• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    DEVICE FOR THE QUANTITATIVE DETECTION OF A SUBSTANCE IN A FLUID SAMPLE, USE OF A DEVICE, AND METHOD FOR THE QUANTITATIVE DETERMINATION OF A SUBSTANCE IN A SAMPLE FLUID USING A DEVICE The present invention refers to a device (100) for the detection a concentration of a substance in a fluid sample, the device comprising: a substrate (102); an insulating layer (104) disposed on the substrate (102); a plurality of individually and electrically addressable semiconductor nanowires (106, 108, 110) arranged in the insulating layer (104), each of the plurality of nanowires being covered by an insulating material (202, 204, 206) and arranged for the detection of the substance through an electrical characteristic of the nanowire; and a sample compartment (118) for providing the fluid sample in contact with each of the plurality of nanowires; where for each of the plurality of nanowires (106, 108, 110), at least one of the cross-sectional dimensions, the thickness of the insulator and the type of insulating material are selected, such that each of the nanowires has a different band detection and such that the dynamic range of the device is greater than the dynamic range of each of the individual nanowires.
    公开号:BR112015008202B1
    申请号:R112015008202-5
    申请日:2013-10-07
    公开日:2021-02-09
    发明作者:Johan Hendrik Klootwijk；Marcel Mulder
    申请人:Koninklijke Philips N.V；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to a device for detecting a concentration of a substance in a fluid. In particular, the present invention relates to a nanowire based device. BACKGROUND OF THE INVENTION
    [002] Sensors for the detection of biological substances based on nanoscale field effect transistors such as, for example, silicon nanowire FETs and carbon nanotubes with properly functionalized surfaces, have enormous potential for very sensitive detection of concentrations minute (even fentomolar) biomolecules such as proteins and DNA. In addition, when appropriate interface layers are applied through the functionalization of the surface in contact with the active substance, these devices are likewise potentially interesting for gas detection.
    [003] In all applications where the nanoscale field effect transistor is used, there is a strong desire to detect multiple target molecules simultaneously. In a liquid or gas environment, the use of a reference transistor of crucial and critical importance in order to compensate for time-related deviation.
    [004] For many gas sensor applications, such as indoor air quality management (IAQ), HVAC, asthma, cardiovascular diagnosis and greenhouse control, high sensitivity combined with a wide dynamic range is required. Mass spectrometry is the standard method for gas detection. This technique is sensitive, selective and has a wide dynamic range, but it is also costly and very large. Alternatively, optical detection, more specifically, infrared absorption spectroscopy (IR), is being used as a gas sensor. This technique is sensitive and selective, but a module can only detect one type of molecule and the measurement equipment is expensive and very large. Electrochemical detection can also be used, but it does not provide the appropriate sensitivity or selectivity.
    [005] The document US2010 / 0243990 discloses a sensor device based on nanowire for the detection of biomolecules. The devices are based on a silicon nanowire field effect transistor, where the nanowire can be doped with n-type or p-type impurity. The nanowire surface is functionalized by molecules that are specifically coupled to their targeted counterparts. The charges on the target molecules affect the conductivity of the nanowire channel as an access electrode. SUMMARY OF THE INVENTION
    [006] The inventors recognized that, for the practical application of detection devices, a high dynamic range is necessary, often in combination with a low detection limit. It is a problem with known detection devices that a high sensitivity sensor comes with a low dynamic range.
    [007] It is an objective of the present invention to provide a sensor based on nanowires that is capable of providing an improved dynamic range, preferably in combination with a high sensitivity.
    [008] The objective is achieved with the invention, as defined by the independent claims. The dependent claims provide advantageous achievements.
    [009] According to the invention, a device is provided to detect a concentration of a substance in a fluid sample.
    [010] A fluid can refer to both a gas and a liquid and the device is therefore suitable for detecting substances in liquids and gases. Substances can be dissolved or suspended in the sample. Substances can comprise ions, molecules, molecular complexes, particles. In particular, they may be substances that may be present in the fluid at low or high concentrations not previously known. The substances can be toxic to life, requiring determination of adequate concentration and also continuous determination preventing extensive pre-processing (dilution) before detection.
    [011] The fact that the nanowires are electrically addressable means that it is possible to form an electrical contact for each end of each nanowire, to carry out the electrical characterization of the respective nanowires in relation to the characteristics of the nanowire sensitive to the presence of the substance, when the fluid with the substance is brought into the vicinity of the nanowire. The nanowires of the plurality of nanowires are individually addressable. For this purpose, the nanowires are preferably electrically connected in parallel between various electrical contact points. Thus, while one end of each nanowire can be electrically connected to one and the same connection point, each end must be contacted individually. Sequential addressing of the nanowire can be achieved using individual access structures if the nanowires are part of one or more transistors. Alternatively, each nanowire is completely addressable electrically and individually, so that its ends form separate contact points for each nanowire, whether on the transistor or not.
    [012] When a molecule or particle of substance to be detected reaches the vicinity of, or even attaches to, the nanowire, the measurable electrical characteristic of the nanowire is influenced according to the amount of substance and by measuring the characteristic the amount of substance can thereby be deducted. The amount can be an absolute amount or concentration amounts as in the amount of substance per sample volume, sample mass or moles of sample.
    [013] The plurality of nanowires comprises at least two nanowires. The amount of nanowires can be equal to and / or greater than 3, 4, 5, 10, 20 and up to 50. They can be conveniently manufactured in the same standardization process as the device. Each nanowire can be duplicated to allow reliable measurement. The insulating material can be any electrically insulating material. The material first prevents the nanowires from being short-circuited with the sample fluid. The insulating material is preferably an oxide, such as, for example, silicon oxide (SiO2) or titanium oxide (TiO2) or mixtures thereof. The insulating material may comprise a surface that is exposed to the sample fluid.
    [014] The sample compartment is arranged so that the sample is brought close to, or in contact with, each nanowire including, at least, the insulating material. Each of the nanowires coated with the respective insulating material is then arranged to detect the presence of the substance in the fluid sample by measuring an electrical characteristic of the nanowire. Any characteristic that is influenced by the possible presence of a substance in the sample compartment can be used for detection purposes. The measured electrical characteristic is preferably, for example, the current versus voltage characteristics of the nanowire. Preferably, this characteristic is of a nanowire that makes up a transistor with an access. By analyzing the measured characteristics, the quantity (concentration) of a substance in the sample can be determined. Calibration curves can be used, if necessary. Preferably, there are reference nanowires that are only in the vicinity of the fluid sample without the substance.
    [015] The nanowires different from a plurality of nanowires in a device are configured so that the detection range of each nanowire is different. The detection range is the range between the lowest and the highest detectable concentration or amount of a substance in the fluid sample. The smallest amount is defined by the amount of substance that did not change the electrical characteristic of the nanowire, while the highest detectable quantity is the amount above which no increase in the same electrical characteristic was observed, both are related to the saturation signal. The total detection range of the detection device is given by the set of nanowires, that is, it is then, the sum of the detection range of each nanowire.
    [016] Therefore, the present invention is based on the realization that a nanowire based on the detector with a high dynamic range can be obtained, organizing a number of individually addressable nanowires, having different dynamic bands in parallel to measure a substance in a fluid. In this way, the device can be configured so that the total dynamic range of the device is greater than the respective dynamic range of the individual nanowires. Preferably, the nanowires of the plurality of nanowires are configured so that the different detection ranges of each of the pluralities of nanowires together form a substantially continuous detection range, which is greater than each different detection range. As an example, if a first nanowire can measure a substance concentration between 1 and 10, and a second nanowire can measure a concentration between 10 and 100, the dynamic range of each nanowire will be 10, while the dynamic range of one The device comprising the two nanowires in combination can be 100. The device of the invention is advantageous since the samples now do not need dilution before being provided to a sensor to avoid saturation. In addition, a detection device can be made, where the detection range can be chosen by means of the number of nanowires and their dynamic range configuration. In addition, the sensitivity of the device (related to the detection limit) can be defined independently by the configuration of the most sensitive nanowire. The device can be designed to be able to detect substances with a concentration of 100 ppm or greater up to 10 ppb. Thus, a detection device with improved dynamic range and a state of sensitivity of the technique can be obtained.
    [017] The device can, in this sense, be made using conventional semiconductor materials and is therefore suitable for integration with CMOS-based circuits or with lab-on-a-chip lab solutions using pre-existing techniques. well-developed manufacturing processes that require minimal adaptation to existing manufacturing processes. The device can also advantageously be combined with other types of sensors such as temperature sensors, conductivity sensors, etc. In addition, by selecting different insulating materials for different nanowires, different substances can be detected simultaneously by a device. An additional advantage of the present invention is that compatibility with established processing methods means that the sensor devices can be manufactured at a relatively low cost.
    [018] The degree of influence that the substance will have on the characteristic of the nanowire depends on the compositional as well as structural parameters of the nanowires and the additional layers. Each nanowire of said plurality of nanowires can comprise a surface area and a volume of nanowire, wherein the range of the surface area and the volume are different for the nanowires different from said plurality of nanowires. The higher the ratio, the more sensitive the nanowire will be to the presence of the substance in its vicinity and vice versa. The change in the detection range, that is, not necessarily an increase or decrease in the detection range, but simply a different range, comes with a change in the ratio. The nanowire may have an exposed detection surface beside it where the sample compartment extends. The detection surface can be arranged to detect the presence of the substance.
    [019] To vary the ratio between nanowires other than the plurality of nanowires, the length, width or height (thickness) of the nanowire can be used. Preferably, then the length or width is varied while the thickness (perpendicular to subtract the extent of the layer) is kept constant. If the plurality of nanowires is arranged on a flat substrate, the plurality of different dimensions of the nanowires can be defined in the single and equal standardization step (masks) again, saving additional costs. Also, on many regular substrates the layer, on which the nanowires are made, is a deposited layer of uniform semiconductor thickness, such as silicon. Therefore, standard substrates can be used and the etching steps to vary the thickness of such a layer are not necessary to reduce processing complexity and cost savings. It is preferable that the width of the nanowire is varied, while the length is also kept constant for the plurality of nanowires. The width of the nanowires is preferably in the range of 8 nm to 1 micrometer. The smallest range is in practice limited to the smallest characteristic sizes that can be standardized using lithography or printing techniques. A preferred range is 50 nm to 500 nm. A more preferred range is 10 nm to 500 nm. Within these ranges, there may be nanowires with widths of 10, 15, 20, 25, 30, 50, 100, 200, 300 and 400 nm or any combination. This results in nanowires that, due to their length, still offer resistors that can be used in regular IC structures. (it is observed that the cross-section of the nanowire determines its resistance). The lengths of the nanowires can be between 1 to 10 micrometers. They can be less than 2 micrometers, less than 1 micrometer, or less than 500 nm.
    [020] Alternatively or in addition to the dimensional variation between the nanowires of the plurality of nanowires, the thickness of the insulating material and the choice of the insulating material covering the nanowire can be changed to implement variations in the detection range. The influence of the substance on the characteristics of the nanowire can be through capacitive coupling. Thus, an increase in the thickness of the insulator provides a smaller coupling and less sensitivity and vice versa. Also, the material variation with the highest dielectric constant will result in increased coupling and increased sensitivity and vice versa. Again, the arrangement of these parameters comes with a different detection range. As the dielectric constant is largely determined by the insulating material which is, in general, compatible with the processing and substrate materials, the layer thickness is the preferred parameter to vary between the nanowires of the plurality of nanowires. The thickness is preferably between 1 nm and 10 nm to provide good sensitivity. If increased sensitivity is required, the thickness will be in the range of 1 to 4 nm, more preferably 3 nm. If increased reliability with regard to the electrical insulation of the layer of insulating material is required, the thickness will preferably be in the range of 6 to 10 nm, more preferably 7 nm. A thickness of 5 nm provides a good compromise between sensitivity and reliability.
    [021] As an example, a nanowire with a smaller cross-sectional area and a thinner insulation layer will be more influenced by a substance molecule than a wire with a larger area and a thicker insulation layer. Such influence can be through capacitive or inductive changes in the nanowire between the situation with substance or without substance.
    [022] The device of the invention can be a pH detection device. The insulation layer on the nanowire may be silicon oxide for this purpose. The silicon oxide surface generally has Si-OH groups of which the H + (substance) is reversibly interchangeable with the sample fluid (preferably comprising or consisting of water for a good pH definition). Therefore, the charge of a surface layer of silicon oxide (Si-O-) depends on the pH of the fluid, that is, high pH reduced the surface charge of voluminous and limited H + and at low pH all groups would be converted Si-OH and no charge on the surface. The load determines a.o. the conductivity of the nanowire and it can be used as a characteristic of the nanowire to measure.
    [023] The device may also comprise a functionalization layer disposed in the nanowire or in the insulation material of at least one of the nanowires. Adding specific functionalization layers on one or more nanowires makes it possible to adapt the device to detect a particular substance or group of substances. A simple (covalent) chemical reaction of the substance with the functionalization layer can be used. Alternatively, molecular recognition by means of all types or non-covalent reactions, adhesion effects can be used.
    [024] In addition, by adding different functionalization layers to different nanowires, it also makes it possible to detect several different substances or groups of substances simultaneously. Such a device can be used for fingerprint printing.
    [025] For example, a TiO2 layer can be arranged as the insulation layer or, preferably, on the nanowire insulation layer to act as a functionalization layer. Since TiO2 is known to react with and decompose CO2, a CO2 sensor can be formed. Other layers of functionalization can be used. The NiOx layer can reduce / oxidize in the presence of formaldehyde and can be used to build a responsive nanowire for formaldehyde. Those skilled in the art will know which layers need to be used to recognize specific substances or specific groups of substances. An example can provide layers for the detection of blood markers, such as those for the detection of heart disease. In another example, the layer is configured to detect carbohydrates or other organic molecules as contamination in, for example, water fluid.
    [026] According to one embodiment of the invention, at least two of the nanowires can have different doping concentrations. Varying the doping of the nanowire is an additional means of influencing the electrical characteristics of the nanowire in order to adapt the properties of the sensor for various applications. For example, different doping can be used to recognize threshold voltages other than nanowires. This can provide a different sensitivity to nanowires.
    [027] The sample compartment can be configured to allow a fluid to flow over a plurality of nanowires. In this way, a concentration of a flow fluid can be detected which, for example, facilitates the integration of the device in the laboratory devices on an existing chip. In addition, the sample compartments can be arranged as an opening in a protective layer so that the contact structures for electrically contacting the nanowires are protected, thus avoiding a short circuit between the contact structures, in the case of a sample fluid conductor.
    [028] The substrate part (such as the back of the substrate) can be used as an access terminal for a transistor, of which at least one of the nanowires of the plurality of nanowires comprises it. The device then forms a triple terminal device with the rear as an access terminal and the contact structures as drain and source terminals. Using the rear as an access terminal can serve to intensify the current response to an applied voltage, or it can be used as a control switch if any current flows through the nanowire. In this way, the electrical characteristics of the nanowires can be controlled by the access terminal. The substrate can be standardized to provide individual access structures for each nanowire required.
    [029] The device may comprise a second sample compartment allowing simultaneous detection of more than one substance. A second sample compartment can be used to provide different fluids in contact with sets of nanowires to perform several analyzes simultaneously. In addition, the use of two or more sample compartments can further facilitate having nanowires with different characteristics in different sample compartments. In particular, different wire configurations, which due to the complexity of the manufacturing process can be difficult to combine in one sample compartment, can be more easily achieved using several sample compartments.
    [030] The device may comprise electrical circuits connected to each of said nanowires of the plurality of nanowires for reading the nanowires. The device can be a measuring device, ready for use for sample analysis.
    [031] The electrical circuits are preferably configured to:
    [032] determine an electrical characteristic of each nanowire of said plurality of nanowires;
    [033] determine, for each nanowire of said plurality of nanowires, when the electrical characteristic indicates that the nanowire is saturated;
    [034] identify a subset of nanowires of said plurality of nanowires for which the nanowires are not saturated;
    [035] from the nanowire subset, identify the nanowire having the highest sensitivity; and
    [036] based on the specific electrical characteristic of the nanowire having the highest sensitivity, determine the amount of said substance in said fluid.
    [037] The device may comprise one or more reference nanowires (each defined in accordance with the invention) that are covered by a reference sample compartment instead of the sample compartment. Such a compartment can be easily integrated. These nanowires can be used to determine the effect of the sample without the substance and be responsible for the background signal during sample detection.
    [038] According to the invention there is also provided a method for determining the concentration of a substance in a sample fluid using a device comprising a plurality of individually addressable nanowires.
    [039] Measuring the amount or concentration of a substance in a fluid using a high dynamic range nanowire based device as described above can be achieved by detecting which of the nanowires are unsaturated and selecting the most sensitive unsaturated nanowires reading. The resulting amount and / or concentration can also obviously be derived from a combination of measured unsaturated nanowires, either by averaging the results of the unsaturated wires or by using more complex determination algorithms. In addition, it can be assumed that the device is calibrated or that it also knows how different nanowires respond to different concentrations of a specific substance, thus making it possible to determine whether a given nanowire is saturated or not. According to an embodiment of the invention, the determined electrical characteristic of the nanowires can advantageously have the current as a function of an applied voltage.
    [040] In one embodiment of the invention, the device can be advantageously restarted by applying an access voltage so that the molecules that adhere to the nanowires are removed. It is highly advantageous to be able to restart the device in order to avoid the need to know the measurement history of the device and also in order to reuse a device that was once saturated. Consequently, the device can be restarted by applying a voltage to the rear of the substrate that acts as an access terminal. The applied access voltage is of opposite polarity to the operational access voltage so that the electrostatic repulsion causes the molecules that adhere to the nanowires to be released, thus cleaning and restarting the device.
    [041] According to an embodiment of the invention, the device can be advantageously restarted by heating the device so that the molecules that adhere to said nanowires are removed. By applying a sufficiently high voltage to the nanowires, so that the temperature in the nanowires is increased through resistive heating, the molecules that adhere to the nanowire are released through thermal desorption and the device is thus restarted.
    [042] Other effects and characteristics of this second aspect of the present invention are largely analogous to those described above in connection with the first aspect of the invention.
    [043] It is noted that the invention relates to all possible combinations of characteristics recited in the claims. BRIEF DESCRIPTION OF THE DRAWINGS
    [044] These and other aspects of the present invention will now be described in more detail with reference to the accompanying drawings showing an exemplary embodiment of the invention, in which:
    [045] Figure 1 schematically illustrates a device according to an embodiment of the invention and;
    [046] Figure 2 schematically illustrates nanowires according to various embodiments of the invention;
    [047] Figure 3 schematically outlines a method for manufacturing a device according to an embodiment of the invention and;
    [048] Figure 4 is a flow chart outlining the general steps of the manufacturing method illustrated in Figure 3. DETAILED DESCRIPTION
    [049] In the present detailed description, various embodiments of a device according to the present invention are mainly discussed with reference to a device comprising silicon nanowires based on a substrate of SOI (silicon on insulator). It should be noted that this in no way limits the scope of the present invention which is equally applicable to devices comprising nanowires based on other semiconductor materials which can also be formed on other types of substrates.
    [050] Figure 1 schematically illustrates a device 100 according to an embodiment of the invention. It should be noted that the device in figure 1 is not drawn to scale and that the purpose of the drawing is merely to illustrate the general concepts of the invention.
    [051] Device 100 comprises a substrate 102, an insulating layer 104 arranged on substrate 102, three nanowires 106, 108, 110 arranged in parallel are formed in the upper silicon layer of an SOI substrate. Conductive contact structures 112, 114 that lead to the contact pads (not shown) are also illustrated for the electrical contact of the respective end of each of the nanowires. Contact structures 112, 114 can be viewed as the source and drain in a three-terminal device where the rear of substrate 102 is used as an access terminal. In this case, all contacts are individually contactable giving individually addressable nanowires. However, contacts 112 or 114 can be connected together without losing the possibility of individual targeting. A protective layer (electrically insulating layer) 116 is arranged to cover contact structures 112, 114 to prevent electrical short-circuits in the case of a conductive fluid. An opening 118 in the coating layer forms a sample compartment 118 where a sample fluid can come in contact with nanowires 106, 108, 110.
    [052] Figure 2 schematically illustrates a cross-sectional view of nanowires 106, 108, 110. Each nanowire has a thickness (vertical in the design plane) and a width (horizontal in the design plane). The dimensions of nanowires typically range from a few nanometers to hundreds of nanometers. The nanowires are in turn coated with an insulating material 202, 204 206. The insulating material can typically be an oxide such as SiO2 (thermally developed), TiO2 or A12O3. Various rare earth oxides such as ZrO2, HfO2 or the like can also be used. Here it is illustrated that wires within the same device 100 can have different geometries as shown by the different widths of nanowires 106 and 108 and that nanowires having the same geometry can have different thickness of the insulating layer as illustrated by nanowires 108 and 110 and the insulating layers 204 and 206 correspondents. In this way, nanowires having different electrical characteristics can be formed. A device can typically comprise a large number of nanowires in each sample compartment, such as, for example, 2 to 50 nanowires or more. Preferably, there are 20 to 50 nanowires.
    [053] Different layers of functionalization can be arranged in the nanowires or in the insulating layer of the different nanowires. The functionalization layers can be, for example, chemical layers such as APTES or layers based on metal and oxides such as TiO2, ZrO2 or HfO2. In this way, applying different layers of functionalization to separate nanowires, a sensor array can be made that is sensitive to different substances so that a kind of fingerprint of the sample fluid under analysis can be determined. The different layers of functionalization can have different dielectric constants to provide different capacitive coupling to the wires to implement the range differences. Dielectric constants of different materials are widely tabulated in standard texts such as the Handbook of Chemistry and Physics and will not be mentioned here.
    [054] Nanowires can be part of a collector of different types of electrical devices in the device. Such electrical devices include access devices such as: devices based on field effect having an access (MOSFET, EGFET) or without an access (CHEMFET, ISFET, ImmunoFET, HEMFET, ESFET or ENFET.
    [055] The device can be a part of or it can be an electrical device for monitoring the purity of the gas or fluid. This can be an air pollution monitoring device. The substance to be detected may be formaldehyde as it is very toxic to humans. Alternatively, the device can be a water quality monitoring system. Such devices may have particulate filters or activated carbon filters to remove hazardous substances from the fluid sample before determining the amount of substance.
    [056] Figure 3 schematically outlines the general steps for manufacturing a device according to various embodiments of the invention. Figure 3 will be discussed with reference to the flowchart in Figure 4 which outlines the general processing steps.
    [057] In a first step 402, a SOI substrate is provided comprising a silicon carrier layer 102, a buried oxide layer (BOX) 104 and an upper silicon layer 302.
    [058] Next in step 404, a mask is formed and corresponding silicon nanowires and contact structures 304 are etched into the top silicon layer 302. A nanowire mask can, for example, be formed through photolithography, beam lithography and or printing. Etching is followed by step 406 comprising the deposition of an insulating layer 306. The deposition of an insulating layer may, for example, be preferable if subcaustication occurs such that the parts of the BOX layer 104 adjacent to or under the nanowires are damaged during the caustication of the nanowires. In this way, any damage that results from subcaustication can be repaired by depositing the insulating layer 306.
    [059] In steps 408 and 410, a protective silicon nitride (SiN) layer 308 is deposited followed by the deposition and standardization of a resistance mask (310) that exposes the nanowires. Next, the SiN 308 and the insulating layer 306 are removed at the location of the openings in the mask 310 in the regions where the nanowires are located in order to expose the nanowires.
    [060] In step 414, the resistance mask 310 is removed and in the final step 416, a thermal oxide 310 is developed on the nanowires to form an insulating layer on the nanowire. The thickness and properties of the thermal oxide developed can be controlled by the control process parameters such as time, temperature and pressure.
    [061] Steps 410 to 416 can be repeated for the same device in such a way that different nanowires or subsets of nanowires are exposed by different resistance masks, which in turn make it possible to form nanowires having layers of developed oxide 312 of different thicknesses or different properties. The growth of a thermal oxide also makes it possible to control the geometry of the nanowire by controlling the development time. As an alternative to thermal oxidation, an oxide can be deposited in step 416, thereby increasing flexibility in choosing the insulating material. The deposition can, for example, be carried out by CVD, ALD, cathodic deposition or other known deposition methods. Thus, by protecting different wires by different masks, nanowires, having different insulating materials and different thicknesses of the insulating layer, can be formed. In addition, several functionalizations of the nanowires can also be performed in step 416 by depositing functionalization layers such that a device capable of detecting a wide range of substances can be formed.
    [062] Nanowires with different length and / or width can be advantageously made in a set of steps since these are determined by mask dimensions and do not require repeated exposure of different sets of nanowires for depositions etc. In an exemplary embodiment, nanowires having different widths can be formed in step 404. Thus, after carrying out the remaining steps as described above, nanowires of different width, but with the same insulating material and insulating thickness are provided.
    [063] Electrical contacts with contact structures are also formed and an omic contact is formed at the rear of the substrate to form a rear access contact. In addition, as a result of the CMOS-compliant manufacturing process, a reference transistor is readily achievable on the same chip as an addition to the measurement device to allow differential measurements so that, for example, temperature changes and other environmental variations can be considered.
    [064] In addition, using the nanowire based device according to various embodiments of the invention, a method for determining a concentration of a substance in a fluid using the device is provided. In the following, an exemplary realization will be discussed with reference to current versus voltage measurements, carried out by a measurement arrangement comprising the device. First, the current versus voltage characteristic for each of the nanowires in a device is determined for a constant access voltage. Next, it is determined which of the nanowires, if any, are saturated. Saturation of the current in a nanowire can, for example, occur if the conductive channel is saturated, that is, if the conductive channel is completely closed or completely open. Saturation can also occur as a result of the saturation of the surface, that is, if the entire surface of the nanowire is coated with a substance. Current saturation can, for example, be determined by comparing the resulting measured characteristic with previously established reference values.
    [065] From the subset of unsaturated nanowires, the nanowire having the highest sensitivity is selected. The nanowire having the highest sensitivity is the nanowire capable of detecting the smallest change in concentration of the particular substance. It is considered that the sensitivity of each of the nanowires is known from the manufacture and / or more recent calibrations of devices has the same layout.
    [066] When identifying the most sensitive, unsaturated nanowire, a result indicating the concentration of a substance can be provided with the highest possible sensitivity for the given device.
    [067] If a device capable of detecting different substances is used, the method described above is performed for each subset of nanowires adapted to detect a respective substance.
    [068] An exemplary application for the device is as a reversible CO2 sensor. A CO2 sensor can be formed by coating the nanowires with a thin layer (approximately 1 nm) of TiO2. Since CO2 has a zero dipole moment, it will not induce an electric field in the channel if connected to an insulating layer comprising, for example, SiO2. Therefore, TiO2 can be used which is known to decompose CO2 into CO and O2, which is polar and thus induces a field in the conductive channel of the device.
    [069] However, oxides such as TiO2, ZrO2 and HfO2 tend to be hydrophilic, thus adsorbing water molecules on the surface which will affect the adsorption of CO2 and subsequently affect the electrical measurement. Therefore, in order to increase selectivity and reduce the interference of adsorbed water, a hydrophilic layer that is permeable to CO2, but not to water molecules can be deposited in the insulating layer. The hydrophilic layer can, for example, be a polymer such as parylene.
    [070] As an alternative to current versus voltage analysis, the transient behavior of the device can be analyzed by applying a constant voltage to the source, drain and access terminals and observing the time dependence of the measured current. In this way, the concentration of one or more substances in a fluid under analysis can be determined.
    [071] In addition, a fluid reference access for tilting the sample fluid can also be incorporated if it is required for a particular application.
    [072] The person skilled in the art notes that the present invention is by no means limited to the preferred embodiments described above. On the contrary, many modifications and variations are possible within the scope of the appended claims. For example, variations in the method of manufacture and the choice of materials are entirely possible although still linked to the general concept of the invention.
    权利要求:
    Claims (15)
    [0001]
    1. DEVICE (100) FOR THE QUANTITATIVE DETECTION OF A SUBSTANCE IN A FLUID SAMPLE, said device comprising: a substrate (102); an electrically insulating layer (104) disposed on said substrate (102); a plurality of individually addressable nanowires (106, 108, 110) disposed in said electrically insulating layer (104), each nanowire of said plurality of nanowires being covered by an insulating material (202, 204, 206), the plurality of nanowires being arranged for detecting the presence of the substance in the fluid sample by measuring an electrical characteristic of a nanowire from the plurality of nanowires, each said nanowire having a length, a width and a thickness; a sample compartment (118) for comprising said fluid sample, wherein said sample compartment is arranged such that it covers at least a part of each nanowire of said plurality of nanowires, wherein each of the individual insulating material of each nanowire is separated from each other; and characterized by the individual insulating material of each of the at least two nanowires of said plurality of nanowires having a thickness that is different from each other to form different detection ranges for the substance.
    [0002]
    2. DEVICE, according to claim 1, characterized by a combination of the different detection ranges forming a continuous detection range that is greater than each different detection range.
    [0003]
    3. DEVICE, according to claim 1 or 2, characterized in that each nanowire of said plurality of nanowires (106, 108, 110) comprises a surface area and a volume of nanowire, in which the ratio of the surface area and the volume is different due to the different nanowires of the said plurality of nanowires.
    [0004]
    4. DEVICE, according to claim 3, characterized in that the thickness of the nanowires of the plurality of nanowires is the same and one or more of the width and length of each of the nanowires of said plurality of nanowires is different.
    [0005]
    5. DEVICE according to any one of the preceding claims, characterized in that the individual insulating material is the same for each of the nanowires of the plurality of nanowires and in which the insulating material comprises a thickness that is different for each nanowire of the plurality of nanowires ( 106, 108, 110).
    [0006]
    DEVICE (100) according to any one of the preceding claims, characterized in that at least one nanowire (106, 108, 110) of said plurality of nanowires (106, 108, 110) comprises at least one functionalization layer which is for interaction with a substance.
    [0007]
    7. DEVICE (100) according to any one of the preceding claims, characterized in that each of at least two nanowires (106, 108, 110) of said plurality of nanowires (106, 108, 110) comprises a functionalization layer that it is for interaction with a substance, in which at least two layers of functionalization are different from each other.
    [0008]
    DEVICE (100) according to claim 6 or 7, characterized in that the at least one functionalization layer comprises or consists of TiO2.
    [0009]
    DEVICE (100) according to any one of the preceding claims, characterized in that said sample compartment (118) is configured to include a fluid over said plurality of nanowires (106, 108, 110).
    [0010]
    10. DEVICE (100) according to any one of the preceding claims, characterized in that at least two of said nanowires have a different sensitivity.
    [0011]
    11. DEVICE (100) according to any one of the preceding claims, characterized in that each of the at least two nanowires (106, 108, 110) of said plurality of nanowires (106, 108, 110) have a different doping concentration of a dopant.
    [0012]
    DEVICE (100) according to any one of the preceding claims, characterized in that at least one nanowire of the plurality of nanowires forms a channel of a transistor and a part of the substrate (102) is used as an access terminal of said transistor .
    [0013]
    13. DEVICE (100) according to any one of the preceding claims, characterized in that it comprises an additional sample compartment.
    [0014]
    14. DEVICE, according to any one of the preceding claims, characterized by comprising an electrical circuit connected to each nanowire (106, 108, 110) of the plurality of said nanowires (106, 108, 110) for reading the nanowires.
    [0015]
    15. USE OF A DEVICE, as defined in any one of claims 1 to 14, characterized in that it is for the quantitative detection of a substance in a fluid sample.
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-02| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-12-01| B09A| Decision: intention to grant|
    2021-02-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261714418P| true| 2012-10-16|2012-10-16|
    US61/714,418|2012-10-16|
    PCT/IB2013/059160|WO2014060894A2|2012-10-16|2013-10-07|Wide dynamic range fluid sensor based on nanowire platform|
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