This disclosure relates generally to sensor devices and particularly to a method of manufacturing a gas sensor device using atomic layer deposition techniques to form a gas-sensitive portion of the sensor device.
A metal oxide semiconductor (MOS) gas sensor is used to detect the presence of a particular gas or gasses in an environment to which the sensor is exposed. The typical MOS gas sensor includes a heating element and a gas-sensitive portion located between two electrodes. The heating element is activated to heat the gas-sensitive portion to a temperature that is suitable for detecting a target gas. The gas-sensitive portion undergoes an electrical change in the presence of the target gas. The electrical change of the gas-sensitive portion is detected by an external circuit that is electrically connected to the gas sensor.
Chemisorption is one type of adsorption that may occur at the grain boundaries 22 in the presence of the target gas. To illustrate the effects of chemisorption,
In
Heterogeneous catalysis is another process that may occur at the grain boundaries 22, depending on the type gas near the gas-sensitive portion 10. One example of heterogeneous catalysis, referred to as carbon monoxide (CO) oxidation, results in the oxidation of a carbon dioxide (CO2) molecule, due to the presence of a carbon monoxide molecule and an oxygen molecule located near one of the grain boundaries 22 of the gas-sensitive portion 10. Heterogeneous catalysis, in at least some instances, results in an electrical change of the gas-sensitive portion 10, which is detectable by the external circuit connected to the gas sensor as being indicative of the presence of a target gas.
In the above examples the reactions resulting in an electrical change of the gas-sensitive portion 10 are described as occurring at or near the grain boundaries 22 of the material forming the gas-sensitive portion. It is desirable to increase the number of grain boundaries of a gas-sensitive portion of a MOS gas sensor in order to increase the degree of electrical change undergone by the gas-sensitive portion in the presence of a target gas. Therefore, further developments in the area of MOS gas sensors are desirable.
According to an exemplary embodiment of the disclosure, a semiconductor sensor device includes a substrate, a non-suitable seed layer located above the substrate, at least one electrode located above the non-suitable seed layer, and a porous sensing layer supported directly by the non-suitable seed layer and in electrical communication with the at least one electrode. The porous sensing layer defines a plurality of grain boundaries formed by spaced-apart nucleation on the non-suitable seed layer using atomic layer deposition.
According to another exemplary embodiment of the disclosure, a method of fabricating a semiconductor sensor device includes forming a non-suitable seed layer above a substrate, forming at least one electrode above the non-suitable seed layer, forming a porous sensing layer on the non-suitable seed layer and in electrical communication with the at least one electrode, and nucleating, at spaced apart sites on the non-suitable seed layer, a sensing material, thereby forming a plurality of grain boundaries resulting in the porous sensing layer.
The above-described features and advantages, as well as others, should become more readily apparent to those of ordinary skill in the art by reference to the following detailed description and the accompanying figures in which:
For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiments illustrated in the drawings and described in the following written specification. It is understood that no limitation to the scope of the disclosure is thereby intended. It is further understood that this disclosure includes any alterations and modifications to the illustrated embodiments and includes further applications of the principles of the disclosure as would normally occur to one skilled in the art to which this disclosure pertains.
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With additional reference to
The oxide layer 118 is located between the handle layer 116 and the heater layer 120 and is configured to isolate the handle layer from the heater layer. The oxide layer 118 is formed from silicon dioxide (SiO2), sapphire, or another suitable insulative material.
The heater layer 120 is formed on the oxide layer 118 and is electrically connected to the voltage source 108. The heater layer 120 is a material that generates heat when exposed to an electrical current or other form of energy. The heater layer 120 is configured to heat the sensing layer 136 to a desired temperature. The heater layer 120 is also referred to herein as a heater, a heating layer, a resistive heater, a heater structure, and a heating structure. In the illustrated embodiment, the handle layer 116, the oxide layer 118, and the heater layer 120 are formed from a typical SOI wafer with the heater layer 120 being the “device layer” of the SOI wafer. Accordingly, the heater layer 120, in at least one embodiment, is formed from silicon. Other suitable materials for forming the heater layer 120 include doped silicon, composite materials, and the like. Furthermore, in some embodiments a separate heater material is used to form the heater layer 120. Exemplary materials suitable for forming the separate heater include silicon dioxide and platinum or other metals.
As shown in
In another embodiment, the non-suitable seed layer 124 is structured with trenching (or any other desired process) to further encourage spaced-apart nucleation of the sensing layer 136. In one specific embodiment, the “structuring” includes patterning the seed layer 124 and/or chemically activating certain spaced-apart nucleation sites 182 in order to encourage spaced-apart nucleation of the sensing layer 136. In yet another embodiment, the “structuring” includes ion-milling the seed layer 124 with passive gasses, such as argon, to make the seed layer more dense or less dense at spaced-apart nucleation sites 182, thereby resulting in selective encouragement of spaced-apart nucleation of the sensing layer 136. In general, the seed layer 124 is formed and/or structured from any material(s) and by any process(s) that encourages spaced-apart nucleation of the sensing layer 136 on the seed layer.
The electrodes 128, 132 are formed above the non-suitable seed layer 124 from an electrically conductive material using any process as desired by those of ordinary skill in the art. In one embodiment, the electrodes 128, 132 are formed from platinum and are electrically isolated from each other. The electrodes 128, 132 are spaced-apart from each other by a distance 140, and define a height 144. The distance 140 and the height 144 are selected based on the gas to be sensed/detected (referred to herein as a target gas), the material of the sensing layer 136, the structure of the sensing layer, and the application of the sensor device 102, among other considerations. Although the sensor device 102 is shown as including two of the electrodes 128, 132, in other embodiments, the sensor device includes any number of electrodes, as desired by those of ordinary skill in the art.
With continued reference to
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In operation, the sensor device 102 is configured to sense the presence of a target gas or target gasses in a space. Exemplary target gasses include carbon monoxide, nitrogen dioxide (NO2), ammonia (NH3), methane (CH4), volatile organic compounds (VOCs), and the like. Due to the small size of the sensor device 102, as compared to prior art MOS gas sensors, it is usable to detect gasses in a variety of applications such as automobile exhaust systems, home appliances, laptops, handheld or portable computers, mobile telephones, smart phones, wireless devices, tablets, personal data assistants (PDAs), portable music players, film cameras, digital cameras, GPS receivers and other satellite navigation systems, electronic reading displays, projectors, cockpit controls, game consoles, earpieces, headsets, hearing aids, wearable display devices, security systems, and other applications as desired by those ordinary skill in the art. In one embodiment, the sensor device 102 measures approximately two millimeters by three millimeters by one millimeter, but may be either smaller or larger depending on the desired application.
Use of the sensor device 102 includes applying a voltage to the heater 120 with the voltage source 108. In response to the voltage, the heater 120 is heated to a temperature that is based at least on the magnitude of the voltage source 108 and the electrical resistance of the heater 120. Heat energy from the heater 120 is transferred to the sensing layer 136.
The sensing layer 136 is heated by the heater 120 to a sensing temperature within a heating time period. The sensing temperature is based on at least properties of the target gas and the environment/space in which the sensor device 102 is positioned. Exemplary sensing temperatures range from one hundred fifty degrees Celsius to five hundred degrees Celsius; however, the sensor device 102 is configurable to operate at any sensing temperature desired by those of ordinary skill in the art. Since the sensing layer 136 is only about ten nanometers to one hundred nanometers thick (i.e. thickness 146,
After the sensor device 102 has been heated to the sensing temperature, voltage from the voltage source 104 is applied to the electrode 128, the sensing layer 136, the electrode 132, and the resistance 112. The voltage from the voltage source 104 establishes an electrical current (referred to as a sensor current) through the electrodes 128, 132, the sensing layer 136, and the resistance 112. The magnitude of the sensor current is based on at least the combined resistance of the electrodes 128, 132, the sensing layer 136, and the resistance 112, and is the same through the electrodes 128, 132, the sensing layer 136, and the resistance 112.
Next, the sensor device 102 is exposed to a space in which the target gas may or may not be present. The sensor device 102 and the resistance 112 form a voltage divider circuit, and an external circuit (not shown) monitors a voltage drop across the resistance 112 to determine if the target gas is present in the space. In particular, if the target gas is present and is an oxidizing gas, then as the target gas binds to the grain boundaries 152 via adsorption, the electrical resistance of the sensing layer 136 is increased and the sensor current is decreased. The decrease in sensor current is monitored by the external circuit as a decrease in voltage dropped across the resistance 112. If the target gas is present and is a reducing gas, then as the target gas binds to the grain boundaries 152, the electrical resistance of the sensing layer 136 is decreased and the sensor current is increased. The increase in sensor current is monitored by the external circuit as an increase in voltage dropped across the resistance 112.
With reference to
In block 408 the seed layer 124 is applied to the heater 120. The material of the seed layer 124 is selected to be a “non-suitable” material. The term “non-suitable material” is defined herein as a material that when used as a seed layer for a particular sensor layer material, causes spaced-apart nucleation of the grains 148 during depositing/formation of the sensing layer 136. The seed layer 124 is applied to the heater 120 using any process as desired by those of ordinary skill in the art.
Then, in block 412, a sacrificial material 170 is applied to the seed layer 124. The sacrificial material 170 is deposited/formed on the seed layer 124 using any process, as desired by those of ordinary skill in the art.
With reference to
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Next, with reference to
With reference again to
ALD is used to deposit materials by exposing a substrate to several different precursors sequentially. A typical deposition cycle begins by exposing a substrate to a precursor “A” which reacts with the substrate surface until saturation. This is referred to as a “self-terminating reaction.” Next, the substrate is exposed to a precursor “B” which reacts with the surface until saturation. The second self-terminating reaction reactivates the surface. Reactivation allows the precursor “A” to react with the surface. Typically, the precursors used in ALD include an organometallic precursor and an oxidizing agent such as water vapor or ozone.
The deposition cycle results, ideally, in one atomic layer being formed on the substrate. Thereafter, another layer may be formed by repeating the process. Accordingly, the final thickness of the layer is controlled by the number of cycles the substrate is exposed to. Moreover, deposition using an ALD process is substantially unaffected by the orientation of the particular surface upon which material is to be deposited. Accordingly, an extremely uniform thickness of material may be realized both on the upper and lower horizontal surfaces and on the vertical surfaces.
Typically, ALD is used to deposit a generally contiguous (non-porous) thin film of a material onto a seed layer formed from a “suitable material.” The seed layer material is referred to as being “suitable” for the deposited material when, after a predetermined number of ALD cycles, the deposited material forms a polycrystalline thin film that is contiguous (i.e. non-porous) across at least a portion of the seed layer material. That is, the grains of deposited material formed by ALD on a “suitable” seed layer are positioned tightly against each other so that there are substantially no air spaces therebetween. The materials therefore form a suitable pair of materials, since the resulting layer of deposited material is generally contiguous. Accordingly, a gas-sensing layer formed from a material deposited on a “suitable” seed layer using ALD includes very few grain boundaries that are available to interact with a gas, because most of the grain boundaries are unexposed to the air space around the deposited material. It turns out, however, that the structure of the material deposited using ALD, is heavily dependent on the interaction of the deposited material with the material forming the seed layer.
When forming the sensing layer 136, ALD is used to deposit the material of the sensing layer 136 onto the “non-suitable” seed layer material. The seed layer 124 is referred to as being “non-suitable” since the deposited material forms a conforming polycrystalline layer (thin film) that is porous. The material of the sensing layer 136 and the non-suitable material of the seed layer 124 are referred to herein as a non-suitable pair of materials. Typically, the porous layer of deposited material is undesirable; however, when used as the sensing layer 136, the porous film of deposited material functions extraordinarily well. In particular, the non-suitable material of the seed layer 124 causes nucleation of the grains 148 of the deposited sensing material at the spaced-apart nucleation sites 182 (
The large number of grain boundaries 152 and the near instant heating of the sensing layer 136 encourages more rapid and more complete adsorption of the target gas on the sensing layer, as well as a more pronounced electrical change of the sensing layer in response to being exposed to the target gas. In short, using ALD to deposit a material onto a non-suitable seed layer 124 results in a sensing layer 136 that has enhanced gas sensing performance with a very fast response rate.
With reference again to
Using ALD, as described above, results in a sensing layer 136, 236, 336 that includes large amounts of three-interface regions between gas, metal/metal oxide, and the seed layer. Additionally, the ALD process results in a gas-sensing region 190, 290, 390 being formed at the interface of the sensing layer 136, 236, 336 and the seed layer 124, 224, 324.
In another embodiment, nucleation of a plurality of grains of a sensing material is encouraged/developed between a suitable pair of materials. For example, the seed layer 124 is formed from a first material and the sensing layer 136 is formed from a second material that is “suitable” for depositing on the seed layer using ALD. To prevent the formation of a contiguous layer of the deposited sensing material, the material of the seed layer 124 is processed into a non-suitable seed layer to encourage spaced apart nucleation of the deposited sensing material into a plurality of grains that form the porous sensing layer 136.
One way that the material of the seed layer 124 is processed is by selectively removing material of the seed layer to form the non-suitable seed layer. For example, in one embodiment, the suitable material is trenched to form the non-suitable seed layer 124. The seed layer 124 may be trenched with any suitable number and arrangement of trenches that results in spaced apart nucleation of the deposited sensing material of the sensing layer 136.
Another way that the material of the seed layer 124 is processed is by defining spaced apart nucleation sites 182 in the material of the seed layer. Desired nucleation sites 182 are defined, in one embodiment, by ion-milling the material of the seed layer 124 with passive gasses at the desired nucleation sites. Desired nucleation sites 182 are defined, in another embodiment, by chemically activating the material of the seed layer 124 at the desired nucleation sites.
In yet another embodiment, upon adsorption of the target gas by the sensing layer 136, 236, 336, the presence of the target gas is detected by the external circuit in response to the sensing layer undergoing a change in resonant frequency and/or a change in capacitance between the electrodes 128, 132.
While the disclosure has been illustrated and described in detail in the drawings and foregoing description, the same should be considered as illustrative and not restrictive in character. It is understood that only the preferred embodiments have been presented and that all changes, modifications and further applications that come within the spirit of the disclosure are desired to be protected.
This application claims the benefit of priority of U.S. provisional application Ser. No. 61/897,269, filed on Oct. 30, 2013, the disclosure of which is herein incorporated by reference in its entirety.
Number | Date | Country | |
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61897269 | Oct 2013 | US |