CN106556627B - Sensor based on nano material - Google Patents

Sensor based on nano material Download PDF

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Publication number
CN106556627B
CN106556627B CN201611030002.0A CN201611030002A CN106556627B CN 106556627 B CN106556627 B CN 106556627B CN 201611030002 A CN201611030002 A CN 201611030002A CN 106556627 B CN106556627 B CN 106556627B
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transmission line
mos
sensor
equivalent
nanostructure
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CN106556627A (en
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骆兴芳
袁彩雷
易强
俞挺
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Jiangxi Normal University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G01N27/227—Sensors changing capacitance upon adsorption or absorption of fluid components, e.g. electrolyte-insulator-semiconductor sensors, MOS capacitors

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
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  • Nanotechnology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

A kind of sensor based on nano material, comprising: the semiconductor substrate with first surface and the second surface opposite with first surface；Positioned at the first medium layer of first surface；Positioned at the second dielectric layer of second surface；Positioned at the transmission line of first medium layer surface, and transmission line has interval；Fill the MoS at the interval2Nanostructure；Positioned at the ground plane of second dielectric layer, there is complementary openings resonant ring, the position of complementary openings resonant ring and the interval of transmission line are corresponding in the ground plane.The sensor of the embodiment of the present invention is without power drives and line transmission signal or detection data, and high sensitivity, detection accuracy are high, good compatibility.

Description

Sensor based on nano material
Technical field
The present invention relates to field of gas detection, in particular to a kind of sensor based on nano material.
Background technique
Environmental security and industry security monitoring are the prerequisite and basic guarantee of Sustainable Socioeconomic Development.In the whole world Under the influence of rapid economic development and various high pressure of human activities, Environmental security and industry security are faced with huge challenge, Main environment safety problem and industrial safety issues include: atmosphere pollution, water pollution, soil pollution, Safety of Coal Mine Production etc..
And one of the key factor of main environment safety problem and industrial safety issues is solved, exactly advanced sensors part Research and development, advanced sensor can be used in monitoring all kinds of toxic and harmful gas, by taking haze as an example, sulfur dioxide, nitrogen oxides and Pellet is the main composition of haze.
Therefore, in the case where current people increasingly focus on environmental protection and living safety, to some pernicious gases and The detection of hazardous gas just becomes more and more important.
And gas sensor is a kind of for sensing the sensing equipment of gas to be detected, gas sensor can apply to detect Such as the various gases such as carbon monoxide, hydrogen sulfide, sulfur dioxide, hydrogen or ethyl alcohol, it is widely used in safety detection, environment measuring Etc. various environment.
Common gas sensor includes linear sensor, solid-state electrolyte gas sensor, electrochemical gas sensing Device and optical gas sensor,
But above-mentioned most of gas sensitivity is poor, detection accuracy is low, compatibility is low, and the power supply that needs are additional Driving, and need line transmission signal or detection data.
Summary of the invention
Problems solved by the invention is to provide one kind and transmits signal or detection data without power drives and line, and sensitive Degree is high, detection accuracy is high, good compatibility gas sensor.
To solve the above problems, the present invention provides a kind of forming method of sensor, semiconductor substrate is provided, it is described partly to lead Body substrate has first surface and the second surface opposite with first surface, and the first surface of the semiconductor substrate has first Dielectric layer, second surface have second dielectric layer；Several MoS are formed in the first medium layer surface2Nanostructure, it is several MoS2Nanostructure linearly arranges；Transmission line is formed in the first medium layer surface, the transmission line has interval, described Interval is suitable for accommodating the MoS2Nanostructure；Ground plane is formed in the second medium layer surface of the semiconductor substrate, it is described Ground plane is formed with complementary openings resonant ring, the position of the complementary openings resonant ring and the MoS2The position pair of nanostructure It answers.
Optionally, several MoS are formed in the first medium layer surface2Nanostructure includes: offer quartz tube furnace, institute State the first warm area and the second warm area that quartz tube furnace has connection, molybdenum trioxide powder, sulphur powder；Molybdenum trioxide powder is placed In the first warm area in quartz tube furnace, the semiconductor substrate for being formed with dielectric layer is set to the top of molybdenum trioxide powder, and half The spacing of conductor substrate and molybdenum trioxide powder is 1 centimetre to 5 centimetres；Sulphur powder is placed in the second warm area of quartz tube furnace, Wherein sulphur powder and the spacing of molybdenum trioxide powder are 17 centimetres to 20 centimetres；Wherein, the temperature setting of the first warm area is 650 Celsius Degree is to 800 degrees Celsius, and the temperature setting of the second warm area is 180 degrees Celsius to 300 degrees Celsius, and quartz tube furnace is during the preparation process Always it is passed through the argon gas of 30sccm, and argon gas flows to the first warm area along the second warm area；Keep the first warm area 650 degrees Celsius to 800 Degree Celsius time be after five minutes, tube furnace to be allowed to naturally cool to room temperature, take out and form MoS in the dielectric layer surface2Nanometer The semiconductor substrate of line layer；Photoetching offset plate figure, the photoetching offset plate figure covering part are formed on 100 surface of semiconductor substrate MoS2Nano wire and the photoetching offset plate figure and linearly aligned MoS to be formed2Nano wire is corresponding, is removed using etching technics Uncovered MoS2Then nano wire removes the photoetching offset plate figure, form the MoS at several intervals2Nano wire and several MoS2 Nano wire linearly arranges.
Optionally, the formation process of the transmission line includes: to cover the MoS using photoetching offset plate figure2Nanostructure, institute It states photoetching offset plate figure and exposes several dielectric layer surfaces, the photoetching offset plate figure is corresponding with transmission line to be formed, uses Physical gas-phase deposition forms metallic film in the dielectric layer surface；Photoetching offset plate figure is removed, is formed and has spaced biography Defeated line.
Optionally, the structure of the complementary openings resonant ring is two mutual oppositely positioned concentric split ring resonators, institute The formation process for stating complementary openings resonant ring includes: to form photoetching offset plate figure, the photoetching offset plate figure in the ground connection layer surface With figure corresponding with complementary openings resonant ring；Using the photoetching offset plate figure as exposure mask, the ground plane is etched, until exposure Second dielectric layer out；The photoetching offset plate figure is removed, complementary openings resonant ring is formed.
The present invention also provides a kind of sensors, comprising: with first surface and the second surface opposite with first surface Semiconductor substrate；Positioned at the first medium layer of first surface；Positioned at the second dielectric layer of second surface；Positioned at first medium layer table The transmission line in face, and transmission line has interval；Fill the MoS at the interval2Nanostructure；Positioned at the ground connection of second dielectric layer Layer, the ground plane is interior to have complementary openings resonant ring, and the position of complementary openings resonant ring and the interval of transmission line are corresponding.
Optionally, semiconductive substrate thickness is 400 microns to 600 microns, and dielectric constant is about 11.9；The first medium Layer material be silica, the first medium layer 110 with a thickness of 10 to 30 microns, the dielectric constant of the first medium layer It is 4；The material of the second dielectric layer be silica, the second dielectric layer with a thickness of 10 to 30 microns, it is described second be situated between The dielectric constant of matter layer is 4；The length of transmission line is 11 millimeters to 13 millimeters, and width is 0.6 millimeter；The thickness of the ground plane Degree is 5 microns to 20 microns.
Optionally, the structure of the complementary openings resonant ring is two mutual oppositely positioned concentric split ring resonators, In, the size of biggish split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 5.52 millimeters, and the outer diameter of ring is 5.92 millis Rice.The size of lesser split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 4.72 millimeters, and the outer diameter of ring is 5.12 millis Rice.The spacing of biggish split ring resonator and lesser split ring resonator is 0.2 millimeter.
Optionally, as the MoS of the sensor2When nanostructure quantity is 1, the equivalent circuit of the sensor are as follows: defeated Enter end, the first end of input terminal connection first equivalent inductance of transmission line, the second end connection of the first equivalent inductance of transmission line MoS2The first end of the equivalent resistance of nanostructure, MoS2The second end of the equivalent resistance of nanostructure connects MoS2Nanostructure Equivalent inductance first end, MoS2The second end of the equivalent inductance of nanostructure connects MoS2The equivalent capacity of nanostructure First end, MoS2The first end of second end connection the second equivalent inductance of transmission line of the equivalent capacity of nanostructure, transmission line the The second end of two equivalent inductances connects output end, and the first end of the first equivalent capacity of transmission line connects the first equivalent inductance of transmission line Second end, the first equivalent capacity of transmission line second end connection the second equivalent capacity of transmission line first end, transmission line second The first end of second end connection the second equivalent inductance of transmission line of equivalent capacity；The first of the equivalent inductance of complementary openings resonant ring The second end of end connection the first equivalent capacity of transmission line, the first end connection transmission line the of the equivalent capacity of complementary openings resonant ring The second end of one equivalent capacity, the equivalent electricity of the second end connection complementary openings resonant ring of the equivalent inductance of complementary openings resonant ring The second end of appearance and ground connection.
The present invention also provides a kind of methods of sensor detection gas, comprising: obtains the first curve, first curve Are as follows: in the environment of no gas to be detected, the frequency and S of the sensor11Curve；Sensor is placed in ring to be detected Border obtains the second curve, second curve are as follows: under environment to be detected, the frequency and S of the sensor11Curve；Pass through Whether comparing the resonance frequency variation of the frequency displacement of the first curve and the second curve, detect under environment to be detected with the presence or absence of to be detected Gas.
Optionally, further includes: by obtaining a plurality of second curve of environment to be detected, according to a plurality of second curve frequency displacement Resonance frequency amplitude of variation, to obtain the gas concentration to be detected of environment to be detected.
Compared with prior art, technical solution of the present invention has the advantage that
The embodiment of sensor of the invention uses nano material MoS2It is applied to sensor in conjunction with complementary openings resonant ring, Pass through nano material MoS2After absorbing gas, the dielectric constant and electric conductivity of material all change, to finally cause to pass The variation of sensor resonance frequency, to obtain the concentration variation of gas, plays detection alarm by measuring the offset of resonance frequency Effect, and complementary openings resonant ring is used to be applied to sensor, the edge capacitance effect between the concentric circles of complementary openings resonant ring Resonance should occur, complementary openings resonant ring is applied to sensor and device is made to have negative permittivity and negative magnetic conductance in special frequency channel Rate, so that the size of sensor compares the quality factor that very little, Miniaturizable, and sensor have had with working frequency, it can Sensor sensitivity is improved, the application of left-handed material and nano material in modern detecting has been expanded.
The forming method of sensor of the invention forms microwave device unit using lsi technology, optimizes base In the processing step of the sensor of nano material.
The method of sensor of the invention detection gas is able to detect the gas of various concentration, is obtained by resonance frequency variation Know the concentration variation of detection gas, detection accuracy is high.
Detailed description of the invention
Fig. 1 is the flow diagram of an embodiment of the forming method of inventive sensor；
Fig. 2 to Fig. 8 is the process schematic of one embodiment of forming method of sensor of the invention；
Fig. 9 is the schematic equivalent circuit of one embodiment of sensor of the invention；
Figure 10 is the test gas schematic diagram of one embodiment of inventive sensor.
Specific embodiment
Existing major part gas sensitivity is poor, detection accuracy is low, compatibility is low, and additional power supply is needed to drive It is dynamic, and need line transmission signal or detection data.By taking linear sensor as an example, linear sensor is to utilize thermal conductivity The semiconductor transducer of variation is to apply SnO in Pt wire coil2Layer, Pt in addition to playing heat effect, are also detected temperature and become The function of change.Applying voltage semiconductor heating, surface oxygen uptake declines free electronic concentration, in the presence of imflammable gas, due to Burning consumes the increase of oxygen free electronic concentration, and thermal conductivity increases with free electronic concentration and increased, and rate of heat dissipation accordingly increases, and makes Pt Silk temperature decline, resistance value reduce, and Pt change in resistance and gas concentration are linear relationship.
But SnO is applied in Pt wire coil2Layer can not be manufactured using integrated circuit technology, and compatibility is low, in addition be needed Linear sensor is connected using additional power drives and line.And with the rise of Internet of Things, existing sensing Device can not be compatible with radio-frequency devices, thus can not be compatible with Internet of things system.
For this purpose, the present inventor proposes a kind of sensor and forming method thereof based on nano material, will use Integrated circuit technology manufactures the sensor based on nano material, the sensor based on nano material and complementary openings resonant ring come Probe gas is a kind of wireless and passive gas sensor；It can be used for inflammable, explosive, high temperature, low temperature, strong-electromagnetic field, moving object The special occasions that body and other sensors can not be applied, has the advantages that be widely used；The sensor is that excellent sensing carries Body and passive device, and use complementary openings resonant ring and be applied to sensor, between the concentric circles of complementary openings resonant ring Edge capacitance effect occur resonance, complementary openings resonant ring be applied to sensor make device special frequency channel have negative dielectric Constant and negative magnetoconductivity, so that the size of sensor compares what very little, Miniaturizable, and sensor had had with working frequency Sensor sensitivity can be improved in quality factor, has expanded the application of left-handed material and nano material in modern detecting.
Further, by the way that the parameter of sensor is arranged, so that the working range of sensor is frequency microwave field, it can be straight Transceiving radio frequency and microwave electromagnetic waves are connect, realizes non-contact wireless sensing, there is non-transformer and signal link, it is small in size, at low cost, The advantages that high sensitivity, low in energy consumption, strong antijamming capability, the application being suitble under complex environment.It can also be used for moving component and not The detection of accessible object.
The sensor is using with the mutual of the inverse opening of DNG feature (negative permittivity and negative magnetoconductivity) left-handed material Mend the resonator combination gas sensitive MoS of split ring resonator2It develops, passes through nano material MoS2After absorbing gas with various, material Dielectric constant and electric conductivity all change, to finally cause the variation of sensor resonant frequency, pass through measurement resonance frequency The offset of rate plays detection alarm function to obtain the concentration variation of gas.
The sensor, which has, is not necessarily to battery supplied energy, transmits signal without interconnection line, can greatly widen sensor Service life and application environment, solve under adverse circumstances lead difficulty and it is unstable the problems such as, additionally be able to be applied to tested pair As that can not be connect with cable, optical fiber etc. between signal processing system, it has not been convenient to provide power supply or in adverse circumstances.
To make the above purposes, features and advantages of the invention more obvious and understandable, with reference to the accompanying drawing to the present invention Specific embodiment be described in detail.
The embodiment of the present invention provides a kind of forming method of sensor based on nano material, referring to FIG. 1, including such as Lower step:
S101, provides semiconductor substrate, and the semiconductor substrate has first surface and opposite with first surface second Surface, the first surface of the semiconductor substrate have first medium layer, and second surface has second dielectric layer；
S102 forms several MoS in the first medium layer surface2Nanostructure, several MoS2Nanostructure is linearly arranged Column；
S103 forms transmission line in the first medium layer surface, and the transmission line has interval, and the interval is suitable for holding Receive the MoS2Nanostructure；
S104 forms ground plane in the second medium layer surface of the semiconductor substrate, and the ground plane is formed with complementation Split ring resonator, the position of the complementary openings resonant ring and the MoS2The position of nanostructure is corresponding.
Specifically, referring to FIG. 2, provide semiconductor substrate 100, the semiconductor substrate 100 have first surface I and with First surface I opposite second surface II.
The semiconductor substrate 100 can be semiconductor material, such as the semiconductor substrate 100 can for monocrystalline silicon, The semiconductor material of the monocrystalline such as monocrystalline germanium silicon, monocrystalline GaAs, monocrystalline GaN (for example partly lead by II-VI group, III-V compound Body), the material of the semiconductor substrate 100 can also be n-type doping or p-type doping silicon substrate, polycrystalline substrates either amorphous Substrate, such as 100 material of the semiconductor substrate can be polysilicon or other materials.
It should be noted that the semiconductor substrate 100 is used to provide carrier platform for the sensor being subsequently formed, it is subsequent The microwave devices unit such as transmission line and complementary openings resonant ring will be formed on the platform, and those skilled in the art should know Dawn, microwave device unit is generally formed on microwave pcb board carrier platform, but microwave pcb board can not be with integrated circuit technology It is compatible, for this purpose, the embodiment of the present invention selects the semiconductor substrate 100 with ic process compatibility, and using integrated Circuit technology forms microwave device unit, to optimize the processing step of the sensor based on nano material.
It should be pointed out that existing semiconductor devices typically forms only the working face in semiconductor substrate, and due to this The semiconductor substrate 100 of embodiment is used to provide carrier platform for the sensor being subsequently formed, and needs in the semiconductor The first surface I and second surface II of substrate 100 respectively correspond to form microwave device unit.As an embodiment, first surface I It can be the working face of semiconductor substrate；As another embodiment, second surface II can be the working face of semiconductor substrate.
In the present embodiment, the semiconductor substrate selects the p-type silicon substrate that dielectric constant is about 11.9.
Fig. 2 please be still referred to, first medium layer 110 is formed in the first surface I of the semiconductor substrate 100, second Surface forms second dielectric layer 150.
The microwave device unit of the first medium layer 110 being subsequently formed for electric isolation and the semiconductor substrate 100。
The material of the first medium layer 110 is the dielectric materials such as silica, silicon nitride, silicon oxynitride；Described first is situated between Matter layer 110 with a thickness of 10 to 30 microns, as an embodiment, the first medium layer 110 with a thickness of 20 microns；As one Embodiment, the material of the first medium layer 110 are silica, and formation process is oxidation technology or chemical vapor deposition process.
It should be noted that the semiconductor substrate of the first surface with first medium layer 110 can also be selected directly 100, without additionally re-forming first medium layer 110；Those skilled in the art can be according to actual process to select The semiconductor substrate needed, specially illustrates herein, should not excessively limit the scope of the invention.
In the present embodiment, the material of the first medium layer 110 is silica, and with a thickness of 20 microns, dielectric constant is about It is 4.
The complementary openings resonant ring of the second dielectric layer 150 being subsequently formed for electric isolation and semiconductor lining Bottom 100.
The material of the second dielectric layer 150 is the dielectric materials such as silica, silicon nitride, silicon oxynitride；Described second is situated between Matter layer 150 with a thickness of 10 to 30 microns, as an embodiment, the second dielectric layer 150 with a thickness of 20 microns；As one Embodiment, the material of the second dielectric layer 150 are silica, and formation process is oxidation technology or chemical vapor deposition process.
It should be noted that the semiconductor substrate of the second surface with second dielectric layer 150 can also be selected directly 100, without additionally re-forming second dielectric layer 150；Those skilled in the art can be according to actual process to select The semiconductor substrate needed, specially illustrates herein, should not excessively limit the scope of the invention.
In the present embodiment, the material of the second dielectric layer 150 is silica, and with a thickness of 20 microns, dielectric constant is about It is 4.
Referring to FIG. 3, forming several MoS on 110 surface of first medium layer2Nanostructure 122, several MoS2It receives Rice structure 122 linearly arranges.
The MoS2Nanostructure 122 is suitable for adsorbing gas to be detected, so as to cause MoS2The dielectric constant of nanostructure and Electric conductivity all changes, thus finally cause the variation of sensor resonant frequency, by measuring the offset of resonance frequency, thus Obtain the concentration variation of gas.In addition, MoS2Nanostructure 122 due to biggish specific surface area, adsorbed gas it is corresponding Time is short, so that probe gas is sensitiveer.
MoS2The quantity of nanostructure 122 can be 1,2,3,4 ...；It should be noted that MoS2The number of nanostructure 122 Amount is more, and the sensitivity of sensor detection is higher, but due to MoS2The large specific surface area of nanostructure adsorbs gas to be detected Dielectric constant and electric conductivity all change obviously afterwards, therefore, work as MoS2When the quantity of nanostructure 122 is 1, sensor detection Sensitivity also value with higher, the sensitivity that those skilled in the art can detect according to sensor selects MoS2Nanometer The quantity of structure 122.
It should be noted that if dry MoS2The spacing of nanostructure 122 can be the same or different, and the present invention is with several MoS2The spacing of nanostructure 122 is identical do it is exemplary illustrated, still, in other embodiments, several MoS2Nanostructure 122 Spacing can also be different or not all the same；Inventor has found several MoS2The selection of the spacing of nanostructure 122 will affect subsequent The resonant frequency value of sensor.
As an embodiment, with MoS2Done for nano wire it is exemplary illustrated, if the first medium layer surface formation The MoS at dry interval2Nanostructure 122, several MoS2Linearly arrangement includes the following steps: using chemical gaseous phase nanostructure 122 Depositing operation forms MoS in the dielectric layer surface2Nano wire layer；The MoS at several intervals is formed using photoetching process2Nano wire And several MoS2Nanostructure linearly arranges.
As an embodiment, referring to FIG. 4, forming MoS in the dielectric layer surface using chemical vapor deposition process2It receives Rice noodles layer, specifically includes: providing quartz tube furnace 200, the quartz tube furnace 200 has the first warm area 201 and the of connection Two warm areas 202, molybdenum trioxide (MoO3) powder 203, sulphur powder (S) 204 and the semiconductor lining for being formed with dielectric layer (Fig. 4 is not shown) Bottom 100；Molybdenum trioxide powder 203 is placed in the first warm area 201 in quartz tube furnace 200, is formed with partly leading for dielectric layer Body substrate 100 is set to the top of molybdenum trioxide powder 203, and the spacing of semiconductor substrate 100 and molybdenum trioxide powder 203 is 1 Centimetre to 5 centimetres；Sulphur powder 204 is placed in the second warm area 202 of quartz tube furnace, wherein sulphur powder 204 and molybdenum trioxide powder 203 spacing is 17 centimetres to 20 centimetres；Wherein, the temperature setting of the first warm area 201 is 650 degrees Celsius to 800 degrees Celsius, the The temperature setting of two warm areas 202 is 180 degrees Celsius to 300 degrees Celsius, and quartz tube furnace 200 is passed through always during the preparation process The argon gas (Ar) of 30sccm, and argon gas flows to the first warm area 201 along the second warm area 202；Keep 650 degrees Celsius of the first warm area extremely 800 degrees Celsius of time is after five minutes, tube furnace to be allowed to naturally cool to room temperature, takes out and forms MoS in the dielectric layer surface2 The semiconductor substrate 100 of nano wire layer.
Referring to FIG. 5, Fig. 5 is to form MoS in the dielectric layer surface using chemical vapor deposition process2In nano wire layer Single MoS2The atomic force microscope images of nano wire can be known, MoS from Fig. 52The length of nano wire is greater than 1000 nanometers, Width is about 20 nanometers to 50 nanometers, and MoS2Nano wire has section, and above-mentioned nanostructure has biggish specific surface area, can Gas to be detected is adsorbed, so as to cause MoS2The dielectric constant and electric conductivity of nanostructure all change.
The MoS at several intervals is formed using photoetching process2Nano wire and several MoS2Nano wire linearly arranges, including such as Lower step: photoetching offset plate figure (not shown), the photoetching offset plate figure covering part are formed on 100 surface of semiconductor substrate MoS2Nano wire and the photoetching offset plate figure and linearly aligned MoS to be formed2Nano wire is corresponding, is removed using etching technics Uncovered MoS2Then nano wire removes the photoetching offset plate figure, form the MoS at several intervals2Nano wire and several MoS2 Nano wire linearly arranges.
It should also be noted that, control MoS2The growth temperature of nanostructure, spacing, gas flow can also be prepared MoS2The nanostructures such as nanometer rods, nanobelt, nano whisker, specially illustrate herein, should not excessively limit protection of the invention Range.
Referring to FIG. 6, forming transmission line 120 on 110 surface of first medium layer, the transmission line 120 has interval 121, the interval 121 is suitable for accommodating the MoS2Nanostructure 122；
The transmission line 120 is used for transmission microwave signal, and the material of the transmission line is metal, such as copper, gold, silver etc..
The transmission line 120 is strip, and transmission line 120 arranges along its length, wherein the length of transmission line is 11 For millimeter to 13 millimeters, width is 0.6 millimeter, and interval 121 is 0.3 millimeter.
As an embodiment, the formation process of the transmission line 120 includes: to cover the MoS using photoetching offset plate figure2It receives Rice structure 122, the photoetching offset plate figure expose several 110 surfaces of first medium layer, the photoetching offset plate figure with to shape At transmission line 120 it is corresponding, metallic film is formed (not on 110 surface of first medium layer using physical gas-phase deposition Mark)；Photoetching offset plate figure is removed, the transmission line 120 with interval 121 is formed.
Please also refer to Fig. 7 and Fig. 8, wherein Fig. 8 is the top view of Fig. 7 along the direction vertical second surface II, second 150 surface of dielectric layer forms ground plane 130, and the ground plane is formed with complementary openings resonant ring 131.
Wherein, complementary openings resonant ring 131 acts on are as follows: when electromagnetic wave incident, if magnetic direction is humorous perpendicular to being open Shake plane of a loop, then metal structure surface metal strap portions generate current loop on split ring resonator, is equivalent to inductance；Displacement current Metal interannular gap and each ring opening, are equivalent to capacitor inside and outside split ring resonator.Therefore, swash in incident electromagnetic wave magnetic field It encourages down, split ring resonator generates resonance, and equivalent permeability is negative.Complementary openings resonant ring is the complementary knot of split ring resonator Structure.By transmission line theory, Quasi-TEM mode makes the field distribution for having strong between metal strap and floor, when electric field strength is sufficiently large And just it is parallel to complementary openings resonant ring central axis, it will be able to preferably motivate, and produce to complementary openings resonant ring The negative dielectric constant of life, complementary openings resonant ring are applied to sensor and device are made to have negative permittivity in special frequency channel and bear Magnetic conductivity so that the size of sensor compared with working frequency quality that very little, Miniaturizable, and sensor have had because Number, can be improved sensor sensitivity.
Therefore, the complementary openings resonant ring 131 can amplify evanescent waves, so that resonance ring region electric-field strength, enhancing is passed Sensor sensitivity, and the Meta Materials characteristic of 131 structure of complementary openings resonant ring has double negativity, can reduce device Part size, such as the Meta Materials of 131 structure of complementary openings resonant ring can be in λ/8 to λ // 12 resonance (it should be understood that λ It is the corresponding wavelength of working sensor frequency), to reduce device size.
Further, selecting the gas sensor of the complementary openings resonant ring 131 has low-power consumption.
As an embodiment, the structure of complementary openings resonant ring 131 is two mutual oppositely positioned concentric opening resonance Ring, wherein the size of biggish split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 5.52 millimeters, and the outer diameter of ring is 5.92 millimeter.The size of lesser split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 4.72 millimeters, and the outer diameter of ring is 5.12 millimeter.The spacing of biggish split ring resonator and lesser split ring resonator is 0.2 millimeter.
The position of complementary openings resonant ring 131 is corresponding with the interval 121 of transmission line 120, as an embodiment, interval 121 The position of projection is located at the center of complementary openings resonant ring 131.In order to illustrate, the projection of the transmission line 120 in fig. 8 It is shown in dotted line.
Specifically, forming the technique of ground plane 130 on the surface of second dielectric layer 150 includes: using physical vapour deposition (PVD) Technique forms ground plane 130 on the surface of the second dielectric layer 150.
Ground plane 130 with a thickness of 5 microns to 20 microns, the material of ground plane is metal, such as copper, gold, silver etc..
The step of complementary openings resonant ring 131 is formed in the ground plane 130 includes: on 130 surface of ground plane Photoetching offset plate figure (not shown) is formed, the photoetching offset plate figure has figure corresponding with complementary openings resonant ring 131；With described Photoetching offset plate figure is exposure mask, etches the ground plane 130, until exposing the surface of the second dielectric layer 150；Described in removal Photoetching offset plate figure forms complementary openings resonant ring 131.
The present invention also provides a kind of embodiments of sensor, comprising: has first surface I and opposite with first surface I The semiconductor substrate 100 of second surface II；Positioned at the first medium layer 110 of first surface I；Second positioned at second surface II is situated between Matter layer 150；Transmission line 120 positioned at 110 surface of first medium layer, and transmission line 120 has interval 121；Fill the interval 121 MoS2Nanostructure；Positioned at the ground plane 130 of second dielectric layer 150, have complementary openings humorous in the ground plane 130 Shake ring 131, and the position of complementary openings resonant ring 131 and the interval 121 of transmission line are corresponding.
Specifically, for semiconductor substrate 100 with a thickness of 400 microns to 600 microns, dielectric constant is about 11.9；
The material of the first medium layer 110 is the dielectric materials such as silica, silicon nitride, silicon oxynitride；Described first is situated between Matter layer 110 with a thickness of 10 to 30 microns, the dielectric constant of the first medium layer 110 is about 4.
The material of the second dielectric layer 150 is the dielectric materials such as silica, silicon nitride, silicon oxynitride；Described second is situated between Matter layer 150 with a thickness of 10 to 30 microns, the dielectric constant of the second dielectric layer 150 is about 4.
The transmission line 120 is strip, and transmission line 120 arranges along its length, wherein the length of transmission line is 11 For millimeter to 13 millimeters, width is 0.6 millimeter, and interval 121 is 0.3 millimeter.The MoS2Nanostructure 122 is suitable for adsorbing to be detected Gas, so as to cause MoS2The dielectric constant and electric conductivity of nanostructure all change, to finally cause sensor resonant The variation of frequency, by measuring the offset of resonance frequency, to obtain the concentration variation of gas.MoS2The number of nanostructure 122 Amount can be 1,2,3,4 ...；MoS2Nanostructure can be MoS2The nanostructures such as nanometer rods, nanobelt, nano whisker.
The structure of complementary openings resonant ring 131 is two mutual oppositely positioned concentric split ring resonators, wherein biggish The size of split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 5.52 millimeters, and the outer diameter of ring is 5.92 millimeters.It is lesser The size of split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 4.72 millimeters, and the outer diameter of ring is 5.12 millimeters.It is biggish The spacing of split ring resonator and lesser split ring resonator is 0.2 millimeter.
It should be noted that the sensor can be done with lower aprons: complementary openings resonant ring 131 is ignored to resonance frequency Influence lesser resistance, performance is close to a LC network；Transmission line 120 can be equivalent to capacitor and inductance, MoS2Nanometer Structure 122 is equivalent to rlc circuit, carrys out the frequency of tuned resonance.
Wherein, to have a MoS2For the sensor of nanostructure 122, wherein the transmission line 120 of the sensor For strip, the transmission line 120 only has 1 interval, and Fig. 9 is the equivalent circuit of the sensor, comprising: input terminal, it is described Input terminal connects the first equivalent inductance of transmission line LTransmission lineFirst end, the first equivalent inductance of transmission line LTransmission lineSecond end connection MoS2The equivalent resistance R of nanostructureMoS2First end, MoS2The equivalent resistance R of nanostructureMoS2Second end connect MoS2It receives The equivalent inductance L of rice structureMoS2First end, MoS2The equivalent inductance L of nanostructureMoS2Second end connect MoS2Nano junction The equivalent capacity C of structureMoS2First end, MoS2The equivalent capacity C of nanostructureMoS2Second end connection transmission line second it is equivalent Inductance L 'Transmission lineFirst end, the second equivalent inductance of transmission line L 'Transmission lineSecond end connect output end, the equivalent electricity of transmission line first Hold CTransmission lineFirst end connect the first equivalent inductance of transmission line LTransmission lineSecond end, the first equivalent capacity of transmission line CTransmission lineSecond End connection the second equivalent capacity of transmission line C 'Transmission lineFirst end, the second equivalent capacity of transmission line C 'Transmission lineSecond end connect transmission The second equivalent inductance of line L 'Transmission lineFirst end；The equivalent inductance L of complementary openings resonant ringCSRRFirst end connection transmission line the One equivalent capacity CTransmission lineSecond end, the equivalent capacity C of complementary openings resonant ringCSRRFirst end connection transmission line first it is equivalent Capacitor CTransmission lineSecond end, the equivalent inductance L of complementary openings resonant ringCSRRSecond end connection complementary openings resonant ring it is equivalent Capacitor CCSRRSecond end and ground connection.
By the equivalent circuit of the sensor it is found that the MoS2Nanostructure 122 be equivalent to concatenated resistance, inductance and Capacitor, when the sensor is placed in environment to be detected, when microwave signal passes through the transmission line 120, the MoS2It receives Rice structure 122 adsorbs gas to be detected, and the capacitance and resistance value of equivalent capacity change, so as to cause the frequency and S of sensor11 Curve resonance frequency variation so that the sensor is able to detect gas to be detected.
The present invention also provides a kind of methods of sensor detection gas using above-described embodiment, include the following steps:
S201, provides sensor, and the sensor includes: with first surface and the second surface opposite with first surface Semiconductor substrate；Positioned at the first medium layer of first surface；Positioned at the second dielectric layer of second surface；Positioned at first medium layer The transmission line on surface, and transmission line has interval；Fill the MoS at the interval2Nanostructure；Positioned at the ground connection of second dielectric layer Layer, the ground plane is interior to have complementary openings resonant ring, and the position of complementary openings resonant ring and the interval of transmission line are corresponding；
S202 obtains the first curve, first curve are as follows: in the environment of no gas to be detected, the sensor Frequency and S11Curve；
Sensor is placed in environment to be detected, obtains the second curve, second curve are as follows: in ring to be detected by S203 Under border, the frequency and S of the sensor11Curve；
S204 detects ring to be detected whether variation by comparing the resonance frequency of the frequency displacement of the first curve and the second curve It whether there is gas to be detected under border.
Wherein, the acquisition modes of the first curve and the second curve are that sensor is tested using vector network analyzer to sensing Device is tested.
It in another embodiment, can also be bent according to a plurality of second by a plurality of second curve of acquisition environment to be detected The resonance frequency amplitude of variation of line frequency displacement, to obtain the gas concentration to be detected of environment to be detected.
It specifically, is NO with the gas to be detected2For do it is exemplary illustrated, by be arranged sensor parameter, make Working sensor opens for free frequency range in mobile communication or WIFI etc., as an embodiment, semiconductive substrate thickness 530 Micron, dielectric constant is about 11.9, and first medium layer is with a thickness of 20 microns, and dielectric constant is about 4, and second dielectric layer is with a thickness of 20 Micron, dielectric constant is about 4, and the structure of complementary openings resonant ring is two mutual oppositely positioned concentric split ring resonators, In, the size of biggish split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 5.52 millimeters, and the outer diameter of ring is 5.92 millis Rice.The size of lesser split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 4.72 millimeters, and the outer diameter of ring is 5.12 millis Rice.The spacing of biggish split ring resonator and lesser split ring resonator is 0.2 millimeter.Length of transmission line is 12.1 millimeters, wide Degree is 0.6 millimeter, and interval 121 is 0.3 millimeter.
(atmospheric environment, temperature are 20 degrees Celsius, and nitrogen accounts for about in the environment of sensor is placed in no gas to be detected 78%, oxygen accounts for about 21%, and rare gas accounts for about 0.94%, and carbon dioxide accounts for about 0.03%, 0.03%) other gases account for about, and adopts The frequency and S of the sensor are tested at 2.0GHz to 3.0GHz frequency with vector network analyzer test sensor11's Curve 3, the resonance frequency for obtaining curve 3 is 2.46GHz；Later, sensor is placed in environment to be detected, wherein NO2's Concentration is 10ppm, tests the sensing at 2.0GHz to 3.0GHz frequency using vector network analyzer test sensor The frequency and S of device11Curve 2, obtain curve 2 resonance frequency be 2.41GHz；Curve 2 relative to 3 frequency displacement 0.05GHz of curve, Later, sensor is placed in another environment to be detected, wherein NO2Concentration be 100ppm, using vector network analyzer Test sensor tests the frequency and S of the sensor at 2.0GHz to 3.0GHz frequency11Curve 1, obtain curve 1 Resonance frequency is 2.32GHz, and curve 1 is relative to 3 frequency displacement 0.14GHz of curve；According to the frequency and S of sensor11Curve it is humorous Vibration frequency transformation, can learning environment to be detected, there are gas NO to be detected2, and can be according to the transformation of curve resonance frequency Know gas NO to be detected2Concentration.
The embodiment of sensor of the invention uses nano material MoS2It is applied to sensor in conjunction with complementary openings resonant ring, Pass through nano material MoS2After absorbing gas, the dielectric constant and electric conductivity of material all change, to finally cause to pass The variation of sensor resonance frequency, to obtain the concentration variation of gas, plays detection alarm by measuring the offset of resonance frequency Effect, and complementary openings resonant ring is used to be applied to sensor, the edge capacitance effect between the concentric circles of complementary openings resonant ring Resonance should occur, complementary openings resonant ring is applied to sensor and device is made to have negative permittivity and negative magnetic conductance in special frequency channel Rate, so that the size of sensor compares the quality factor that very little, Miniaturizable, and sensor have had with working frequency, it can Sensor sensitivity is improved, the application of left-handed material and nano material in modern detecting has been expanded.
The forming method of sensor of the invention forms microwave device unit using lsi technology, optimizes base In the processing step of the sensor of nano material.
The method of sensor of the invention detection gas is able to detect the gas of various concentration, is obtained by resonance frequency variation Know the concentration variation of detection gas, detection accuracy is high.
Although present disclosure is as above, present invention is not limited to this.Anyone skilled in the art are not departing from this It in the spirit and scope of invention, can make various changes or modifications, therefore protection scope of the present invention should be with claim institute Subject to the range of restriction.

Claims (4)

1. a kind of sensor based on nano material characterized by comprising
Semiconductor substrate with first surface and the second surface opposite with first surface；Positioned at the first medium of first surface Layer；Positioned at the second dielectric layer of second surface；Positioned at the transmission line of first medium layer surface, and transmission line has interval；Filling The MoS at the interval2Nanostructure；Positioned at the ground plane of second medium layer surface, have complementary openings humorous in the ground plane Shake ring, and the position of complementary openings resonant ring and the interval of transmission line are corresponding.
2. sensor as described in claim 1, which is characterized in that semiconductive substrate thickness is 400 microns to 600 microns, is situated between Electric constant is 11.9；The material of the first medium layer be silica, the first medium layer with a thickness of 10 to 30 microns, institute The dielectric constant for stating first medium layer is 4；The material of the second dielectric layer be silica, the second dielectric layer with a thickness of 10 to 30 microns, the dielectric constant of the second dielectric layer is 4；The length of transmission line is 11 millimeters to 13 millimeters, and width is 0.6 millimeter；The ground plane with a thickness of 5 microns to 20 microns.
3. sensor as described in claim 1, which is characterized in that the structure of the complementary openings resonant ring is two mutually opposite To the concentric split ring resonator of placement, wherein the size of biggish split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 5.52 millimeters, the outer diameter of ring is 5.92 millimeters；The size of lesser split ring resonator are as follows: being open is 0.3 millimeter, and the internal diameter of ring is 4.72 millimeters, the outer diameter of ring is 5.12 millimeters；The spacing of biggish split ring resonator and lesser split ring resonator is 0.2 milli Rice.
4. sensor as described in claim 1, which is characterized in that as the MoS of the sensor2When nanostructure quantity is 1, The equivalent circuit of the sensor includes: input terminal, the first end of input terminal connection first equivalent inductance of transmission line, transmission The second end of the first equivalent inductance of line connects MoS2The first end of the equivalent resistance of nanostructure, MoS2The equivalent electricity of nanostructure The second end of resistance connects MoS2The first end of the equivalent inductance of nanostructure, MoS2The second end of the equivalent inductance of nanostructure connects Meet MoS2The first end of the equivalent capacity of nanostructure, MoS2The second end of the equivalent capacity of nanostructure connects transmission line second The first end of equivalent inductance, the second end of the second equivalent inductance of transmission line connect output end, and the of the first equivalent capacity of transmission line One end connects the second end of the first equivalent inductance of transmission line, the second end connection transmission line second of the first equivalent capacity of transmission line etc. Imitate the first end of capacitor, the first end of second end connection the second equivalent inductance of transmission line of the second equivalent capacity of transmission line；It is complementary The second end of first end connection the first equivalent capacity of transmission line of the equivalent inductance of split ring resonator, complementary openings resonant ring etc. Imitate the second end of first end connection the first equivalent capacity of transmission line of capacitor, the second end of the equivalent inductance of complementary openings resonant ring Connect the second end of the equivalent capacity of complementary openings resonant ring and ground connection.
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