100 wavelets are chosen from the
original ca. 1800-14000 variables
5.00E-011

12

10

4.00E-011

Discrimination

varians

3.00E-011

2.00E-011

1.00E-011

0
0.00E+000
0

100

200

variables

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300

400

500

2000

4000

6000

8000

Variables

10000

12000

14000

Reconstruction

The original signal can be reconstructed from the

compressed data
Different results from different wavelet selection
criteria
Variance selected

Discrimination selected

0.000018

0.00012
0.00011

0.000016

0.00010
0.00009

0.000012

0.00008

0.000010

0.00007

response

response

0.000014

0.000008
0.000006
0.000004

0.00006
0.00005
0.00004
0.00003
0.00002

0.000002

0.00001

0.000000

0.00000

-0.000002

-0.00001

200

400

600

800

1000

1200

variables

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Platina

-0.00002

-0.000004
1400

1600

1800

2000

2000

4000

Rhodium
6000

8000

variables

10000

12000

Pattern recognition

After reducing initial obstacles with different preprocessing techniques, a model that gives the user
something he/she can understand must be made

sensor chamber(s)

odour

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chemical sensors

computer
preprocessing

pattern
recognition

information

Data models

Classification or quantification?
Statistical tools for class membership
Scores vs. scores
6
2
222
22 2 2
2 2
22 2 2

Scores for PC# 2

4.1 %

2
1
0

-2

-4

3 3 33
333
3 33 3 3
3

1
111 111 1
1
111 1
1

4 44 44
444
44 4 4
4 4
4

-6
5
5555555
55 555
5 5
5

-8

-10
5

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10

15
20
Scores for PC# 1 95.6 %

25

30

Data models

Quantification of gases or liquids:

Regression models (e.g. PLS) for linear
relationships
Artificial neural networks (ANN) for non-linear
black-box modeling

Important always to validate data, especially when

many parameters are used in the models!!!

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