CMOS Hydrogen Sensor

CMOS Hydrogen Sensor

Prepared by:

Steve Pyke

Peterson Ridge LLC (dba. Fluence)

PO Box 1257
Sisters, OR 97759
541-390-9572

Abstract

Peterson Ridge LLC (dba Fluence) has developed a silicon based CMOS FET (field effect transistor)
sensor for hydrogen. The CMOS sensor technology described below has the potential for being part of a
low-cost product. Sensitivity to hydrogen, resolution from interference sources and reliability is
enhanced when the sensor is used in combination with two other CMOS FET sensors in an array.
Additional cost reduction can be cost-effective for high-volume sales by the custom integration of the
sensor with ASIC electronics for signal processing and communication. An ASIC approach to integrating
sensor control, signal processing, analysis and communications can be produced in CMOS on silicon.
Depending on the volume, this approach to system development can also be one of the lowest cost
approaches to WAN and LAN available.

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The Fluence technology is an array of silicon-based field effect transistors (FETs) for the low-cost,
selective, sensitive and reliable detection of hydrogen. Two FET sensors will have a catalytic gate and
one will have an inert gate for temperature and humidity compensation. The two catalytic gate sensors
are sensitive to and selective for hydrogen and insensitive to saturated and unsaturated hydrocarbon gases
and vapors (e.g. methane, ethylene). The two sensors with catalytic gates will be produced side by side
on the silicon wafer and physically identical in-so-far as can be achieved by the CMOS process. These
two sensors will have identical sensitivities to hydrogen. This redundancy increases the product
reliability. Any difference in the response of these two sensors would be a fault of either one or both
sensors and will alert the user to a problem requiring his or her attention. The FET sensor with the inert
gate will respond to temperature and humidity in the same way as the pair with catalytic gates. All three
sensors will have very similar dependence on ambient temperature and humidity. The inert sensor will
not respond to hydrogen, and a true hydrogen effect can be resolved from changes due to temperature and
humidity interference and can be measured with greater accuracy, precision and reliability.

Sensor Background

The need for low-cost hydrogen sensors (Hoffheins et al, 1999) and gas sensors for combustible and toxic
gases has supported a variety of technologies (Ho, 2001). The catalytic bead sensor is the oldest of the
commercial combustible gas sensors. Any combustible gas including hydrogen is oxidized by
atmospheric oxygen on a heated wire coated with a catalyst. The reaction increases the temperature of the
wire and decreases its electrical resistance. The change in resistance is proportional to the concentration
of combustible gas.

A related sensor is the metal-oxide-semiconductor sensor. Metal oxide semiconductors (e.g. tin oxide,
iron oxide) are electrically conductive as the result of oxide ion conductivity at high temperatures
typically above 400C. These materials when pressed into pellet form and sintered at high temperature
form the basis for a sensor which can detect combustible gases by the change to the electrical
conductivity of the material. The technology was commercialized by Figaro Engineering in the early
1970s (Taguchi, 1972) and was reviewed (Morrison, 1982 and Kohl, 1989). The selectivity of the tin
oxide Figaro sensors was very poor to start but has been improved by diluting the powdered starting
materials with small amounts of catalyst (e.g. palladium, platinum and other metals) before sintering.
Arrays of these sensors have been proposed for resolving the composition of gas mixtures using pattern
recognition software for analysis, but temperatures above 300 C are required for the measurement. The
large heater current requires large batteries precluding products such as small monitors powered by watch
batteries. Another disadvantage is drift due to temperature due to field driven ionic migration and
recrystallization of the sintered material.

Electrochemical sensors were recently reviewed (Bakker and Telting-Diaz, 2002). These sensors produce
a current from hydrogen and using atmospheric oxygen as the oxidant. The electrochemical sensor
typically uses a liquid based electrolyte, typically water, and the operational temperature range is limited,
and they cannot operate without a source of oxygen. Electrochemical sensors with solid oxide
electrolytes have been reported recently (Martin, 2003), but like the Figaro technology, solid oxide
electrolytes typically require high temperature for electrical conductivity.

These technologies are limited by the need for high temperature or oxygen and sometimes both and a
custom manufacturing process developed specifically for the sensor product.

The Fluence CMOS FET sensor does not require high temperature or oxygen to detect hydrogen.

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CMOS FET Sensor for Hydrogen

The manufacture of the CMOS sensor exploits the tightly controlled contract performance and quality
specifications and the maturity and sophistication of the CMOS process and is the most important
advantage for pursuing this technology for hydrogen sensors. The FET sensors can be combined with a
CMOS application specific integrated circuit (ASIC) for sensor control and communication.

The FET sensor has been the subject of research and development for thirty years beginning in Sweden
and including recently the development of GaN FET sensors for the resolution and measurement of
carbon monoxide (CO) in process hydrogen (Pyke and Sadwick, 2003).

The CMOS approach brings state-of-the-art silicon processing to the concept of the FET sensor with a
catalytic gate metal. This technology offers three major advantages in comparison with all of the
commercial sensors listed above:
• CMOS foundry capabilities and resources have resulted in very low unit manufacturing cost
• The sophistication and maturity of the semiconductor fabrication process used for both CMOS
electronics and the FET sensors results in much greater product consistency than is possible with
current commercial sensor technology
• The FET does the initial signal conditioning and amplification simplifying the electronics for
control and analysis

The cost of manufacturing commercial sensor products is dominated by the time and resources required to
select, test and calibrate each sensor that is shipped in a product. Consistent sensor performance will be
significantly greater for CMOS FET sensors, and the reduction in the cost for selecting, testing and
calibration will be significantly reduced. Consistent sensor performance is directly related to the
repeatability of key process parameters that quality improvement teams work to improve daily. The
uniformity of the electrical properties of the typical silicon wafer continues to improve. Process controls
necessary for consistent CMOS memories and large area microprocessors have become more stringent as
device geometry shrinks. The CMOS FET sensor for hydrogen will completely capture the advantage of
the industry standard CMOS process.

The use of the FET to transduce the effect of hydrogen on the catalytic gate is an effective way to convert
the chemical effect to an electrical effect which can be easily measured.

FET Sensor Background

Lundstrom first described the silicon FET with a palladium gate for hydrogen detection (Lundstrom et al,
1974). Figure 1 illustrates the structure of the FET. The palladium gate FET was part of a hydrogen leak
detector manufactured by Sensistor AB starting in 1981. The selectivity to hydrogen is due to the
solubility of hydrogen in palladium and the formation of palladium hydride. The change in composition
results in a change in the chemical potential or work function of the metal and is measured by a change in
the threshold voltage VT of the FET shown in Figure 2. The effect on VT was clearly demonstrated by
current/voltage measurements with FETs. The hypothesis that work function was changing with
hydrogen was the natural extension of these measurements since the correlation of metal work function
with VT had been established early in the development of transistors. While there are other hypotheses
that could also account for the change in VT, the work function explanation is now commonly used to
explain the hydrogen sensitivity.

The palladium gate had disadvantages overcome by different catalytic metals. While the palladium gate
provides sensitivity to very low concentrations of hydrogen, the sensor saturates well below 1%(vol)

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hydrogen in air or nitrogen. Also, multiple cycles of hydrogen exposure followed by air or nitrogen result
in the expansion and contraction of the crystal structure leading to stress and mechanical failure of the
material. Work in the early 1980s at Bell Labs (Poteat et al, 1983) demonstrated sensitivity to hydrogen,
ethylene and carbon monoxide on platinum and iridium metal-insulator-semiconductor (MIS) capacitors.
This work received little attention, and an explanation for the mechanism was never given. By the mid
1980s, using FETs and MIS capacitors for detecting hydrogen with palladium gates had been reproduced
in many laboratories. Continuing work on the MIS structure at Sandia showed the mechanical problems
with pure palladium could be eliminated with palladium-nickel alloys increasing the hydrogen
concentration where the structural problems occur. Hughes et al 1987 reported sensitivity to hydrogen
sulfide, propylene oxide, ethylene, formic acid, CO and NO2 using catalytic metals in MIS capacitors in
the presence of hydrogen. This work formed the basis for a hydrogen detector manufactured currently by
H2Scan, Valencia, CA. This H2Scan product combines a palladium-nickel FET for low concentration
measurements and a palladium-nickel resistor for higher concentrations of hydrogen.

The catalytic gate was suspended over the channel region of the FET (SGFET) to allow gas penetration to
the metal surface facing the channel and increase the sensitivity of catalytic metals like platinum and
iridium where the solubility for hydrogen is orders of magnitude less than palladium (Cassidy et al 1986,
Eisele et al, 2001, Feinstein et al, 1997, Fleitner et al, 1994, and Pyke, 1987). As with the work reported
by Poteat, sensitivity to hydrogen and gases other than hydrogen was observed. The suspended catalytic
gate has the disadvantage of involving several fabrication steps not part of the standard CMOS foundry
process.

Recent work in this laboratory on aluminum gallium nitride-gallium nitride (AlGaN-GaN) modulation
doped MODFET sensors with solid platinum and rhodium gates produced using standard planar
metallization has demonstrated hydrogen sensitivities equivalent to the palladium with greater dynamic
range (Pyke and Sadwick, 2003 and references therein). The planar gate configuration eliminates the
need for the complex suspended gate. Figure 3 shows the layout of the AlGaN-GaN FET sensor. Figure
4 is a plot of the sensitivity of both metals. The gate voltage depends on the logarithm of the hydrogen
concentration and does not saturate.

AlGaN/GaN MODFET Platinum Gate Rhodium Gate

Sensitivity (mV/decade) -93 -150
Range in Air*§ 0-2%vol 0-2%vol
Range in Nitrogen* 0-100%vol 0-100%vol
CO2 Sensitivity <10mV (0-15%vol) <10mV (0-15%vol)
Methane Sensitivity <10mV (0-1%vol) <10mV (0-1%vol)
* Neither gate is saturated at with hydrogen (tested to 1atm).
§
There is a dependence on oxygen that would affect the hydrogen sensitivity, but the data indicate a
logarithmic response up to 2% hydrogen.

This work also confirmed the reversible sensitivity to carbon monoxide in a hydrogen background
reported earlier (Hughes et al, 1987). Detection of CO in hydrogen used as a fuel is important in order to
avoid poisoning the electrodes in a fuel cell. Platinum and rhodium gate metals were used to resolve CO
in the 0-80 ppm level with hydrogen concentration varied 30-70%.

CMOS Processing

The standard CMOS process cannot be customized without becoming a nonstandard process. Any
process steps not part of the standard CMOS process will in a higher price and more inconsistency in the
product. Fewer foundries are willing to engage in a nonstandard process and when they do the work
invariably will take longer to complete and result in lower yields. The CMOS process flow is shown in
Figure 5. While aluminum metal gates are a standard in CMOS processing, the catalytic metals are not.

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Platinum is exotic, and this part of the process is usually outsourced. There are few resources available
for exotic metal deposition collaborating with CMOS foundries. Batch to batch variance will be greater
than for the standard process, but sensor performance within a batch should be as consistent as the
performance of any device produced in a standard CMOS process.

Dielectric Layer Separating the Gate Metal from the Silicon

The dielectric layer plays an important role in determining threshold voltage and sensitivity. The
standard primary dielectric is an oxidized layer of silicon grown at high temperature. This layer of silicon
oxide form a barrier to the flow of electric current, but it is a medium through which ions and hydrogen
can diffuse. Low-pressure chemical vapor deposition (LPCVD) silicon nitride was chosen as a second
layer of dielectric to prevent hydrogen from diffusing into and altering the electrical properties of the
silicon under the dielectric layer.

Gate Architecture and Composition

Fluence planar catalytic gate starts with a robust bond to the LPCVD silicon nitride. The gate pattern
increases the surface area for hydrogen adsorption for a maximum sensitivity. The sensors have longer
and wider channels where the effects of defects in the silicon are averaged over a larger area.

The design for the gate is a ladder with the rungs extending from drain to source and connected at each
end by two lines running along the inside edge of the source and drain regions respectively (see Figure 6).
The gate-source voltage VGS and VT control the current in the channel region directly under the
metallization. Current will flow in the channel region between the rungs depending on the applied VGS
and any influence on VT by exposure to gas (see Figure 7). Both the catalytic and aluminum gates will
share the same gate structure.

Platinum was sputtered onto to the channel with an intermediate adhesion layer of thin film sputtered
titanium. A lift-off process was used to remove the metals everywhere on the wafer except for the
platinum fingers spanning the channel regions of the FETs. The CMOS foundry produced the aluminum
gates using their standard process.

Cross-Sensitivity: Temperature, Interfering Gases and Moisture

Temperature testing and calibration will cover the range from –20C to 100C. In previous work (see
Figure 8), we observed a value of drain-source current IDS and VGS where the dIDS/dVGS curves crossed.
At the crossing point the device temperature sensitivity approached zero. Multiple devices will be tested
to determine the wafer and batch variance of these values with the goal of a temperature independent
sensor output.

Interference or cross sensitivity by other gases and moisture are potential barriers to this and any sensor
technology. Sensitivity to other gases and environmental conditions greater than 10% of the sensitivity to
hydrogen is a potential interference.

Moisture is a known interferent in silicon based devices. Water changes the surface composition of the
native oxide which forms on the LPCVD silicon nitride layer between the gate fingers. The aluminum
gate FET has the identical native oxynitride and will be used to directly compensate for the effect of
moisture.

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Control Circuit and Reliability

Electronics developed in this laboratory is used for an array of three sensors. The sensor control circuit is
adjusted for specific value of drain current IDS, and a feedback loop adjusts the gate-source voltage VGS to
compensate for any changes in IDS due to hydrogen.

Two platinum gate sensors will provide redundant measurements for reliability. Equivalent changes in
VGS on both sensors will be sufficient evidence for a hydrogen effect and will provide a real-time
measurement of concentration and precision. The absence of a simultaneous and equivalent change is
evidence of a fault condition and the need for maintenance or sensor replacement.

References

Bakker, E., and M. Telting-Diaz, 2002, Anal. Chem., 74, 2781.

Cassidy, J., S. Pons and J. Janata, 1986, Anal. Chem., 58, 1757.
Feinstein, D.I., C. Renn, M. Scharff and S.C. Pyke, 1997, “Metal-Insulator-Semiconductor (MIS) Gas Sensor Array
for Gas Analysis and Diagnosing Faults in Oil-Filled Power Transformers”, 191st Meeting of the Electrochemical
Society, Montreal, Quebec, Canada, May 4-9.
Hedborg, E., F. Winquist, and I. Lundstrom, 1994, Appl. Phys. Lett., 64(4), 420.
Ho, C.K., M.T. Itamura, M. Kelley and R.C. Hughes, 2001, “Review of Chemical Sensors for In-Situ Monitoring of
Volatile Contaminants”, Sandia Report SAND2001-0643, http://www.sandia.gov/sensor/SAND2001-0643.pdf
Hoffheins, B.S., L.C. Maxey, W. Holmes Jr., R.J. Lauf, C. Salter and D. Walker, 1999, “Development of Low Cost
Sensors for Hydrogen Safety Applications”, DOE Report,
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/26938rr.pdf
Hughes, R.C., W.K. Schubert, T.E. Zipperian, J.L. Rodriguez and T.A. Plut, 1987, J. Appl. Phys., 62, 1074
Kohl, D., 1989, Sensors and Actuators, 18, 71.
Lundstrom, I., M.S. Shivaraman, C. Svensson, and L. Lundqvist, 1975, J. Appl. Phys., 26, 55.
Lundstrom, I. and L.G. Petersson, 1996, J. Vac. Sci. Technol., A, 14(3), 1539
Martin, L.P., R.S. Glass, 2003, “Electrochemical Sensors for Proton Exchange Fuel Cell Vehicles”, DOE Report,
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/viib2_martin.pdf
Morrison, S.R., Sensors and Actuators, 1982, 2, 329.
Poteat, T.L., B. Lalevic, B. Kuliyev, M. Yousef and M. Chem, 1983, J. Electron.Mater., 12, 181
Pyke, S.C., 1987, US Patent No. 4,671,852, 1990, US Patent No. 4,947,104, 1995, US Patent 5,417,821, 1997, US
Patent 5,591,321, and 2000, US Patent Application 09/820,037.
Pyke S.C. and L. Sadwick, 2002, “Gallium Nitride Integrated Gas/Temperature Sensors for Fuel-Cell System
Monitoring for Hydrogen and Carbon Monoxide”, DOE Report,
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/32405b16.pdf
Pyke S.C., and L. Sadwick, 2001, “Gallium Nitride Integrated Gas/Temperature Sensors for Fuel-Cell System
Monitoring for Hydrogen and Carbon Monoxide”, DOE Report,
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/30535ay.pdf
Pyke, S.C., J-H. Chern, J. Hwu and L. Sadwick, 2000, “Gallium Nitride Integrated Gas/Temperature Sensors for
Fuel-Cell System Monitoring for Hydrogen and Carbon Monoxide”, DOE Report,
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/28890ii.pdf
Pyke S.C. and L. Sadwick, 2003, “Resolution of Hydrogen and Carbon Monoxide on Metal Gate GaN MODFET
Sensors”, IEEE Sensors 2003, Toronto, Canada October 22-24
Taguchi, N., 1972, US Patent No. 3,676,820.

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Figure 1. Crossection of the catalytic gate FET showing source, drain and gate electrodes and the
dielectric between the gate and substrate. The region under the dielectric between the source and drain is
the channel. The electrical conductivity of the channel is a sensitive measure of the electric field between
the gate and the substrate.
Label1

Figure 2: The plot of IDS vs VDS on the left shows FET electrical behavior in forward bias where current
can flow in the transistor. When the drain-source voltage reaches the “saturation value”, the gate-source
voltage VGS controls the current. The intercept at zero current in the plot on the right is the threshold
voltage VT .

GaN FET Layout

Single Gate
Source/Drain
Contact
Gate
Contact
Source/Drain
Contact
Slice 1
Slice 2
Thermocouple
Source/Drain Slice 3
Contacts
Contact Slice 4
Gate
Contact
Source/Drain
Contact

Dual Gate 7

Figure 3. Layout of the first generation AlGaN-GaN MODFET sensor with catalytic gate and titanium
aluminum source and drain metallization. The area of the layout in this example is about 1 mm2. The
CMOS sensors would be about the same size.

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Hydrogen Response in Air - 30 ºC

0 .6

Gate-Source Voltage, V
0 .5 5

Pt 0 .5
V g s = -0 .0 9 3 L o g [H 2 ]
0 .4 5

0 .4
0 0 .5 1 1 .5 2
H y d ro g e n , % v o l

0 .9 0

0 .8 5

Gate-Source Voltage, V
0 .8 0
D a ta a t 2 5 0 C
Rh 0 .7 5
V g s = -0 .1 5 L o g [ H 2 ]
0 .7 0

0 .6 5

0 .6 0
0 0 .5 1 1.5 2
H y d ro g e n , % vo l

28

Figure 4: Sensitivity of the platinum and rhodium gate AlGaN-GaN MODFET sensors to hydrogen in air
follows a nearly logarithmic isotherm in the full range from 100 ppm to 2% in air. There is no saturation
unlike the palladium gate FETs. In nitrogen, there is no evidence of saturation up to 100% hydrogen.

Figure 5. Typical stepwise CMOS process steps.

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Figure 6. Fluence CMOS sensor layout showing NMOS and PMOS designs (gate length variation) and
finger density. The pink gates are reference electrodes with complete channel coverage.

Gate Gate
Metal Environmental Metal
Finger Finger

Dielectric

Sillicon
Depletion Layer

Figure 7. Crossection of gate fingers showing the capacitive coupling between the metal and the channel
which controls the channel conductivity. Hydrogen adsorbed on the surface of the metal fingers will
influence this coupling in proportion to its concentration in the medium being measured.

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Figure 8. Current voltage data for three platinum gate SGFET sensors. Where the curves cross, the drain
source current is independent of temperature. Consistency in sensor performance will lead to consistent
values where the curves cross and a temperature independent sensor.

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