Electrochemical Sensors

1. Electrochemical Sensors Electrochemical sensors are the most versatile and highly developed chemical sensors. They are divided into several types: • Potentiometric (measure voltage) • Amperometric (measure current) • Conductometric (measure conductivity) Sometimes the distinction between these types can be blurred. In all these sensors, special electrodes are used.

3. Electrochemical Sensors Either a chemical reaction takes place or the charge transport is modulated by the reaction Electrochemical sensing always requires a closed circuit. Current must flow to make a measurement. Since we need a closed loop we need at least two electrodes. These sensors are often called an electrochemical cell. How the cell is used depends heavily on the sensitivity, selectivity and accuracy.

4. Potentiometric Sensors Potentiometric sensors use the effect of the concentration on the equilibrium of redox reactions occurring at the electrode-electrolyte interface of an electrochemical cell The redox reaction takes on the electrode surface: Oxidant + Ze- => Reduced product Z is the number of electrons involved in the redox reaction www.chemie.uni-greifswald.de/

5. Electrochemical Cell The reaction takes place at the cathode where electrons are “pulled” out of the electrode.

6. Nernst Equation • Co is the oxidant concentration • CR is the Reduced Product Concentration • n is the number of electrons transferred per redox reaction • F is the Faraday constant • T is the temperature • R is the gas Constant • E0 is the electrode potential at a standard state. The Nernst equation gives the potential of each half cell. In a potentiometric sensor, two half-cell reactions take place at each electrode. Only one of the reactions should involve sensing the species of interest. The other should be a well understood reversible and non-interfering reaction

7. CHEMFET Sensors Very popular where small size and low power consumption is essential. (Biological and Medical monitoring). CHEMFETs are chemical potentiometric sensors based on the Field-Effect transistors CHEMFETs are solid state sensors suitable for batch fabrication. The surface field effect can provide high selectivity and sensitivity. These are extended gate field-effect transistors with the electrochemical potential inserted over the gate surface.

8. Four types of CHEMFETs: • Ion Selective • gas selective, • enzyme-selective • immuno-selective sensors. Ion selective are the most widely used, known as ISFETs A lot of the art of CHEMFETs is in engineering the porous layer over the gate.

9. The sensor is given a pH sensitivity by exposing the bare silicon nitride gate insulator to the sample solution. Ion selective CHEMFET with a silicon nitride gate for measuring pH (H+ ion concentration.)

10. Ionic selectivity is determined by the surface complexation of the gate insulator. Selectivity of the sensor can be obtained by varying the composition of the gate insulator. As the ionic concentration varies, the surface charge density at the CHEMFET gate changes as well.

11. Also add ion-selective membranes can be deposited on the top of of the gate to provide a large selection of different chemical sensors. A change in the surface charge density affects the CHEMFET channel conductance, which can be measured as a variation in the drain current. Thus a bias applied to to the drain and source of the FET results in a current I, controlled by the electrochemical potential. This in turn is proportional to the concentration of the interesting ions in solution.

12. A biosensor sensitive to a particular protein or virus can be made by coating the electrode with the appropriate antibody. Extreme care must be taken to electrically isolate the signals from the solution!

13. Carbon nanotubes • Sheets of carbon atoms can be ‘rolled’ up into tubes of nanometer dimensions • Layers of nanotubes have a huge surface to volume ratio

14. Carbon nanotubes • Carbon nanotubes can be grown en masse, or separated as individuals. Nanotube (blue) lying across electrodes Nanotube forest

15. Carbon Nanotube sensors The Scanning Electron Micrograph shows a bridge made from a single nanotube. It is linking two ‘cliffs’ made of Au and Ti. N2 gas is blown up from the bottom The resistance of the sensor increases upon exposure to N2 gas www.bios.el.utwente.nl/internal/Transducers03/Volume_1/2E80.P.pdf

16. CNT FET sensor Can also make FET sensors out of carbon nanotubes A small current in the nanotube causes a much larger current in the FET This particular sensor responds to light. www.echo.nuee.nagoya-u.ac.jp/~yohno/research/cnt/qnn03_abstract_submitted.htm

17. Titanium nanotube sensors • H2 gas is ionised when it hits the walls of the titanium nanotubes • The resulting electron current is a measure of the amount of hydrogen present. www.eurekalert.org/pub_releases/2003-07/ps-tnm072903.php

18. Lecture 10 • Empty?

19. Lecture 11

20. Concentration Sensors • Concentration sensors react to the concentration of a specific chemical. • The concentration modulates some physical property (eg resistance or capacitance). • Generally speaking, no chemical reaction takes place in the sensor. • Often called physical sensors.

21. Resistive Sensors To detect the presence of a liquid phase chemical, a sensor must be specific to that particular agent a certain concentration. Eg. Resistive detector of hydrocarbon fuel leaks. (Bell Corporation). Made of silicone and carbon black composite Polymer matrix is the sensing element. Constructed as a very thin layer with large surface area.

22. Sensor is not susceptible to polar solvents like water. However hydrocarbons are absorbed by the polymer matrix The matrix swells and the resistivityy increases from 10 /cm to 109/cm Response time is less than a second.

23. Sensor returns to normal conductive state when hydrocarbon is removed. The device is reusable and can be placed underground. Ideal for oil exploration.

24. Gravimetric Sensors Measurement of microscopic amount of mass cannot be accomplished using conventional balances. Use oscillating sensor (sometimes called acoustic gravimetric sensor) which measures thin layers. The oscillating sensor measures the shift in the resonant frequency of a piezoelectric quartz oscillator. The resonant frequency is a function of the crystal mass and shape.

25. The device can be described as an oscillating plate whose natural frequency depends on its mass. Adding material to that mass would shift the frequency which can be accurately measured electronically.

26. F0 = the unloaded natural frequency, f is the frequency shift, m is the added mass per unit area and Sm is the sensitivity factor. The numerical value of Sm depends upon the design, material and operating frequency of the sensor. The oscillating detector converts mass value to a frequency shift. It is extremely easy to dtermine frequency, so the sensor’s accuracy is determined by how well Sm is known.

27. Fluid density sensors. Several basic methods are used for determination of fluid density Measurement of inertial mass. Measurement of Gravitational Mass. Buoyant force. Hydrostatic pressure. Attenuation of -rays

28. Density measurement The fluid is forced to flow through the sensor which has a hollow tube. The sensor is made of silicon and the tube forms a double-loop within the device.

29. The tube inlet and outlet are at the side and the entire loop is designed for torsional vibration. The mass of the actual tube is kept small so the total mass of the vibrating object is mostly that of the fluid. The resonant frequency of the vibration is proportional to the total mass of the tube and fluid. Since the volume in the tube is constant, the frequency is proportional to the density of the fluid. Once again we exploit the physical properties of the material to directly measure characteristics of the material (the fluid).