Biopotential

Electrodes
(Ch. 5)

Electrode Electrolyte Interface

Electrode
C

Electrolyte (neutral charge)

C+, A- in solution
Current flow

eeC+ : Cation

C
C

C+
A-

C+

AA- : Anion

e- : electron

Fairly common electrode materials: Pt, Carbon, , Au, Ag,

Electrode metal is use in conjunction with salt, e.g. Ag-AgCl, Pt-Pt
black, or polymer coats (e.g. Nafion, to improve selectivity)

Electrode Electrolyte Interface

General Ionic Equations
a)

C C n ne

b)

Am A me

a) If electrode has same material as cation, then this material gets

oxidized and enters the electrolyte as a cation and electrons remain
at the electrode and flow in the external circuit.
b) If anion can be oxidized at the electrode to form a neutral atom,
one or two electrons are given to the electrode.
The dominating reaction can be inferred from the following :
Current flow from electrode to electrolyte : Oxidation (Loss of e-)
Current flow from electrolyte to electrode : Reduction (Gain of e-)

Half Cell Potential

A characteristic potential difference established by the electrode and its
surrounding electrolyte which depends on the metal, concentration of ions
in solution and temperature (and some second order factors) .

Half cell potential cannot be measured without a second electrode.

The half cell potential of the standard hydrogen electrode has been arbitrarily
set to zero. Other half cell potentials are expressed as a potential difference
with this electrode.

Reason for Half Cell Potential : Charge Separation at Interface

Oxidation or reduction reactions at the electrode-electrolyte interface
lead to a double-charge layer, similar to that which exists along
electrically active biological cell membranes.

Measuring Half Cell Potential

Note: Electrode material is metal + salt or polymer selective membrane

Some half cell potentials

Standard Hydrogen electrode

Note: Ag-AgCl has low

junction potential & it is
also very stable -> hence
used in ECG electrodes!

Polarization
If there is a current between the electrode and electrolyte, the
observed half cell potential is often altered due to polarization.
Overpotential
Difference between observed and zero-current half cell potentials
Resistance
Current changes resistance
of electrolyte and thus,
a voltage drop results.

Concentration
Changes in distribution
of ions at the electrodeelectrolyte interface

Activation
The activation energy
barrier depends on the
direction of current and
determines kinetics

V p VR VC VA
Note: Polarization and impedance of the electrode are two of the
most important electrode properties to consider.

Nernst Equation
When two aqueous ionic solutions of different concentration are
separated by an ion-selective semi-permeable membrane, an electric
potential exists across the membrane.
For the general oxidation-reduction reaction

A B C D ne
The Nernst equation for half cell potential is

RT
a
0
C aD
EE
ln
nF a A a B

where E0 : Standard Half Cell Potential

Note: interested
in ionic activity
at the electrode
(but note temp
dependence

E : Half Cell Potential

a : Ionic Activity (generally same as concentration)

n : Number of valence electrons involved

Polarizable and Non-Polarizable

Electrodes
Perfectly Polarizable Electrodes

Use for
recording

These are electrodes in which no actual charge crosses the electrodeelectrolyte interface when a current is applied. The current across the
interface is a displacement current and the electrode behaves like a
capacitor. Example : Ag/AgCl Electrode
Use for
stimulation
Perfectly Non-Polarizable Electrode
These are electrodes where current passes freely across the electrodeelectrolyte interface, requiring no energy to make the transition. These
electrodes see no overpotentials. Example : Platinum electrode
Example: Ag-AgCl is used in recording while Pt is use in stimulation

Ag/AgCl Electrode
Relevant ionic equations
Ag Ag e
Ag Cl AgCl
Cl2

Governing Nernst Equation

Ag Cl
+

0
E E Ag

RT K s

ln

nF aCl

Fabrication of Ag/AgCl electrodes

1. Electrolytic deposition of AgCl
2. Sintering process forming pellet electrodes

Solubility
product of AgCl

Equivalent Circuit
Cd
Rd
Rs
Ecell

Rd+Rs

: capacitance of electrode-eletrolyte interface

: resistance of electrode-eletrolyte interface
: resistance of electrode lead wire
: cell potential for electrode
Corner frequency

Rs

Frequency Response

Electrode Skin Interface

Ehe
Electrode

Cd

Rd

Gel

100

Stratum Corneum
Epidermis

100

Dermis and
subcutaneous layer
Nerve
endings

Capillary

Ce

Rs

Sweat glands
and ducts

Ese

EP

Re

CP

RP

Alter skin
transport (or
deliver drugs)
by:
Pores
produced by
laser,
ultrasound or
by
iontophoresis

Ru

Skin impedance for 1cm2 patch:

200k @1Hz
200 @ 1MHz

Motion Artifact
Why
When the electrode moves with respect to the electrolyte, the
distribution of the double layer of charge on polarizable electrode
interface changes. This changes the half cell potential temporarily.
What
If a pair of electrodes is in an electrolyte and one moves with
respect to the other, a potential difference appears across the
electrodes known as the motion artifact. This is a source of
noise and interference in biopotential measurements
Motion artifact is minimal for non-polarizable electrodes

Body Surface Recording Electrodes

Electrode metal
Electrolyte

1. Metal Plate Electrodes

(historic)
2. Suction Electrodes
(historic interest)
3. Floating Electrodes
4. Flexible Electrodes

Think of the
construction of
electrosurgical
electrode
And, how does
electro-surgery
work?

Commonly Used Biopotential

Electrodes
Metal plate electrodes
Large surface: Ancient,
therefore still used, ECG
Metal disk with stainless steel;
platinum or gold coated
EMG, EEG
smaller diameters
motion artifacts
Disposable foam-pad: Cheap!
(a) Metal-plate electrode used for application to limbs.
(b) Metal-disk electrode applied with surgical tape.
(c)Disposable foam-pad electrodes, often used with ECG

Commonly Used Biopotential

Electrodes
Suction electrodes
- No straps or adhesives
required
- precordial (chest) ECG
- can only be used for short
periods
Floating electrodes
- metal disk is recessed
- swimming in the electrolyte gel
- not in contact with the skin
- reduces motion artifact

Suction Electrode

Commonly Used Biopotential

Electrodes
Insulating
package

Double-sided
Adhesive-tape
ring

Metal disk

Electrolyte gel
in recess

(a)

(b)
Snap coated with Ag-AgCl
Plastic cup

Foam pad

External snap
Gel-coated sponge
Plastic disk

Reusable
Disposable

Dead cellular material

Tack
Capillary loops Germinating layer
(c)

Floating Electrodes

Commonly Used Biopotential

Electrodes
Flexible electrodes
- Body contours are often
irregular
- Regularly shaped rigid
electrodes
may not always work.
- Special case : infants
- Material :
- Polymer or nylon with silver
- Carbon filled silicon rubber(a) Carbon-filled silicone rubber electrode.
(Mylar film)
(b) Flexible thin-film neonatal electrode.
(c) Cross-sectional view of the thin-film
electrode in (b).

Internal Electrodes
Needle and wire electrodes for
percutaneous measurement of
biopotentials
(a) Insulated needle electrode.
(b) Coaxial needle electrode.
(c) Bipolar coaxial electrode.
(d) Fine-wire electrode connected
to hypodermic needle, before
being inserted.
(e) Cross-sectional view of skin
and muscle, showing coiled
fine-wire electrode in place.
The latest: BION implanted electrode for muscle recording/stimulation
Alfred E. Mann Foundation

Fetal ECG Electrodes

Electrodes for detecting fetal electrocardiogram during labor, by means

of intracutaneous needles (a) Suction electrode. (b) Cross-sectional view of
suction electrode in place, showing penetration of probe through epidermis.
(c) Helical electrode, which is attached to fetal skin by corkscrew type action.

Electrode Arrays
Ag/AgCl electrodes

Contacts

Contacts

Insulated leads
Ag/AgCl electrodes

Insulated leads

Base

(a)
Tines

Exposed tip

Base
(b)

Base
(c)

Examples of microfabricated electrode arrays.

(a) One-dimensional plunge electrode array,
(b) Two-dimensional array, and
(c) Three-dimensional array

Microelectrodes
Why
Measure potential difference across cell membrane
Requirements
Small enough to be placed into cell
Intracellular
Strong enough to penetrate cell membrane
Extracellular
Typical tip diameter: 0.05 10 microns
Types
Solid metal -> Tungsten microelectrodes
Supported metal (metal contained within/outside glass needle)
Glass micropipette -> with Ag-AgCl electrode metal

Metal Microelectrodes
C

Microns!

R
Extracellular recording typically in brain where you
are interested in recording the firing of neurons
(spikes).
Use metal electrode+insulation -> goes to high
impedance amplifiernegative capacitance amplifier!

Metal Supported Microelectrodes

(a) Metal inside glass

(b) Glass inside metal

Glass Micropipette
heat
pull

Fill with
intracellular fluid
or 3M KCl

Ag-AgCl wire+3M
KCl has very low
junction potential
and hence very
accurate for dc
measurements (e.g.
action potential)

A glass micropipet electrode filled

with an electrolytic solution
(a) Section of fine-bore glass
capillary.
(b) Capillary narrowed through
heating and stretching.
(c) Final structure of glass-pipet
microelectrode.

Intracellular recording typically for recording from cells, such as

cardiac myocyte
Need high impedance amplifiernegative capacitance amplifier!

Electrical Properties of
Microelectrodes
Metal Microelectrode

Metal microelectrode with tip placed

within cell
Use metal electrode+insulation -> goes to high impedance
amplifiernegative capacitance amplifier!

Equivalent circuits

Electrical Properties of Glass

Intracellular Microelectrodes
Glass Micropipette Microelectrode

Stimulating Electrodes
Features
Cannot be modeled as a series resistance and capacitance
(there is no single useful model)
The body/electrode has a highly nonlinear response to
stimulation
Platinum electrodes:
Large currents can cause
Applications: neural
Cavitation
stimulation
Cell damage
Heating
Modern day Pt-Ir and other exotic
Types of stimulating electrodes
1. Pacing
2. Ablation
3. Defibrillation

metal combinations to reduce

polarization, improve conductance
and long life/biocompatibility

Steel electrodes for

pacemakers and defibrillators

Intraocular Stimulation
Electrodes

Reference : Lutz Hesse, Thomas Schanze, Marcus Wilms and Marcus Eger, Implantation of retina stimulation
electrodes and recording of electrical stimulation responses in the visual cortex of the cat, Graefes Arch Clin Exp
Ophthalmol (2000) 238:840845

In vivo neural microsystems (FIBE): challenge

In vivo neural microsystems (FIBE): biocompatibility - variant

In vivo neural microsystems (FIBE): state of the art

Introduction: neural microsystems

Instrumentation for
neurophysiology

Neural
Microsystems
Neural
microelectrodes

MEMS Microsystems

Introduction: types of neural microsystems applications

External
electrodes

Subdural
electrodes

Human
level

Microelectrodes

Microsensors

In vivo
applications

Animal
level
Tissue
slice
level

Cellular
level

In vitro
applications

Microelectronic technology
for Microelectrodes

Bonding pads

SiO2 insulated
Au probes

Insulated
lead vias
Exposed
electrodes
Silicon probe

Si substrate

Exposed tips

(a) Beam-lead multiple electrode

Miniature
insulating
chamber

Hole

(b) Multielectrode silicon probe

Channels

Silicon chip

Lead via
Silicon probe

Electrode
(c) Multiple-chamber electrode

Contact
metal film

(d)

Peripheral-nerve electrode

Different types of microelectrodes fabricated using microfabrication/MEMS

technology

Michigan Probes for Neural

Recordings

Neural Recording
Microelectrodes

Reference :
http://www.acreo.se/acreo-rd/IMAGES/PUBLICATIONS/PROCEEDINGS/ABSTRACTKINDLUNDH.PDF

In vivo neural microsystems: 3 examples

University of Michigan
Smart comb-shape microelectrode arrays for
brain stimulation and recording

University of Illinois at Urbana-Champaign

High-density comb-shape metal microelectrode
arrays for recording

Fraunhofer Institute of Biomedical (FIBE)

Engineering
Retina implant

Multi-electrode Neural
Recording

Reference :
http://www.cyberkineticsinc.com/technology.htm

Reference :
http://www.nottingham.ac.uk/neuronal-networks/mmep.htm

WPIs Nitric Oxide

Nanosensor

Nitric Oxide Sensor

Developed at Dr.Thakors Lab, BME, JHU
Electrochemical detection of NO

Left: Schematic of the 16-electrode sensor array. Right: Close-up of a

single site. The underlying metal is Au and appears reddish under the
photoresist. The dark layer is C (300m-x-300m)

A
E

Cartoon of the fabrication sequence for the NO sensor array

A) Bare 4 Si wafer B) 5m of photoresist was spin-coated on to the surface, followed by a prebake for 1min at 90C. C) The samples were then exposed through a mask for 16s using UV
light at 365nm and an intensity of 15mW/cm2. D) Patterned photoresist after development. E)
20nm of Ti, 150nm of Au and 50nm of C were evaporated on. F) The metal on the unexposed
areas was removed by incubation in an acetone bath. G)A 2nd layer of photoresist, which
serves as the insulation layer, was spun on and patterned. H) The windows in the second layer
also defined the microelectrode sites.

NO Sensor Calibration

NO Sensor Calibration

Multichannel NO
Recordings