CN109580724A - Mini type gas sensor and its manufacturing method - Google Patents
Mini type gas sensor and its manufacturing method Download PDFInfo
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- CN109580724A CN109580724A CN201710911000.0A CN201710911000A CN109580724A CN 109580724 A CN109580724 A CN 109580724A CN 201710911000 A CN201710911000 A CN 201710911000A CN 109580724 A CN109580724 A CN 109580724A
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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
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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
- G01N27/128—Microapparatus
Abstract
The present invention is the structure of gas detecting machine, include: gas detecting machine chip, the sensing material back of the chip is a hollow structure, there is an insulating layer under sensing material, there is a microheater around sensing material, sensing material is attached in sensing electrode, and sensing material is the composite construction of a metal-oxide semiconductor (MOS) and a roughening lanthanum carbonate conversion zone；For the metal-oxide semiconductor (MOS) with a thickness of 0.1um~2um, which is 0.5um~4um, and back etch-hole size is less than 1*1mm；, can be in completion levitation gas sensing structure on silicon substrate via gas detecting machine structure provided by the present invention, and chip size can be accomplished to minimize.
Description
Technical field
The present invention be about a kind of gas sensor and its manufacturing method, particularly relate to a kind of miniature gas sensor and
Its manufacturing method.
Background technique
With society's commercialization and industrialized evolution, more and more interior spaces, which are warded off, to be built and more and more carries
Tool is used, provide people have a rest, work and commute it is required, however, when people are in those closed interior spaces,
Those spaces often cause the concentration of pernicious gas to be accumulated because of not circulating for air, gently then influence people in the space
Quality of life, it is heavy then may directly do harm to huamn body, it is however generally that, indoor carbon dioxide concentration is at 1,000ppm or less
Normal and draughty concentration value is generally regarded as, when indoor carbon dioxide concentration promotion to 1,000ppm~2,000ppm
It then may cause oxygen deficiency, make us sleepy, be enough to cause irritated situation, arrived when indoor carbon dioxide concentration is further promoted
When 2,000ppm~5,000ppm, then the discomfort of human body can be initially caused, include headache, drowsiness, and do not concentrated, infuse with energy
The decline of meaning power is palpitated quickly and the phenomenon of slight nausea, and when gas concentration lwevel is greater than 5,000ppm indoors, it is exposed to it
In may severe depletion of oxygen, cause permanent brain damage, stupor even dead.And in daily life actual measurement, Ren Men
Normal movable space can because the ventilation effect of room conditioning is insufficient or space in the factors such as number is excessive, make gas concentration lwevel
Measured value can reach 2,000ppm~3,000ppm or so, be that people can be allowed to start feelings that are drowsiness and causing a little pico- discomfort
Condition, if may result in indoor carbon dioxide concentration without further managing to indoor carbon dioxide concentration at this time
Continue to rise, be exposed to the people in space among danger,
On the other hand, carbon monoxide is also to need to add to notice the gas for managing its concentration in people's daily life, due to
Carbon monoxide is a kind of colorless and odorless and via the incomplete combustion of carbonaceous material chemical substance generated, therefore in ours
Incomplete situations such as waiting of the incomplete or locomotive exhaust burning of the natural gas gas combustion occurred in life, all still make me
Carbon monoxide is touched in living environment, have suitable close relationship.And carbon monoxide is due to the hemoglobin with human body
Affinity be higher by 100 times more compared with the affinity of oxygen and hemoglobin, therefore when human body sucks carbon monoxide, one
Carbonoxide will replace oxygen in conjunction with hemoglobin, make with the intracorporal oxygen competitive binding of people in the chance on hemoglobin
The oxygen content of adult body blood reduces, and makes people in the case where being detectable different shape, and gradually loss of consciousness, stupor are in turn because of the heart
Dirty and brain is impaired to lead to death, causes damages in view of anthracemia to life, confined space is for carbonomonoxide concentration
Raised early detection is a considerable key.
In the streets used gas sensor general at present, the predominantly gas sensor of infrared-type type, with red
Outside line provides energy excitation gas, is changed with generating temperature, displacement or frequency etc., the degree being actually taken up by gas by infrared ray,
And the absorbing state of characteristic absorption peak position is detected, to judge the type and concentration of gas.By infrared sensing gas, although
Measurement result accuracy rate is high, but its it is relatively easy influenced by ambient temperature, and volume is big, price is high, is not easy to be miniaturized,
A degree of difficulty is caused in application and popularizations.
In addition, separately there is a kind of gas sensor to carry out the detecting of gas with semiconductor form, metal oxide materials are burnt
Become semiconductor, in the state of keeping high temperature using heater, contacts metal oxide semiconductor with imflammable gas, to
It hopes resistance variations and gas concentration that certain relationship is presented to achieve the effect that CO gas is detected, is carried out through a thus mode
Monitoring, although device is simple, it is still easy to be influenced its route, and the pyroelectric effect shadow vulnerable to semiconductor by temperature and humidity
It rings, interferes the accuracy rate of detector.
Based on above content, it can be realized that gas concentration detection has great association for the safety of the interior space,
But gas sensor in the streets has the limitation in its use at present, therefore, how to provide a kind of miniature and accurate gas biography
Sensor, thus field want break through technology door.
Summary of the invention
The main object of the present invention is to provide a kind of mini type gas sensor, and the mini type gas sensor is small in size, detects
Survey is quick on the draw, and widely available in various confined spaces, carrying device or carrier etc., usability is high.
It is another object of the present invention to provide the senses that a kind of mini type gas sensor, the mini type gas sensor use
It measures and monitor the growth of standing timber and expects high sensitivity, can effectively reduce required temperature when sensed layer is sensed, avoid thermal energy in sensing process
Middle bring adverse effect.
It is a further object of the present invention to provide a kind of manufacturing methods of mini type gas sensor can using this method
Sensing material is coated on substrate, and makes sensing material tool good adhesion and thickness control.
To achieve the above object, present invention discloses a kind of mini type gas sensors, and it includes a substrate, the substrates
On be provided with a dielectric layer, wherein the dielectric layer include a heating element and two electrodes, in addition a sensed layer is provided, be set to
It is connected on the heating element and with two electrode, which is characterized in that the sensed layer is a metal oxide layer and a reaction
Layer is formed, and wherein the conversion zone is set on the metal oxide layer.
In one embodiment of the invention, the dielectric layer can be further disposed upon by also disclosing the heating device and two electrode
On.
In one embodiment of the invention, also disclosing the substrate is discontinuous structure, makes somebody a mere figurehead the dielectric layer in the substrate
On, generate the heat dissipation region not contacted directly with the substrate.
In one embodiment of the invention, the material of the conversion zone is also disclosed to be constituted selected from lanthanum carbonate and nanometer gold
One of combination person.
In one embodiment of the invention, the material for also disclosing the metal oxide layer is selected from tungstic acid, oxidation
One of the combination that zinc and stannic oxide are constituted person.
In one embodiment of the invention, the material of the heating element is also disclosed to be constituted selected from titanium, platinum, silver and tantalum
One of combination person.
In one embodiment of the invention, the material for also disclosing the dielectric layer is selected from silicon nitride, silica or nitrogen oxygen
One of the combination that SiClx is constituted person and any combination thereof.
To achieve the above object, present invention additionally discloses a kind of manufacturing method of mini type gas sensor, it is
The gas sensor of semiconductor formula includes a substrate, one heating element of a dielectric layer, two electrodes and a sensed layer, manufacture
Method is characterized in that: one metal oxide layer of setting is coated a layer containing lanthanum compound in the gold on the heating element
Belong on oxide skin(coating), a sensed layer is collectively formed, finally the sensed layer is made annealing treatment, this is made to contain the conversion of lanthanum compound layer
A conversion zone is formed, the manufacture that asked mini type gas sensor is invented in this case is completed.
In one embodiment of the invention, the annealing steps are also disclosed, annealing temperature is 300 DEG C~600 DEG C.
In one embodiment of the invention, also disclosing the application step is rotary coating or deposition.
In addition, being the gas of semiconductor formula present invention additionally discloses a kind of manufacturing method of mini type gas sensor
Body sensor is characterized in that comprising a substrate, one heating element of a dielectric layer, two electrodes and a sensed layer, manufacturing method:
One metal oxide layer is set on the heating element, is coated one containing gold metal layer on the metal oxide layer, jointly
A sensed layer is formed, finally the sensed layer is made annealing treatment, so that this is contained gold metal layer and forms a plurality of nanometer gold points, is completed
The manufacture of asked mini type gas sensor is invented in this case.
Detailed description of the invention
Fig. 1: it is the exploded side figure of a preferred embodiment of the invention；
Fig. 2: it is the cross-sectional view of another preferred embodiment of the invention；
Fig. 3: it is the preparation flow figure of a preferred embodiment of the invention；
Fig. 4 A to Fig. 4 B: it is the preparation flow figure of another preferred embodiment of the invention；
Fig. 5: it is the sensed layer structure and annealing time relational graph of a preferred embodiment of the invention；And
Fig. 6 A to Fig. 6 C: it is gas sensing effect schematic diagram of a preferred embodiment of the invention.[figure number is to as directed]
10 first substrates
11 the second substrates
20 dielectric layers
30 heating elements
40 electrodes
50 sensed layers
510 metal oxide layers
520 conversion zones
Specific embodiment
In order to make structure feature of the invention and it is reached the effect of have a better understanding and awareness, spy is with preferable
Embodiment and cooperation detailed description, are described as follows:
In the present invention, for current gas sensor volume is big, price is high, is not easy micromation and the insufficient feelings of accuracy rate
Condition provides a kind of novel mini type gas sensor structure.Using semiconductor-type structure as the base of the mini type gas sensor
Plinth, volume needed for can effectively reducing gas sensor, increases its application, in addition, using lanthanum carbonate or nanometer gold as
The sensing material of semiconductor-type gas sensor can also effectively improve the sensing sensitivity of gas sensor, improve gas biography
The accuracy of sensor.
Therefore, the present invention provides a novel mini type gas sensor structure, is with semiconductor-type gas sensor structure
Basis, the semiconductor structure include a heating sensing element, when a sensed layer is set on the heating element, the sensed layer
Possessed lanthanum carbonate or nanometer gold can by generating free electron after contacting and react with gas, due to lanthanum carbonate or how
The reaction of meter Jin Yu gas contact is quite sensitive, therefore its potential change generated is easy to be heated sensing element and connects measurement, and
Gas concentration is estimated by the variation of its resistance value, reaches highly sensitive testing goal.
Element, property and its preparation method for being included for mini type gas sensor of the invention down carry out further
Illustrate:
Referring to Fig. 1, its sectional view for the mini type gas sensor of the first embodiment of the present invention.As shown, this
Invention provides a substrate 10 and ㄧ dielectric layer 20, the dielectric layer 20 are set on the substrate 10, wherein the dielectric layer 20 packet
Containing a heating unit 30 and two electrodes 40, then, a sensed layer 50 is set on the heating unit 30, and the sensed layer 50
It is connected with two electrode 40, which is made of a metal oxide layer 510 and a conversion zone 520, and wherein this is anti-
Layer 520 is answered to be set on the metal oxide layer 510.
Based on above-mentioned sensor structure, gas sensor provided by the present invention can be by providing different conversion zone material
Material, and different gas can be sensed, it will be illustrated one by one below.
Mini type gas sensor provided by the present invention can be used to be directed to when the material of the conversion zone 520 is lanthanum carbonate
Carbon dioxide gas is detected, because as the oxonium ion (O in air2-) meeting when being reacted with the carbon dioxide of high concentration
Form carbanion (CO3 2-) (as shown in formula one), at this point, the carbanion will be contacted with the lanthanum carbonate of the conversion zone
And reacted, lanthanum carbonate, oxygen, carbon dioxide and free electron (as shown in formula two) are generated, at this point, separated free electricity
The surface conductivity for making the sensed layer 50 is increased and then declines resistivity by son, while the resistance value has with dioxy in environment
The phenomenon that changing the increase of concentration of carbon and declining estimates the concentration of carbon dioxide in environment by this variation, and then reaches this hair
The setting purpose of bright gas sensor.In addition, when the gas concentration lwevel decline in air, the carbonate that dissociates in environment from
Sub- content, which will be not enough to react with the lanthanum carbonate of the conversion zone, generates electronics, at this point, dissociating during sensing to the sense
The free electron for surveying layer 50 will be returned to the conversion zone, and the resistance value of sensor will return back to the state of starting, to prepare into
The gas concentration sensing of row next time.In addition, the conversion zone can further progress roughening treatment in one embodiment of the invention
To form a roughening conversion zone 525, preferably, which can be a roughening lanthanum carbonate conversion zone.
CO2+O2-→CO3 2-(formula one)
La2O2CO3+CO3 2-→La2O2CO3+1/2O2+CO2+2e-(formula two)
In addition, working as mini type gas sensor provided by the present invention, when the material of the conversion zone 520 is nanometer gold, then
It can be used to be detected for CO gas.When being passed through CO gas and as the temperature rises, carbon monoxide meeting
Carbon dioxide and free electron (as shown in formula four) are resolved into, separated free electron also can be such that the surface of the sensed layer 50 leads
Electrically increase and then decline resistivity, the same resistance value that generates has with the increase of concentration and the phenomenon that decline, and then effective
Detect the concentration of carbon monoxide in environment.
CO+O2-→CO2+2e-(formula four)
Foregoing mini type gas sensor, wherein the substrate 10 provided by the present invention is to carry the semiconductor
Formula mini type gas sensor, to make chip maintain the basic physical property of baseplate material in preparation process, not because of preparation process
In high temperature and change, be selected under high temperature operation be prepared with the baseplate material of sufficient stability.Meanwhile to keep away
Exempting from baseplate material influences the electric conductivity of whole chip structure, and then misleads the conductive performance after gas sensing combines, therefore the base
Plate material should not have electric conductivity, based on above-mentioned property, substrate 10 provided by the present invention can be further selected from glass, silicon and
One of group composed by quartz is any combination thereof.
Foregoing mini type gas sensor, wherein disclosed herein the dielectric layer 20 to as semiconductor
Multilayered structure electrical isolation use, to improve the sensing efficiency of the mini type gas sensor, the material of the dielectric layer 20 exists
Be in most cases insulator, when there are extra electric field, the electronics, ion or the molecule that are included can thus generate pole
Change, uses the capacitance for increasing the mini type gas sensor.Based on above-mentioned property, dielectric layer 20 provided by the present invention can be into
One step is selected from one of silicon nitride, silica or silicon oxynitride person and any combination thereof.Preferably uses silicon nitride and oxidation
Silicon, and the silicon nitride material is coated on the silica material.
Hold described in continuous upper section, disclosed herein the dielectric layer 20 include a heating unit 30 and two electrodes 40, should
Heating unit 30 and two electrode 40 can be embedded among the dielectric layer 20, can be also directly arranged on the dielectric layer 20, should
Heating unit is connected with a power supply, to receive the electric energy of the power supply and convert thereof into thermal energy, to provide gas of the invention
The use of body sensor detection gas, and be that the thermal energy for providing it is stablized, the material of the heating unit 30 provided by the present invention
It is first choice with noble metal, based on above-mentioned property, what the material of the heating unit 30 was constituted selected from titanium, platinum, gold, silver and tantalum
One of combination person.In addition, two electrode 40 is configured in a manner of electrically isolating with the heating unit 30, and two electrode
40 are connected with the sensed layer 50, to measure the sensed layer 50 via generated electric current and potential change amount is reacted, to carry out
The judgement of gas concentration and content in environment.
Foregoing mini type gas sensor, wherein the sensed layer 50 provided by the present invention is to contact monitoring ring
Object gas in border is simultaneously reacted, and when object gas and the material of the sensed layer 50 and when being reacted, can be generated
Free electron causes the potential change of the sensed layer 50 and generates electric current, then via two electrode 40 connecting with the sensed layer 50
It is measured to reach the target of gas sensing.The sensed layer 50 includes a metal oxide layer 510 and a conversion zone 520,
It wherein the material of the conversion zone 520 and its all provides in foregoing teachings with the reaction process of object gas, has been repeated no more in this；
In addition, the metal oxide layer 510 provided by the present invention, the use as conductor to transmit electronics, to make it transmit electronics
Function it is more rapid and sharp, the metal oxide layer 510 provided by the present invention is configured using single substance, is based on
Above-mentioned content, the metal oxide layer 510 provided by the present invention are selected from tungstic acid, zinc oxide and stannic oxide and are constituted
One of combination person and any combination thereof.
The second figure for illustrating of the present invention is please referred to, in another preferred embodiment provided by the present invention, as shown,
The substrate 11 of the gas sensor be discontinuous structure, by this one design, the dielectric layer 20 make somebody a mere figurehead in the substrate 11 it
On, generation does not make the dielectric layer by the setting of the heat dissipation region 201 with the heat dissipation region 201 that the substrate 11 directly contacts
20 when carrying out the effect of gas sensing, is able to effectively adjust because of thermal energy caused by the heating element 30, makes the gas sensing
Device bulk temperature is unlikely to excessively high, thus can not only reduce the generation of pyroelectric effect, increases the measurement of gas sensor
Stability and accuracy.
Then, the preparation flow figure for illustrating third figure is invented in collocation below, illustrates the preparation method of mini type gas sensor,
Mini type gas sensor provided by the present invention, be semiconductor formula gas sensor, have a substrate, a dielectric layer,
One heating element, two electrodes and a sensed layer, manufacturing method are characterized in that:
Step S11: one metal oxide layer of setting is on the heating element；
Step S13: a sensed layer is collectively formed on the metal oxide layer in one layer containing lanthanum compound of coating；And
Step S15: making annealing treatment the sensed layer, so that this is contained lanthanum compound layer and converts to form a conversion zone.
The step of S11 as shown, in the preparation method of mini type gas sensor provided by the invention, provides metal oxidation
Nitride layer is used as conductor with transmitting electronics, which is configured in a manner of depositing, the depositional mode
Can be chemical vapor deposition or physical vapour deposition (PVD), in addition, to provide sufficient electron transmission ability, and material properties not vulnerable to
Heating process influences, and metal oxide materials provided by the present invention are selected from tungstic acid, zinc oxide and stannic oxide and are constituted
One of combination person, the scope of the patents that right this case is asked should not be as limit.
The step of S13 as shown, in the preparation method of mini type gas sensor provided by the invention, is coated with a chemical combination containing lanthanum
A sensed layer is collectively formed on the metal oxide layer in nitride layer.Wherein, this contains lanthanum compound layer and is set in a manner of being coated with
The coating method can be rotary coating, chemical vapor deposition or physical vapour deposition (PVD) on the metal oxide layer；In addition,
Described contains lanthanum compound, and referring to can be referred to as by the compound for providing thermal energy and being converted into lanthana, in view of this, provided by the present invention
Layer material containing lanthanum compound be selected from one of the combination that is constituted of lanthanum hydroxide and lanthanum carbonate person；It and is to be formed after making the coating
The inductive layer can have good sensing function and electron transmission ability, which need to be controlled,
Coating with a thickness of 1um~5um, with benefit, this contains lanthanum compound layer contact carbon dioxide molecule, while rapidly carrying out electronics biography
It passs；Based on above-mentioned content, in a preferred embodiment provided by the present invention, by lanthanum hydroxide and isopropanol and cosolvent
After evenly mixing, one 1um~5um layer containing lanthanum compound is formed using spin-on techniques, completes the setting of this layer；In addition,
In one embodiment of the invention, this contain lanthanum compound layer can further progress roughening treatment to form a roughening chemical combination containing lanthanum
Nitride layer.
The step of S15 as shown, in the preparation method of mini type gas sensor provided by the invention, carries out the sensed layer
Annealing, makes this contain lanthanum compound layer and converts to form a conversion zone.Due to the layer containing lanthanum compound can not directly with detection ring
Carbon dioxide molecule in border directly carries out reaction and generates electron stream, it is therefore desirable to via an annealing steps, those be contained lanthanum
It closes object and is transformed into the compound of reaction that can be converted into lanthana via heating.In a preferred embodiment provided by this case,
The annealing temperature of annealing steps is between 300 DEG C -600 DEG C.
Then, below arrange in pairs or groups invention pictorial image 4A preparation flow figure, illustrate the preparation method of mini type gas sensor, this
Mini type gas sensor provided by inventing is the gas sensor of semiconductor formula, has a substrate, a dielectric layer, one
Heating element, two electrodes and a sensed layer, manufacturing method are characterized in that:
Step S21: one metal oxide layer of setting is on the heating sensing element；
Step S23: one is formed containing gold metal layer on the metal oxide layer, a sensed layer is collectively formed；And
Step S25: making annealing treatment the sensed layer, so that this is contained gold metal layer and forms a plurality of nanometer gold points.
The step of S21 as shown, in the preparation method of mini type gas sensor provided by the invention, provides metal oxidation
For nitride layer on the heating sensing element, setting method and material are all same with step S11, repeat no more in this.
The step of S23 as shown, in the preparation method of mini type gas sensor provided by the invention, coating one is containing golden metal
In on the metal oxide layer sensed layer is collectively formed, this, which contains gold metal layer, to be coated by the mode of deposition, institute in layer
The depositional mode stated can be chemical vapor deposition or physical vapour deposition (PVD), due to this one containing gold metal layer be only transition coating knot
Structure can not be successfully to form nanometer gold point after leading to annealing to avoid overweight coating, thus its coating with a thickness of 1nm~
30nm, preferably 3nm~15nm form the structure of a plurality of nanometer gold points with the sharp gold metal.
The step of S25 as shown, in the preparation method of mini type gas sensor provided by the invention, carries out the sensed layer
Annealing, makes this contain gold metal layer and forms a plurality of nanometer gold points, and using the enough electrical conduction abilities of offer makes carbon monoxide
When gas is attached to mini type gas sensor, sensing layer surface is able to conduct electronics caused by the reaction.Wherein, such as Fig. 5
It is shown, have a suitable close relationship due to forming the process of nanometer gold point and reaction time containing gold metal layer, nanometer gold point with how
Hole between meter Jin Dian by with the elongation of annealing time, and with expansion, therefore to make nanometer gold point that there is optimal electricity
Son passes to efficiency, and in a preferred embodiment provided by this case, the time of the heat treatment step of annealing steps is between 10
Between second to 60 seconds, preferably between 20 seconds to 40 seconds；Meanwhile the temperature of the heat treatment step between 300 DEG C -600 DEG C it
Between.
In addition, the preparation flow figure of collocation invention pictorial image 4B, the preparation of mini type gas sensor provided by the present invention
Method, can further in formed one containing gold metal layer before on the metal oxide layer, in advance be coated with a layer containing lanthanum in
On the metal oxide layer.As shown in the step S22 and S24 of invention pictorial image 4B, another preferable reality provided by the present invention
It applies in example, in a metal oxide layer is arranged after on the heating element, is coated with a layer containing lanthanum compound in advance in the gold
Belong on oxide skin(coating), coating one containing gold metal layer on the metal oxide layer for being coated with the layer containing lanthanum, common shape
At a sensed layer, finally the sensed layer is made annealing treatment again, so that this is contained gold metal layer and forms a plurality of nanometer gold points, is completed
The preparation of the mini type gas sensor of another preferred embodiment.Wherein, this contains in the application step of lanthanum layer, used painting
Mode for cloth is rotary coating or deposition；In addition, this contains in the application step of lanthanum layer, used layer containing lanthanum compound
One of the combination that is constituted selected from lanthanum hydroxide and lanthanum carbonate of material person, in one embodiment of the invention, this contains lanthanum
Compound layer can further by do roughening treatment, to form a roughening layer containing lanthanum compound, also that is, the roughening chemical combination containing lanthanum
Nitride layer can be a roughening lanthanum hydroxide layer or a roughening lanthanum carbonate layer.
Using mini type gas sensor obtained by prepared by above-mentioned any preparation method, can be used to for carbon monoxide gas
Body is detected, and when being passed through CO gas and as the temperature rises, carbon monoxide can resolve into carbon dioxide and dissociate
Electronics, separated free electron can make the surface conductivity of the sensed layer increase and then decline resistivity, same to generate electricity
Resistance value has with the increase of concentration and the phenomenon that decline, and then effectively detects the concentration of carbon monoxide in environment.
Hereinafter, the use of the elaboration of organizational technology's content, feature and achievement using the example of specific implementation as the invention, and
It can implement accordingly, but protection scope of the present invention is not limited thereto.
[embodiment 1]
The test of the structural property of mini type gas sensor containing lanthanum compound
Fig. 6 A is please referred to, carries out carbon dioxide gas for mini type gas sensor containing lanthanum compound provided by the present invention
When sensing, the schematic diagram of time and resistance variations is sensed, as shown, the carbon dioxide sensed in environment is dense at first 120 seconds
Degree is 600ppm, in next ten minutes, is improved in sensing environment according to each mode for increasing 400ppm carbon dioxide
Gas concentration lwevel seven times, and observe the resistance change of the mini type gas sensor containing lanthanum compound；As can be observed from Figure,
Gas concentration lwevel in every primary sensing environment of raising, the resistance value of the gas sensor i.e. meeting rapid decrease reach one and stablize
Value, and be maintained at the stationary value until improving the gas concentration lwevel in sensing environment next time, and starting resistance and final
The difference of resistance value is up to six Wan Aomu, the stabilization of obvious its gas sensing ability of the gas sensor and the width of sensing range
Extensively；Finally, when stopping supplying carbon dioxide gas, it, should when making to sense the gas concentration lwevel reply initial state in environment
The resistance value of gas sensor can also return back to initial value in a short period of time, and its resistance value and sensing start before resistance
Value difference is different less, reflects that the high of this gas sensor measures stability.
Fig. 6 B is please referred to, is mini type gas sensor containing lanthanum compound provided by this case and the dioxy under the prior art
The measurement for changing carbon sensor compares figure, and the data of square dot are measured by presently commercially available carbon dioxide gas sensor
Content, circular dot is then content measured by mini type gas sensor containing lanthanum compound provided by the present invention, as shown,
Gas sensor provided by the present invention can not only be sensed under biggish gas concentration lwevel range, and more can be quasi-
True reflects actual gas concentration lwevel in environment, obvious mini type gas sensor containing lanthanum compound provided by the present invention
Really the technology door that the prior art can be broken through provides more sensitive and effective carbon dioxide gas sensor.
[embodiment 2]
The test of nanometer gold mini type gas sensor structural property
Fig. 6 C is please referred to, is nanometer gold mini type gas sensor provided by the present invention in different annealing time conditions
Under, in carbon monoxide environment, the tendency chart of mini type gas sensor power and change of sensitivity, as shown, when this contains
When gold metal layer is not handled via annealing steps (i.e. number of seconds is zero), since this not will form nanometer gold point containing gold metal layer, therefore
When mini type gas sensor operated (i.e. sensor heating power rises), the abilities of sense gasses can't with mention
It rises；In addition, other are via gas sensor made of prepared by different annealing times, although gas prepared under different condition
All there is sensor similar resistivity to change trend, but minitype gas prepared by 30 seconds annealed step process time passes
Sensor not only has maximum sensitivity (~35%), and variation tendency is also compared with the group of annealing steps processing 15 seconds time and 60 seconds
Not more stable, the distribution of its obvious nanometer gold point is the most complete appropriate, is able to adsorb more carbon monoxide, and in measuring range
In obtain highest and most accurate numerical value.
In conclusion the present invention provides the mini type gas sensor and preparation method thereof of the highly stable degree of a tool really, by
Since the sensed layer of different materials being arranged on semiconductor structure, the gas for being able to effectively be directed in sensing environment is monitored,
Current gas sensor, especially carbon dioxide gas sensor are solved, volume is big, price is high, is not easy the case where being miniaturized,
Volume needed for gas sensor can effectively being reduced, increases its application, to provide a kind of novel mini type gas sensor
Structure.In addition, using lanthanum carbonate or nanometer gold as the sensing material of semiconductor-type gas sensor, as shown in embodiment,
Really sensing sensitivity and its accuracy of gas sensor are also effectively improved.In view of this, invention provided by this case has really
The effect of more brilliance progresses greatly compared to the prior art, requirement needed for meeting patent application.
Above is only presently preferred embodiments of the present invention, are not used to limit the scope of implementation of the present invention, Fan Yibenfa
Equivalent changes and modifications carried out by shape described in bright scope of the claims, construction, feature and spirit, should be included in the present invention
Scope of the claims in.
Claims (22)
1. a kind of mini type gas sensor, which is characterized in that it includes a substrate, a dielectric layer, which is set to the base
On plate and include a heating element and two electrodes and a sensed layer, be set on the heating element and with two electricity
Pole is connected, it is characterised in that:
The sensed layer is made of a metal oxide layer and a conversion zone, and wherein the conversion zone is set to the metal oxide layer
On, and the metal oxide layer is conductive.
2. mini type gas sensor as described in claim 1, which is characterized in that wherein the heating element and two electrode can be into
One step is set on the dielectric layer.
3. mini type gas sensor as described in claim 1, which is characterized in that wherein the substrate is discontinuous structure, makes this
Dielectric layer is maked somebody a mere figurehead on the substrate, and the heat dissipation region not contacted directly with the substrate is generated.
4. mini type gas sensor as described in claim 1, which is characterized in that wherein the material of the conversion zone is selected from carbon
One of the combination that sour lanthanum and nanometer gold are constituted person.
5. mini type gas sensor as described in claim 1, which is characterized in that wherein the conversion zone is a roughening conversion zone.
6. mini type gas sensor as claimed in claim 5, which is characterized in that wherein the material of the roughening conversion zone is roughening
Lanthanum carbonate.
7. mini type gas sensor as described in claim 1, which is characterized in that wherein the material of the metal oxide layer is choosing
From one of the combination constituted in tungstic acid, zinc oxide and stannic oxide person.
8. mini type gas sensor as described in claim 1, which is characterized in that wherein the material of the heating element be selected from
One of the combination that titanium, gold, platinum, silver and tantalum are constituted person.
9. mini type gas sensor as described in claim 1, which is characterized in that wherein the material of the dielectric layer is selected from nitrogen
One of the combination that SiClx, silica or silicon oxynitride are constituted person and any combination thereof.
10. a kind of manufacturing method of mini type gas sensor, which is characterized in that it is the gas sensor of semiconductor formula, tool
There is a substrate, a dielectric layer, a heating element, two electrodes and a sensed layer, manufacturing method to be characterized in that:
One metal oxide layer is set on the heating element；
A layer containing lanthanum compound is coated on the metal oxide layer, a sensed layer is collectively formed；And
The sensed layer is made annealing treatment, so that this is contained lanthanum compound layer and converts to form a conversion zone.
11. the manufacturing method of mini type gas sensor as claimed in claim 10, which is characterized in that wherein this contains lanthanum compound
Layer is a roughening layer containing lanthanum compound.
12. the manufacturing method of mini type gas sensor as claimed in claim 10, which is characterized in that the wherein annealing steps,
Its annealing temperature is 300 DEG C ~ 600 DEG C.
13. the manufacturing method of mini type gas sensor as claimed in claim 10, which is characterized in that wherein the application step is
Rotary coating or deposition.
14. the manufacturing method of mini type gas sensor as claimed in claim 10, which is characterized in that the wherein metal oxide
The material of layer is one of the combination that is constituted selected from tungstic acid, zinc oxide and stannic oxide person.
15. the manufacturing method of mini type gas sensor as claimed in claim 8, which is characterized in that wherein layer containing lanthanum compound
Material be one of the combination that is constituted selected from lanthanum hydroxide and lanthanum carbonate person.
16. a kind of manufacturing method of mini type gas sensor, which is characterized in that it is the gas sensor of semiconductor formula, tool
There is a substrate, a dielectric layer, a heating element, two electrodes and a sensed layer, manufacturing method to be characterized in that:
One metal oxide layer is set on the heating element；
One is formed containing gold metal layer on the metal oxide layer, a sensed layer is collectively formed；And it anneals to the sensed layer
Processing, makes this contain gold metal layer and forms a plurality of nanometer gold points.
17. the manufacturing method of mini type gas sensor as claimed in claim 16, which is characterized in that the wherein annealing steps,
Its annealing temperature is 300 DEG C ~ 600 DEG C.
18. the manufacturing method of mini type gas sensor as claimed in claim 16, which is characterized in that wherein the forming step is
Rotary coating or physical vapor deposition coating film.
19. the manufacturing method of mini type gas sensor as claimed in claim 16, which is characterized in that the wherein metal oxide
The material of layer is one of the combination that is constituted selected from tungstic acid, zinc oxide and stannic oxide person.
20. the manufacturing method of mini type gas sensor as claimed in claim 16, which is characterized in that wherein utilize the manufacturer
The prepared mini type gas sensor obtained of method is to carry out induction detecting for CO gas.
21. a kind of mini type gas sensor, which is characterized in that the heating layer and the sensed layer are embedded in the dielectric layer.
22. a kind of mini type gas sensor, which is characterized in that wherein the substrate is discontinuous structure, enables the dielectric layer frame
To form the heat dissipation region being not directly contacted in the substrate on the substrate.
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| CN201710911000.0A CN109580724A (en) | 2017-09-29 | 2017-09-29 | Mini type gas sensor and its manufacturing method |
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| CN201710911000.0A CN109580724A (en) | 2017-09-29 | 2017-09-29 | Mini type gas sensor and its manufacturing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157590A (en) * | 2020-01-21 | 2020-05-15 | 复旦大学 | Semiconductor type carbon monoxide sensor |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158410A1 (en) * | 2003-02-07 | 2004-08-12 | Tdk Corporation | Carbon dioxide sensor |
| CN1766601A (en) * | 2004-10-29 | 2006-05-03 | Tdk株式会社 | Carbon dioxide sensor |
| US20060154401A1 (en) * | 2005-01-10 | 2006-07-13 | University Of Warwick | Gas-sensing semiconductor devices |
| TW200846481A (en) * | 2007-05-25 | 2008-12-01 | Semivac Equipment Co Ltd | Nano-gold material and production method thereof |
| CN101349669A (en) * | 2007-07-19 | 2009-01-21 | 张薰予 | Formaldehyde gas sensor |
| CN101939639A (en) * | 2007-12-10 | 2011-01-05 | 欧洲宇航防务集团德国有限责任公司 | Gas sensor with improved selectivity |
| TW201115140A (en) * | 2009-10-23 | 2011-05-01 | Metal Ind Res & Dev Ct | Gas sensor capable of simultaneously sensing oxygen and carbon dioxide, manufacturing method thereof and its gas sensor system |
| CN102095766A (en) * | 2010-12-02 | 2011-06-15 | 西安交通大学 | Miniature integrated temperature control type CO2 gas sensor and manufacturing method thereof |
| KR20130121407A (en) * | 2012-04-27 | 2013-11-06 | 전자부품연구원 | Method for manufacturing the micro gas sensor |
| CN204330652U (en) * | 2014-07-28 | 2015-05-13 | 长春工业大学 | A kind of organic gas sensor of C-nano tube hetero-junction |
| CN104713915A (en) * | 2015-03-18 | 2015-06-17 | 华中科技大学 | High-performance gas sensor based on laminated structure and preparation method for high-performance gas sensor |
| TWI580971B (en) * | 2016-01-29 | 2017-05-01 | Chip structure for detecting carbon monoxide concentration and method of manufacturing the same | |
| CN107003263A (en) * | 2014-12-22 | 2017-08-01 | 罗伯特·博世有限公司 | Sensor and its manufacture method for measuring the gas concentration lwevel in admixture of gas |
-
2017
- 2017-09-29 CN CN201710911000.0A patent/CN109580724A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158410A1 (en) * | 2003-02-07 | 2004-08-12 | Tdk Corporation | Carbon dioxide sensor |
| CN1766601A (en) * | 2004-10-29 | 2006-05-03 | Tdk株式会社 | Carbon dioxide sensor |
| US20060154401A1 (en) * | 2005-01-10 | 2006-07-13 | University Of Warwick | Gas-sensing semiconductor devices |
| TW200846481A (en) * | 2007-05-25 | 2008-12-01 | Semivac Equipment Co Ltd | Nano-gold material and production method thereof |
| CN101349669A (en) * | 2007-07-19 | 2009-01-21 | 张薰予 | Formaldehyde gas sensor |
| CN101939639A (en) * | 2007-12-10 | 2011-01-05 | 欧洲宇航防务集团德国有限责任公司 | Gas sensor with improved selectivity |
| TW201115140A (en) * | 2009-10-23 | 2011-05-01 | Metal Ind Res & Dev Ct | Gas sensor capable of simultaneously sensing oxygen and carbon dioxide, manufacturing method thereof and its gas sensor system |
| CN102095766A (en) * | 2010-12-02 | 2011-06-15 | 西安交通大学 | Miniature integrated temperature control type CO2 gas sensor and manufacturing method thereof |
| KR20130121407A (en) * | 2012-04-27 | 2013-11-06 | 전자부품연구원 | Method for manufacturing the micro gas sensor |
| CN204330652U (en) * | 2014-07-28 | 2015-05-13 | 长春工业大学 | A kind of organic gas sensor of C-nano tube hetero-junction |
| CN107003263A (en) * | 2014-12-22 | 2017-08-01 | 罗伯特·博世有限公司 | Sensor and its manufacture method for measuring the gas concentration lwevel in admixture of gas |
| CN104713915A (en) * | 2015-03-18 | 2015-06-17 | 华中科技大学 | High-performance gas sensor based on laminated structure and preparation method for high-performance gas sensor |
| TWI580971B (en) * | 2016-01-29 | 2017-05-01 | Chip structure for detecting carbon monoxide concentration and method of manufacturing the same |
Non-Patent Citations (2)
| Title |
|---|
| DEGONG DING ET AL.: "Facile synthesis of La2O2CO3 nanoparticle films and Its CO2 sensing properties and mechanisms", 《APPLIED SURFACE SCIENCE》 * |
| GANG CHEN ET AL.: "Lanthanum Dioxide Carbonate La2O2CO3Nanorods as a Sensing Material for Chemoresistive CO2 Gas Sensor", 《ELECTROCHIMICA ACTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157590A (en) * | 2020-01-21 | 2020-05-15 | 复旦大学 | Semiconductor type carbon monoxide sensor |
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