Fluid sensor and methods
A fluid sensor for use in an environment having an ambient temperature has a field-effect transistor (FET) comprising a functionalized semiconductor nano-wire, an integral heater disposed proximate to the field-effect transistor to heat the field-effect transistor to an elevated temperature relative to the ambient temperature, and integral thermal insulation disposed to maintain the field-effect transistor at the elevated temperature.
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This application is related to co-pending and commonly assigned application Ser. No. 10/423,063, filed Apr. 24, 2003 (attorney docket no. 200300115), the entire disclosure of which is incorporated herein by reference.
TECHNICAL FIELDThis invention relates generally to fluid sensor devices and methods for their fabrication.
BACKGROUNDMany gas sensors require elevated temperatures for their proper operation (e.g., 100°-200° C.). Power consumption required for heating such traditional gas sensors is high because of the relative large volume of material used, either in bulk form or film form. On the other hand, gas sensitivity of these sensors is limited because of the limited surface area available for gas adsorption. The low sensitivity and high power consumption limit their applications.
Nano-scale sensors are used in a large number of applications and have been found particularly useful in the fields of chemical and/or biological sensing and analysis. Such nano-scale sensors have typically been produced individually by non-repetitive (and therefore inefficient) methods that do not use batch processing manufacturing techniques. Nano-scale sensors find application in such analysis techniques as gas chromatography, ion-coupled plasma atomic analysis (ICPAA), wet chemical analysis, PCR (polymerase chain reaction) analysis, electrophoresis, fluorescent tagging methods, and mass spectroscopy by laser volatilization.
Chemical and/or biological sensing and analysis traditionally require a long time to obtain meaningful data, involve remote or cumbersome equipment, require large sample sizes, demand highly trained users, and involve significant direct and indirect costs. Direct costs relate to the labor, procedures, and equipment required for each type of analysis. Indirect costs partially accrue from the delay time before actionable information can be obtained, e.g., in medical analyses or in the monitoring of chemical processes. Indirect costs of certain chemical or biological analyses can outweigh the direct costs.
Certain embodiments of biological and/or chemical analysis equipment use loose cylindrical wires or tubes whose electrical resistance is measured using a two terminal configuration. The term “loose” indicates that the wire or tube is not initially secured to the substrate and so must subsequently be affixed to it.
Advantages of the loose tube type of construction of sensors are simplicity and ease of laboratory demonstration. Minute wires can also be deposited directly on a substrate by a chemical vapor deposition (CVD) process which is also time consuming. However, it is difficult and expensive to manufacture loose nano-scale wires or tubes in a sufficiently reproducible way for useful sensing applications.
Some analytical techniques also require arrays of sensors. Such arrays may be used to sense some parameter over a two-dimensional or three-dimensional configuration or to sense various parameters simultaneously in a common location. It is difficult to fabricate loose tubes or wires into arrays in large quantities, especially when the tubes or wires have nano-scale dimensions. It is time-consuming and expensive to assemble wires or tubes individually into an array of sensors.
There is therefore a need for efficient methods for manufacturing nano-scale fluid sensors in a less expensive, more reproducible, and more production-friendly manner than permitted by present-day techniques.
BRIEF DESCRIPTION OF THE DRAWINGSThe features and advantages of the disclosure will readily be appreciated by persons skilled in the art from the following detailed description when read in conjunction with the drawings, wherein:
For clarity of the description, the drawings are not drawn to a uniform scale. In particular, vertical and horizontal scales may differ from each other and may vary from one drawing to another. In this regard, directional terminology, such as “top,” “bottom,” “front,” “back,” “leading,” “trailing,” etc., is used with reference to the orientation of the drawing figure(s) being described. Because components of the invention can be positioned in a number of different orientations, the directional terminology is used for purposes of illustration and is in no way limiting.
For clarity and simplicity of descriptions, the embodiments of fluid sensors described herein are generally described in terms of sensing gases. However, the invention is not limited to sensing of gases. The embodiments described may also be used in other applications for sensing of plasmas and other fluids, including liquids. If desired, suitable fluidics structures such as conventional fluidic devices may be added.
Various embodiments of fluid sensors are described in the following paragraphs with reference to
Furthermore, functionalized semiconductor nano-wire 40 may also comprise a catalyst 80, e.g. a metallic catalyst. Examples of suitable catalysts include: platinum, palladium, iridium, rhenium, ruthenium, gold, silver, and mixtures or alloys or compounds thereof; carbon; tungsten, titanium, tin, zinc, and oxides thereof; organometallic compounds containing elements from the group consisting of cobalt, iron, and nickel; and transition metal complexes containing elements from Groups IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB of the Periodic Table of Elements. Thus, specifically, functionalized semiconductor nano-wire 40 may comprise a silicon nano-wire functionalized with a catalyst 80 selected from this list of suitable catalysts or their functional equivalents. In general, any material capable of interacting with fluids to be detected and effecting a change of an electrical characteristic of the field-effect transistor (FET) may be selected as a catalyst 80 for use in embodiments of the invention. The change of an electrical characteristic of the field-effect transistor may be, for example, a change of conductance, capacitance, frequency response, transconductance, gain, carrier concentration, or some other electrical change. Catalyst 80 is shown schematically in
Substrate 20 may be provided in a number or ways, some of which incorporate other elements as part of the substrate itself. For example, in
A fifth embodiment of a fluid sensor structure is shown in
While particular arrangements of the various elements are shown in the drawings of these embodiments, those skilled in the art will recognize that other arrangements are also operable. The integral thermal insulation may be disposed on the substrate; the integral heater may be disposed on the substrate or on the integral thermal insulation; and the field-effect transistor (FET) may be disposed on the substrate or on the integral thermal insulation, for example. The benefit of reduced power consumption is improved when both the FET and heater are disposed on the integral thermal insulation. In some embodiments, an insulating substrate is the integral thermal insulator.
Individual fluid sensor structures may be combined and integrated in an array, as shown in
As the section hereinbelow titled “FABRICATION” describes, each of the fluid sensor devices 15 may be fabricated to be “nano-scale,” i.e., to have dimensions of less than about one micrometer. Thus, the various embodiments described above provide nano-scale fluid sensors for use in an environment having an ambient temperature. Each fluid sensor, individually or configured in an array, may comprise a nano-scale fluid detector 15 (such as a functionalized nano-scale field-effect-transistor), an integral heater 110 for heating the nano-scale fluid detector, integral thermal insulation for at least the nano-scale fluid detector, and mechanical support for the nano-scale fluid detector, the integral heater, and the integral thermal insulator. The integral heater 110 can heat each nano-scale fluid detector 15 to an elevated temperature relative to the ambient temperature, and the integral thermal insulator 30 can maintain the nano-scale fluid detector 15 at the elevated temperature.
An integral temperature sensor (such as temperature sensors 150 and 155 shown in
In embodiments using silicon as the semiconductor, thermally insulated silicon nano-wire field-effect transistors (SiNW FET's), in which silicon nano-wires (SiNW's) form the FET conducting channels and are thermally insulated by a dielectric film, are transformed into sensitive and low-power fluid sensors by functionalizing silicon nano-wires with selective catalytic nano-particles or thin films. Chemisorption of gas molecules on the resulting SiNW/catalyst surface at elevated temperatures (for example, 100°-200° C.) changes the conductance of SiNW's due to the field effect of charged adsorbates which are detected. While reference is made herein to a theory of operation related to chemisorption effects, the invention should not be construed as being limited to the consequences of such a theory or of any particular theory of operation. The large surface area/volume ratio of nano-wires leads to increased sensitivity and faster response time, yet their small volume along with their thermal isolation leads to lower power consumption required for heating. In addition to SiNW FET devices, silicon-based resistors and diodes may conveniently be used on each sensor chip to locally heat SiNW's and monitor their temperatures. Moreover, SiNW FET's are amenable to high density array-based sensing which allows multiple gases to be detected simultaneously by functionalizing each SiNW with different catalytic metals or by operating each SiNW FET at different temperatures. In general, a catalyst-functionalized SiNW FET sensor is a versatile platform for multiplexed, highly sensitive, and low-power fluid sensing, and can be mass-produced at low cost by semiconductor fabrication technology, as is described hereinbelow.
As an example, in operation for gas sensing, the nano-wires are heated to the desired temperature (for example, 100°-200° C.) and are exposed to the gases. A catalyst on the nano-wire selectively facilitates the adsorption and decomposition of a specific gas on the Si nano-wire. These adsorbates have a field effect on Si nano-wires and will change their conductance. The selectivity of gas sensing is determined by the catalysts coated on Si nano-wires, and/or the operating temperature of nano-wire FET's, which can be individually selected for each nano-wire FET in a multiplex sensor array.
This utilization of Si nano-wire field-effect transistors fabricated by semiconductor fabrication processes allows low-cost manufacturing of multiplex, highly sensitive and low power-consumption fluid sensors. In particular, silicon nano-wire FET's serve as versatile platforms for various fluid sensors customized by functionalizing nano-wires with various catalyst substances.
Fabrication
Another aspect of the invention is a method of fabricating a fluid sensor. An embodiment of such a fluid-sensor fabrication method is illustrated by the flowchart shown in
In step S30, a nano-wire is formed by patterning the semiconductor film, using techniques of nano-lithography known to those skilled in the semiconductor art, e.g., nano-imprint lithography, electron-beam lithography, ion-beam lithography, deep-UV lithography, and X-ray lithography. In step S50, an integral heater is formed by patterning the semiconductor film and optionally doping the portion of semiconductor patterned to provide a desired resistivity. An integral temperature sensor may be formed in step S40, for example by patterning the semiconductor film and forming a junction to make a diode with known temperature-dependent electrical characteristics. Many detailed methods for formation of diodes in semiconductors are well-known to those skilled in the art. Steps S40 and S50 may be combined and performed simultaneously, and either or both of these steps may be combined and performed simultaneously with step S30 of forming the nano-wire. In step S60, conductive source and drain contacts are formed in electrical contact with the nano-wire, thereby combining the source and drain contacts with the semiconductor nano-wire to form a field-effect transistor (FET). Alternative methods of adding a gate to that FET are discussed below. Steps S40 and S50 of forming conductive source and drain contacts and forming an integral heater may also be performed using a nano-lithography method such as nano-imprint lithography, electron-beam lithography, ion-beam lithography, and X-ray lithography. As indicated by arrows in
In step S70, the nano-wire is functionalized for detection of at least one fluid. While the example of
The catalyst 80 employed in step S70 may be a metallic catalyst, but is not limited to metallic catalysts. The catalyst may be one of the following or the functional equivalents of any of these catalysts, for example: platinum, palladium, iridium, rhenium, ruthenium, gold, silver, and mixtures or alloys or compounds of these elements; carbon; tungsten, titanium, tin, zinc, and their oxides; organometallic compounds containing elements from the group cobalt, iron, or nickel; or transition metal complexes containing elements from Groups IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB of the Periodic Table of Elements. More generally, any material capable of interacting with gases to be analyzed and effecting a change of an electrical characteristic of the FET may be selected as a catalyst 80 and employed in step S70.
In step S80, integral thermal insulation is provided (disposed to maintain the field-effect transistor at an elevated temperature relative to the ambient temperature of the fluid sensor). It should be noted that, by providing a semiconductor-on-insulator (SOI) substrate, e.g., an SOI wafer, steps S10, S20, and S80 of
Not shown in
In the embodiment shown in
Thus, another aspect of the invention is a fabrication method specially adapted to fabricate the fluid sensor in one of the structural embodiments described above or their functional equivalents. The fluid sensor or array of such fluid sensors thus fabricated may be made as an integrated circuit.
The nano-wire FET's are fabricated by methods using steps commonly used in standard silicon semiconductor fabrication technology. In such embodiments, the FET's consist of doped Si nano-wire as a conducting channel, and two conductive electrodes connected to the nano-wire as the source and drain electrodes of the FET. Silicon nano-wires may be conveniently fabricated from silicon-on-insulator (SOI) wafers using nano-lithography and Si etching. Silicon nano-wires are electrically and thermally insulated by the buried oxide of SOI wafers. A thin layer of a gate dielectric such as oxide or nitride is formed on the silicon nano-wire. On the gate dielectric material, a catalyst (such as Pt, Pd, Ir, etc.) in the form of nano-particles or thin film is deposited. Arrays of such nano-wire FET's may be fabricated and each nano-wire may have its own unique catalyst functionalization for specific gas sensing. Each fluid sensor may also have its own integral nano-scale heater and its own integral nano-scale temperature sensor.
INDUSTRIAL APPLICABILITYDevices made in accordance with the invention are useful in detecting gases in an environment while having both high sensitivity and low power consumption. Various embodiments of the fluid sensor including fluid-sensor arrays may be used in applications that require detection of various gases, applications that require a heated sensor, applications that require integral temperature sensing, applications that require redundancy of sensors, applications that require a control device insensitive to gas, or applications that require sensing of fluids over a region of an array. The fabrication methods described are useful in being specially adapted to make structural embodiments of the fluid sensors described herein.
Although the foregoing has been a description and illustration of specific embodiments of the invention, various modifications and changes thereto can be made by persons skilled in the art without departing from the scope and spirit of the invention as defined by the following claims. For example, catalysts or other materials not listed explicitly in the present description may be used to substitute for their functional equivalents as described. The order of steps of the methods may be varied, and some method steps may be combined for more efficient fabrication. Also, in some applications, embodiments of the fluid sensor may be used at the ambient temperature, i.e., without heating the fluid sensor to a temperature elevated above the ambient temperature.
Claims
1. A fluid sensor for use in an environment having an ambient temperature, the fluid sensor comprising:
- a) a field-effect transistor (FET) comprising a functionalized semiconductor nano-wire,
- b) an integral heater disposed proximate to the field-effect transistor to heat the field-effect transistor to an elevated temperature relative to the ambient temperature, and
- c) integral thermal insulation disposed to maintain the field-effect transistor at the elevated temperature.
2. The fluid sensor of claim 1, wherein the functionalized semiconductor nano-wire comprises silicon.
3. The fluid sensor of claim 2, wherein the silicon of the functionalized semiconductor nano-wire is doped to provide a predetermined conductivity type.
4. The fluid sensor of claim 1, wherein the functionalized semiconductor nano-wire comprises a catalyst.
5. The fluid sensor of claim 4, wherein the catalyst comprises a material capable of interacting with a fluid to be sensed and effecting a change of an electrical characteristic of the field-effect transistor (FET).
6. The fluid sensor of claim 4, wherein the catalyst comprises a metallic catalyst.
7. The fluid sensor of claim 4, wherein the catalyst is a material selected from the list consisting of platinum, palladium, iridium, rhenium, ruthenium, gold, silver, and mixtures or alloys or compounds thereof; carbon; tungsten, titanium, tin, zinc, and oxides thereof; organometallic compounds containing elements from the group consisting of cobalt, iron, and nickel; and transition metal complexes containing elements from Groups IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB of the Periodic Table of Elements.
8. The fluid sensor of claim 4, wherein the catalyst comprises a porous thin layer of catalyst material.
9. The fluid sensor of claim 8, wherein pores of the porous thin layer of catalyst material extend at least partially through the thin layer of catalyst material.
10. The fluid sensor of claim 4, wherein the catalyst comprises a mesh formed by thin filaments of catalyst material.
11. The fluid sensor of claim 1, wherein the functionalized semiconductor nano-wire comprises a silicon nano-wire functionalized with a material capable of interacting with a fluid to be sensed and effecting a change of an electrical characteristic of the field-effect transistor (FET).
12. The fluid sensor of claim 1, wherein the functionalized semiconductor nano-wire comprises a silicon nano-wire functionalized with a catalyst selected from the list consisting of: platinum, palladium, iridium, rhenium, ruthenium, gold, silver, and mixtures or alloys or compounds thereof; carbon; tungsten, titanium, tin, zinc, and oxides thereof; carbon; tungsten, titanium and oxides thereof; organometallic compounds containing elements from the group consisting of cobalt, iron, and nickel; and transition metal complexes containing elements from Groups IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB of the Periodic Table of Elements.
13. The fluid sensor of claim 1, further comprising a substrate for supporting the field-effect transistor.
14. The fluid sensor of claim 13, wherein the field-effect transistor and the substrate are formed from a layer of silicon on an insulator (SOI).
15. The fluid sensor of claim 14, wherein the field-effect transistor and the substrate are formed from a layer of silicon on an insulator layer comprising silicon oxide.
16. The fluid sensor of claim 13, wherein the integral thermal insulation is disposed on the substrate.
17. The fluid sensor of claim 13, wherein the integral heater is disposed on the substrate.
18. The fluid sensor of claim 13, wherein the integral heater is disposed on the integral thermal insulation.
19. The fluid sensor of claim 13, wherein the field-effect transistor (FET) is disposed on the substrate.
20. The fluid sensor of claim 13, wherein the field-effect transistor (FET) is disposed on the integral thermal insulation.
21. The fluid sensor of claim 13, wherein a portion of the substrate is removed to form an opening under the field-effect transistor (FET), the opening being at least partially aligned with the field-effect transistor.
22. The fluid sensor of claim 13, wherein the substrate serves as a gate for the field-effect transistor.
23. The fluid sensor of claim 13, wherein the field-effect transistor includes a gate electrically insulated from the substrate.
24. The fluid sensor of claim 13, wherein the functionalized semiconductor nano-wire comprises a conductive catalyst electrically insulated from the substrate to provide a gate for the field-effect transistor.
25. The fluid sensor of claim 1, further comprising at least one integral temperature sensor disposed proximate to the field-effect transistor for determining the temperature thereof.
26. A fluid-sensor array, each fluid sensor of the fluid-sensor array comprising the fluid sensor of claim 25.
27. A fluid-sensor array, each fluid sensor of the fluid-sensor array comprising the fluid sensor of claim 1.
28. The fluid-sensor array of claim 27, further comprising at least one integral temperature sensor for determining a temperature thereof.
29. The fluid-sensor array of claim 27, wherein the field-effect transistor of each fluid sensor of the array is functionalized for detecting a particular substance.
30. The fluid-sensor array of claim 27, wherein the field-effect transistor of each fluid sensor of the array is functionalized for detecting a distinct substance.
31. The fluid-sensor array of claim 27, wherein the field-effect transistors of a number of the fluid sensors of the array are functionalized for detecting the same substance.
32. The fluid-sensor array of claim 27, further comprising at least one field-effect transistor not functionalized for detecting a substance, whereby at least one control device is provided.
33. A fluid sensor for use in an environment having an ambient temperature, the fluid sensor comprising:
- a) functionalized nano-scale field-effect-transistor means for detecting a fluid,
- b) integral means for heating the means for detecting a fluid,
- d) integral means for thermally insulating at least the means for detecting a fluid, and
- e) means for supporting the means for detecting a fluid, the integral means for heating, and the integral means for thermally insulating.
34. The fluid sensor of claim 33, wherein the integral means for heating comprises means for heating the means for detecting a fluid to an elevated temperature relative to the ambient temperature, and the integral means for thermally insulating comprises means for maintaining the means for detecting a fluid at the elevated temperature.
35. The fluid sensor of claim 33, further comprising integral means for determining the temperature of the means for detecting a fluid.
36. The fluid sensor of claim 33, wherein the means for detecting a fluid comprises means for detecting a gas.
37. A method for fabricating a fluid sensor, the method comprising the steps of:
- a) providing an insulating substrate,
- b) depositing a layer of silicon on the insulating substrate to form a silicon-on-insulator (SOI) substrate,
- c) patterning the layer of silicon to form at least one silicon nano-wire and at least one integral heater resistor,
- d) forming conductive source and drain contacts, thereby combining the source and drain contacts with the semiconductor nano-wire to form a field-effect transistor,
- e) functionalizing the at least one silicon nano-wire for detection of at least one gas, and
- f) depositing thermal insulation disposed to maintain the field-effect transistor at an elevated temperature relative to the ambient temperature of the fluid sensor.
38. The method of claim 37, wherein the silicon-layer patterning step c) is performed by nanolithography.
39. The method of claim 37, wherein the silicon-layer patterning step c) is performed using a lithography method selected from the list consisting of nano-imprint lithography, electron-beam lithography, ion-beam lithography, deep-UV lithography, and X-ray lithography.
40. The method of claim 37, wherein the step d) of forming conductive source and drain contacts is performed by nanolithography.
41. The method of claim 37, wherein the step d) of forming conductive source and drain contacts is performed using a lithography method selected from the list consisting of nano-imprint lithography, electron-beam lithography, ion-beam lithography, deep-UV lithography, and X-ray lithography.
42. The method of claim 37, wherein the step of functionalizing the at least one silicon nano-wire comprises depositing a quantity of a material capable of interacting with a fluid to be sensed and effecting a change of an electrical characteristic of the field-effect transistor (FET).
43. The method of claim 37, wherein the step of functionalizing the at least one silicon nano-wire comprises depositing a quantity of catalyst on the silicon nano-wire.
44. The method of claim 37, wherein the step of functionalizing the at least one silicon nano-wire comprises depositing on the silicon nano-wire a quantity of a catalyst selected from the list consisting of: platinum, palladium, iridium, rhenium, ruthenium, gold, silver, and mixtures or alloys or compounds thereof; carbon; tungsten, titanium, tin, zinc, and oxides thereof; organometallic compounds containing elements from the group consisting of cobalt, iron, and nickel; and transition metal complexes containing elements from Groups IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB of the Periodic Table of Elements.
45. The method of claim 37, wherein the step of functionalizing the at least one silicon nano-wire includes forming a gate for the field-effect transistor (FET).
46. The method of claim 37, further comprising the step of removing at least a portion of the substrate under the field-effect transistor (FET).
47. The method of claim 46, wherein the step of removing at least a portion of the substrate is performed by etching the back side of the substrate to form an opening at least partially aligned with the field-effect transistor (FET).
48. The method of claim 37, further comprising the steps of patterning the semiconductor film and forming a junction to make a diode with known temperature-dependent electrical characteristics, whereby an integral temperature sensor is formed.
49. A fluid sensor fabricated by the method of claim 48.
50. A method of using the fluid sensor of claim 49, comprising the steps of:
- a) associating with each of two or more fluids to be sensed a different operating temperature range effective for sensing the fluid to be sensed,
- b) sensing a temperature of the fluid sensor by operating the integral temperature sensor, and
- c) actuating the integral heater to adjust the temperature of the fluid sensor to within a selected operating temperature range, whereby one of the two or more fluids to be sensed is selected for sensing.
51. A fluid sensor fabricated by the method of claim 37.
52. An integrated circuit comprising the fluid sensor of claim 51.
53. A fluid-sensor array, each fluid sensor of the fluid-sensor array being fabricated by the method of claim 37.
54. An integrated circuit comprising the fluid-sensor array of claim 53.
55. A method of using a fluid sensor having an integral heater and an integral temperature sensor, the method comprising the steps of:
- a) associating with each of two or more fluids to be sensed a different operating temperature range effective for sensing the fluid to be sensed,
- b) sensing a temperature of the fluid sensor by operating the integral temperature sensor, and
- c) actuating the integral heater to adjust the temperature of the fluid sensor to within a selected operating temperature range, whereby one of the two or more fluids to be sensed is selected for sensing.
Type: Application
Filed: Mar 23, 2004
Publication Date: Sep 29, 2005
Applicant: Hewlett-Packard Development Company, L.P. Intellectual Property Administration (Fort Collins, CO)
Inventor: Qingqiao Wei (Corvallis, OR)
Application Number: 10/807,932