In a very general level the current invention belongs to the field of sensors, but in more specifically concerns a solid state micro gas sensor component as indicated in the preamble of an independent claim on the gas sensor structure. The invention also concerns a measurement method as indicated in the preamble of an independent claim thereof. The invention also concerns a gas sensor matrix of gas sensors as indicated in the preamble of an independent claim thereof. The invention also concerns gas measurement device with a gas sensor as indicated in the preamble of an independent claim thereof. The invention also concerns gas measurement device with a gas sensor matrix of gas sensors as indicated in the preamble of an independent claim thereof. The invention also concerns a software program product as indicated in the preamble of an independent claim thereof.
Metal oxide semiconductor (MOS) gas sensor is a mature innovation [1, 2] and has many advantageous features such as high sensitivity, fast response and recovery, versatile selectivity through operational temperature and sensor materials as well as good capabilities for low-cost mass production and small size mobile applications. It has been widely applied in automatic ventilation control systems, household applications and recently also in toxic gas sensor devices. The known sensor technology as such is suitable for measuring various volatile organic compounds, toxic chemical vapours as well as gases such as NO2, CO, CH4 and H2S.
However, many drawbacks can be addressed restricting the use of MOS gas sensors more widely. Those include: frequently observed drift, poor quality due to reproducibility challenges, narrow dynamic range and non-linear response. The main consequences of these drawbacks are poor accuracy and poor precision. Therefore, typical application is to trigger predetermined less-accurate concentration level of the given gas—not performing quantitative measurement for wide concentration range.
Furthermore, the basic feature of the MOS gas sensor is high operational temperature, typically 200-400° C. In order to reach that, the known MOS sensor requires integrated heater resistor. If the mass and heat conductivity of the sensor is high, the power consumption of the sensor will be also high. That feature restricts significantly capabilities for mobile applications and for consumer electronics. An excellent solution of the known techniques for reducing the power consumption of the MOS gas sensor is so called micro hot plate structure [3-6] where sensor is miniaturized to only a few micrometer thickness as illustrated in
The gas sensor material of the conventional known MOS gas sensor as such is prepared by thick film technology or through colloidal liquids by drop deposition [4, 5] while the micro hot plate based structures are prepared by using semiconductor CMOS and MEMS technologies. The problems in quality and reproducibility are generally associated to the thick film sensor material. However, it has been demonstrated that the MOS gas sensor material can be prepared by vapour phase deposited thin film technologies also. In that case, both chemical vapour deposition (CVD) and physical vapour deposition (PVD) methods are basically feasible. A good quality and reproducibility by the thin film methods is expected. However, it is commonly believed that high surface area and porous microstructure are important properties to obtain sufficient sensitivity. These properties are easily reached by thick films or extremely porous thin films like those formed by nanometer size grains. High quality and reliability has not been the main aim for the developers so far, although especially CVD-type thin films exhibit evidently good performance in that respect. Of the thin film deposition methods, PVD thin films have been more favourable than CVD thin films. That is because the combination of CVD sensor material to the micro hot plate structure is challenging for the fabrication and, on the other hand, PVD sensor materials possess typically more porous microstructure than dense CVD thin films.
Furthermore, the typical cost-efficient manufacturing favours outsourcing the fabrication of CMOS components, like micro hot plate platforms, to the CMOS foundries, like proposed by Muller et al [6]. However, typically CMOS foundry does not have processes available to deposit less-common sensor materials, like semiconductor metal oxides and transition metal catalysts. Therefore sensor manufacturer needs to focus on development of the metal oxide sensor material on top of the pre-fabricated platform and that last, in-house, process step forms the core technology expertise. In order to reach cost-efficiency, the thick film processes are typically favoured.
However, the current invention focuses to the commercially less-common thin films as such and, especially to thin films with dense microstructure. The dense thin film materials can exhibit significantly different transducer mechanisms than porous materials since in the latter case the grain boundary potential apparently dominates whereas in the former case the role of surface, interface and contact potentials can be much more significant. If the contribution of these factors is not controlled, the result may be regarded as poor quality and poor reproducibility. This aspect is not always understood properly when MOS gas sensors are designed.
The availability of accurate and reliable MOS gas sensor would enhance significantly the capabilities of the sensor in its present applications as well can be the way to find new applications. The present invention shows an innovative MOS gas sensor chip, component and measurement principle to achieve the high accuracy and good precision and overcome the problems of the present state-of-art.
The micro hot plate based MOS gas sensors as such in known techniques contain the crucial elements such as a sensing layer, sensing electrodes, heater electrodes and an insulator layers between them as shown in the
It is an aim of the invention to solve, or at least mitigate, the problems of the known techniques. The aim is achieved with embodiments of the invention as relating to a gas sensor structure.
A micro hot-plate solid-state gas sensor structure according to the invention is characterized in that what has been indicated in the characterizing part of an independent claim thereof. A measurement method according to the invention has been characterized in that what has been indicated in the characterizing part of an independent claim thereof. A gas sensor matrix according to the invention has been characterized in that what has been indicated in the characterizing part of an independent claim thereof. A gas measurement device with a gas sensor according to the invention has been characterized in that what has been indicated in the characterizing part of an independent claim thereof. A gas measurement device with a gas sensor matrix of gas sensors according to the invention has been characterized in that what has been indicated in the characterizing part of an independent claim thereof. A software program product according to the invention has been characterized in that what has been indicated in the characterizing part of an independent claim thereof.
Further embodiments of the invention are shown in the dependent claims.
The present invention concerns a structure for a micro hot plate based MOS gas sensor with thin film, preferably CVD thin film, sensor materials. It also involves an electronic measurement principle as well as it involves fabrication methods to improve the quality of the device. In a combination of those mentioned, the embodiments of the invention sensor drift can be controlled, sensor fabricated in a reproducible manner as well as the dynamic range extended and the selectivity to gases enhanced in respect to the known techniques. Generally, the sensor reliability and accuracy can be thus enhanced and new utilisation of applications expected.
Because the
a illustrates a cross section of an active area according to an embodiment of the invention,
b illustrates a cross section of an active area according to another embodiment of the invention,
a illustrates a top view of two active areas according to an embodiment of the invention,
b illustrates a top view of a multielectrode configuration of two active areas according to another embodiment of the invention,
c illustrates a view of a multielectrode configuration and transmission lines according to an embodiment of the invention,
The same reference numerals are used for same kind of parts in the Figs, although the parts should not be necessary exactly the same in the shown embodiments. The various embodiments of the invention are combinable in suitable part.
Nevertheless, as shown in the
According to an embodiment of the invention, the semiconductor metal oxide layer has well-controlled microstructure, dopant concentration and/or lattice imperfections, such as oxygen vacancies. An embodiment of the invention concerning a gas sensor structure is not easily influenced by the prolonged heating and operation. Preferably, that is obtained, while manufacturing, by applying CVD-type ALD (Atomic Layer Deposition) thin film deposition method or other deposition method facilitating good control and reproducibility. The thickness of the semiconductor oxide layer 3 is close to Debye length of the employed oxide semiconductor. In an embodiment of the invention a practical Debye length is in the range 10-100 nm. A preferred semiconductor material is a metal oxide exhibiting n-type semiconductor properties and surface potential variations due to exposes to low concentrations of volatile compounds or gases in the elevated temperatures. Examples of such materials are SnO2, WO3, In2O3 and TiO2.
According to an embodiment of the invention, the selectivity of the metal oxide is tailored by applying a catalytic overlayer 2 on top of the semiconductor oxide layer in a manufacturing phase. Those materials are typically transition metals, noble metals as well as earth alkaline and rare earth metals and/or their oxides. According to an embodiment of the invention a theoretical thickness of the overlayer is in the range of one nanometer. According to another embodiment of the invention a theoretical thickness of the overlayer is less than one nanometer. According to an embodiment of the invention a theoretical thickness of the overlayer is less than ten nanometers. According to another embodiment of the invention a theoretical thickness of the overlayer is less than 20 nm. According to an embodiment of the invention a theoretical thickness of the overlayer is less than fifty nanometers. According to an embodiment of the invention the theoretical thickness of the overlayer is between 5 and 15 nm. According to an embodiment of the invention the theoretical thickness of the overlayer is between 12 and 25 nm.
According to an embodiment of the invention the overlayer material is uniformly a monolayer. However, according to another embodiment of the invention, the overlayer material is not necessarily uniformly a monolayer, but can be distributed forming nanometer-scale islands. The distribution and structure of the overlayer depends on the applied material and the fabrication process details. Preferably, the overlayer is deposited by using conventional thin film deposition methods as such.
In
In an embodiment of the present invention, the electrode configuration is a conventional electrode pair as shown in
According to an embodiment of the invention the interdigital electrode gap is similarly wide as the electrodes. According to an embodiment of the invention the interdigital electrode gap is less than 5 times wider as the electrodes. According to an embodiment of the invention the interdigital electrode gap is less than 10 times wider as the electrodes. The wide gap enhances sensitivity to gases. The main part of the total sensor resistance originates from one metal oxide layer 3 between electrodes.
In another preferred embodiment, the electrode configuration is a multielectrode configuration as shown in the
b shows two differently sized active area configurations. In this exemplary embodiment of
The active area structure as exemplary embodied in accordance to
In order to control accurately the heater power, characteristic feature of the present invention is also that the favoured material in the heater layer 6 is thermally stable and inert metal that exhibit high thermal coefficient of resistance in the 200-400° C. operational temperature range. That facilitates high accuracy for the temperature measurement and control that is crucial for accurate measurements. Examples of such materials are tungsten and platinum.
In order to manufacture a sensor according to an embodiment of the invention, a metal oxide semiconductor layer 3 is processed as a similar step as other layers 1,4,5,6,7,8. Such a method comprises process steps for deposition of the thin film and its patterning either by wet etching or dry etching. Such an approach simplifies the integration of CVD-type thin film process to the micro hot plate structure.
According to an embodiment of the invention the sensor area is a plane like structure. According to an embodiment of the invention the sensor area has several such plane like structures in parallel or in series to be operated as gas sensors. According to an embodiment of the invention the sensor area is curved into a non-planar structure. According to an embodiment of the invention the sensor area is curved into tube-like structure, to provide the gas as flow through the tube.
In an embodiment of the invention concerning a matrix of gas sensors according to an embodiment of the invention, such a matrix comprises one type of gas sensors, large sensor type or small sensor type, of which sensors all have same active area structure. However, the sensitive layers 2,3 are not necessary of same material, but can be different so to provide different selectivity to gases. In an example, SnO2 as such can be used as metal oxide layer 3 and SnO2 in combination with Pd catalyst layer 2 in another sensor.
A gas sensor matrix according to another embodiment of the invention has at least two types of gas sensors according to an embodiment of the invention, large sensor type and small sensor type. A gas sensor matrix according to another embodiment of the invention has at least two types of gas sensors according to an embodiment of the invention, but one type has a great sensitivity and another one has a lesser sensitivity for the same gas in same conditions. This can be achieved by the number of the electrodes in the active area in one embodiment, but in another embodiment by the mechanical size. A gas sensor matrix according to an embodiment of the invention comprises at least one gas sensor according to the known techniques in combination with a gas sensor of the type of large sensor type or a small sensor type, according to an embodiment of the invention. In such an embodiment, intercalibration of various sensors can be achieved. According to an embodiment of the invention the matrix can be curved, according to another embodiment of the invention even into tubular geometry to provide the flow through the tube.
According to an embodiment of the invention the substrate on which the active area with the electrodes are formed is silicon. In another exemplary embodiment the substrate can be a polymer of high temperature resistant below 300° C., or a ceramic substrate suitable for the elevated temperatures even up to 500° C. However, the temperature values are just examples and are not limiting the substrate only to mentioned. According to an embodiment of the invention even a lower temperature-resistant substrate can be used, if in such an embodiment the heating were limited according to the substrate temperature behaviour.
A gas measurement device according to an embodiment of the invention comprises at least a sensor according to an embodiment of the sensor. A gas measurement device according to another embodiment of the invention comprises at least a sensor matrix according to an embodiment of the sensor.
A gas measurement system according to an embodiment of the invention comprises at least two gas measurement devices according to an embodiment of the sensor. In such an embodiment, a further variant comprises also a means to be used accordingly to be used for collecting data and/or transfer data from at least one of said devices. In an even a further variant of such an embodiment of the invention, the system comprises means for performing calibration, measurement, and/or control of the heating of the active area. At least one of mentioned operations can be performed by a software means arranged to implement the measurement and/or the maintaining routines to control at least one sensor in a device and/or in a system.
A measurement circuit according to an embodiment of the invention, for the MOS gas sensor, is illustrated in
In a preferred embodiment of the present invention, where the electrode configuration facilitates transmission line model test pattern (
According to an embodiment of the invention, in an electrode configuration, the L/W values cover at least one order of magnitude of the L/W-range. In an embodiment concerning a sensor matrix, in such an embodiment there can be a first plurality of sensors with a first L/W values in a first range. According to an embodiment of the invention there can be additionally also a second plurality of sensors with a second L/W values in a second range. According to an embodiment of the invention the ranges are different. According to an embodiment of the invention the ranges overlap.
Although
According to an embodiment of the invention, the sensor contains a buried electrode 5. It can be utilized several ways in sensor measurements. According to an embodiment of the invention utilising micro hot plate structure, the heater resistor relatively close to the sensor layer, typically isolated by a dielectric material, like silicon oxide or silicon nitride. Especially, if the exact temperature will be maintained in the sensor, regardless of lifetime and outdoor conditions, the heater voltage is needed to be varied. Furthermore, high accuracy measurement requires also correct absolute temperature set-point for the sensor, which leads also to the slight differences in heater voltages between individual sensors. The heater voltage can influence on the sensor measurement uncontrollable way through capacitive coupling between sensor and heater layers. In a preferred embodiment of the invention, the contribution of the heater voltage to the sensor measurement can be improved or even eliminated, in an embodiment of the invention, by grounding the buried electrode 5.
In a preferred embodiment, the bias voltage is applied to the buried electrode. The influence of this bias voltage is illustrated theoretically in the
Usually the transducer model of the MOS gas sensor assumes the electronic charge carriers contribute only—not ionic charge carriers. In one preferred embodiment of the present invention this problem is overcome by applying ac voltages for the sensor resistance measurement. According to an embodiment of the invention, a suitable frequency is 10-100000 Hz, but in a preferred embodiment 10-1000 Hz. According to an embodiment of the invention, the frequency is in the range 100-10000. According to an embodiment of the invention, the frequency is in the range 1000-1000000. By using ac voltage, the polarization effects on the material interfaces and grain boundaries due to slow contribution of the ionic carriers can be significantly reduced in an embodiment of the invention, thus reducing the drift. In a preferred embodiment, the ac voltage is applied in all electrode-pairs, namely in all sensor electrodes as well as the bias in buried electrode is modulated.
Temperature measurement circuit, according to an embodiment of the invention, measures either resistance of the heater resistor or resistance of the temperature sensor integrated into the heater layer. In another preferred embodiment heater voltage and heater current are measured facilitating heater power measurement. In both cases it is crucial to select the heater resistor material so that resistor's temperature coefficient of resistance is high. Examples of such materials are platinum and tungsten. The result is sensitive temperature measurement and control circuit that facilitates highly accurate and reliable sensor measurement. Furthermore, in another preferred embodiment, the sensitive temperature measurement facilitates measurement of calorimetric output due to combustion reactions taking place in heated sensor surface as demonstrated in
It is exemplary demonstrated in
a) Sensor resistance in Sensor#1 with Pt-heater due to exposure to 4000 mg/m3 hexane vapour.
b) Heater resistance in Sensor#1 with Pt-heater due to exposure to 4000 mg/m3 hexane vapour.
c) Sensor resistance in Sensor#2 with silicon-heater due to exposure to 4000 mg/m3 hexane vapour.
d) Heater resistance in Sensor#2 with silicon-heater due to exposure to 4000 mg/m3 hexane vapour.
In this example, Pt heater exhibit sufficient temperature coefficient of resistance for successful measurement while silicon heater does not.
In general, the gas sensor device and measurement method of the present invention facilitate mass fabrication compatibility with very high quality and reproducibility. By combining all advantages provided by the present sensor device and its measurement principle, the absolute sensor resistance can be deployed as a sensor signal and the result is extremely reliable and accurate MOS gas sensor.
Number | Date | Country | Kind |
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20060389 | Apr 2006 | FI | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/FI2007/000107 | 4/23/2007 | WO | 00 | 3/4/2009 |