CN106124572A - alarm based on CO gas detection function - Google Patents

Abstract

The application relates to alarm based on CO gas detection function, this alarm include alarm device and CO gas sensor, described CO gas sensor include Si substrate, be formed at the suprabasil silicon oxide film of described Si, the W film that is placed on described silicon oxide film, the WO that is formed on W film₃Nano wire film, it is overlying on WO₃SnO on nano wire film₂Nano thin-film, at SnO₂On nano thin-film make two Pt electrodes and be positioned at the suprabasil heating module of described Si.This alarm is highly sensitive to CO gas, and response time is short, and repeatability and stability are the most preferable.

Description

Alarm based on CO gas detection function

Technical field

The application relates to alarm field, particularly relates to alarm based on CO gas detection function.

Background technology

Gas alarm is Leakage inspection alarm, and operation principle is for flammable or poisonous etc. when having in working environment During specific gas leakage, after gas alarm detects the setting value of this gas concentration, alarm will send alarm signal, with Prompting takes safety measures.

MOS type gas sensor has the advantages such as corrosion-resistant, cost of manufacture is low, Cleaning Principle is simple, But, existing metal oxide semiconductor sensor based on CO gas detecting still has selectivity, less stable, response not Reach the problems such as the sensitiveest.

Summary of the invention

For overcoming problem present in correlation technique, the application provides alarm based on CO gas detection function.

The present invention is achieved through the following technical solutions: alarm based on CO gas detection function, and this alarm includes report Alarm device and CO gas sensor；Described CO gas sensor includes Si substrate, to be formed at the suprabasil silicon oxide of described Si thin Film, the W film being placed on described silicon oxide film, the WO that is formed on W film₃Nano wire film, it is overlying on WO₃On nano wire film SnO₂Nano thin-film, at SnO₂On nano thin-film make two Pt electrodes and be positioned at the heating module below described Si substrate；Institute State WO₃Nanowire length is 500～8000nm.

Preferably, the preparation method of CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 600nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 300nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.01wt%～ 0.1wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

The technical scheme that embodiments herein provides can include following beneficial effect:

(1) alarm based on CO gas detection function that embodiments herein is provided, this alarm includes reporting to the police Device and CO gas sensor, and this CO gas sensor is based on SnO₂The resistor-type CO sensor of nano material, passes through WO₃ Nano wire and SnO₂The combination of nano material, enhances the aspect effects such as selectivity, stability that CO detects by CO gas sensor Really；CO gas sensor is at WO₃On the basis of nano wire film, coat one layer of SnO₂Nano material, is filled between nano wire sky Gap, due to WO₃Nano wire has bigger specific surface area so that itself and SnO₂Nano material contact area substantially increases, WO₃Receive Rice noodle is cooked catalyst and substantially increases SnO₂Sensitivity and selectivity to CO, and then improve the sensitivity of alarm.

(2) alarm based on CO gas detection function that embodiments herein is provided, the CO gas used due to it Body sensor uses SnO₂Nano material is prepared by sol-gal process, and SnO₂Nano material increases with the contact area of gas, enters And improve SnO₂The nano material absorbability to gas, simultaneously because doping TiO₂Nanoparticle, it is possible to promote material surface Oxonium ion and the reaction of reducibility gas CO, and then improve the sensor sensitivity to CO.

Aspect and advantage that the application adds will part be given in the following description, and part will become from the following description Obtain substantially, or recognized by the practice of the application.It should be appreciated that above general description and details hereinafter only describe It is exemplary and explanatory, the application can not be limited.

Accompanying drawing explanation

Accompanying drawing herein is merged in description and constitutes the part of this specification, it is shown that meet the enforcement of the present invention Example, and for explaining the principle of the present invention together with description.

Fig. 1 be the present invention alarm in the structural representation of CO gas sensor.Wherein: 01-Si substrate, 02-oxidation Silicon thin film, 03-W film, 04-WO₃Nano wire film, 05-SnO₂Nano thin-film, 06-Pt electrode, 07-heating module.

Fig. 2 is to prepare CO gas sensor flow chart.

Detailed description of the invention

Here will illustrate exemplary embodiment in detail, its example represents in the accompanying drawings.Explained below relates to During accompanying drawing, unless otherwise indicated, the same numbers in different accompanying drawings represents same or analogous key element.Following exemplary embodiment Described in embodiment do not represent all embodiments consistent with the present invention.On the contrary, they are only with the most appended The example of the apparatus and method that some aspects that described in detail in claims, the present invention are consistent.

Following disclosure provides many different embodiments or example for realizing the different structure of the application.For letter Changing disclosure herein, hereinafter parts and setting to specific examples are described.Certainly, they are the most merely illustrative, and It is not intended to limit the application.Additionally, the application can in different examples repeat reference numerals and/or letter.This heavy It is for purposes of simplicity and clarity again, itself is more than the relation between various embodiment being discussed and/or arranging.This Outward, the various specific technique that this application provides and the example of material, but those of ordinary skill in the art it can be appreciated that The applicability of other techniques and/or the use of other materials.It addition, fisrt feature described below Second Eigenvalue " on " Structure can include that the first and second features are formed as the embodiment directly contacted, it is also possible to include that other feature is formed at Embodiment between first and second features, such first and second features are not likely to be directly contact.

In the description of the present application, it should be noted that unless otherwise prescribed and limit, term " is installed ", " being connected ", " connect " and should be interpreted broadly, for example, it may be mechanically connected or electrical connection, it is also possible to be the connection of two element internals, can Being to be joined directly together, it is also possible to be indirectly connected to by intermediary, for the ordinary skill in the art, can basis Concrete condition understands the concrete meaning of above-mentioned term.

At present, sensor technology has become as the pith of modern development in science and technology, itself and computer technology, communication technology Three broad aspect of composition modern information technologies.It is a weight of sensor based on gas detecting and the gas sensor identifying warning Want branch.At aspects such as breed of crop, beverage industry, food industry, atmospheric monitoring, commercial production, sensor plays more Carry out the most important effect.

CO gas is a kind of gas harmful to human body and environmental toxic.After people suck a small amount of CO, its easily with blood In liquid, haemachrome combines and forms stable associated complex, causes hemoglobin to lose the ability of conveying oxygen, eventually causes human body group Knitting anoxia, the lighter produces the symptoms such as headache, vomiting, and severe patient can cause brain injury or death.

In productive life, the source of CO is a lot.In coke plant, steel mill, chemical plant etc., operator are likely to be exposed at In high concentration CO gas, family's coal heating, the accident leakage of terminal coal gas, scene of fire etc. also can produce a large amount of CO, easily Cause the poisoning of people.It addition, CO is a kind of inflammable and explosive gas simultaneously, when in air CO content 12%～74% Time can explode.

The sensor being currently based on CO gas detecting mainly has MOS type, electrochemistry type, solid electrolytic Matter type, catalytic combustion type etc., MOS type sensor has Heat stability is good, low cost, components and parts making letter The advantages such as list, have become as the class sensor that research is more.

Stannum is a kind of common elements, is positioned at IVA race in periodic chart, and it can be combined into many oxide with oxygen, wherein, SnO₂It is most stable of.SnO₂Belong to a kind of typical wide bandgap semiconductor metal-oxide, due to self crystal structure, table Face characteristic and characterization of adsorption etc., SnO₂The fields such as gas sensor, solaode, electrochemistry are widely used.SnO₂Make For a kind of important gas sensor sensitive material, there is the advantages such as response is sensitive, cost of manufacture is low, technological process is simple, warp It is commonly used for the detection of reducibility gas.

The probe gas principle of MOS type gas sensor is based on sensing element and object gas Interact.Metal-oxide semiconductor (MOS) has stronger physically or chemically absorbability for gas, when itself and air contact Time, the oxygen in air can be adsorbed in the surface of metal-oxide semiconductor (MOS) sensitive material, and interact with sensitive material, produce Negative oxygen ion；When, after contact reducibility gas, reducibility gas reacts with the negative oxygen ion on this sensitive material surface, causes partly leading Body sensitive material carrier concentration becomes big, thus causes this sensitive material electrical conductivity to become big, and resistance declines, based on sensitive material electricity The change of characteristic, it is achieved the detection to reducibility gas.

MOS type gas sensor has the advantages such as corrosion-resistant, cost of manufacture is low, Cleaning Principle is simple, But, existing metal oxide semiconductor sensor based on CO gas detecting still has selectivity, less stable, response not Reach the problems such as the sensitiveest.

Embodiment one:

Embodiments herein relates to alarm based on CO gas detection function, and this alarm includes alarm device and CO Gas sensor；As it is shown in figure 1, described CO gas sensor includes Si substrate (01), is formed on described Si substrate (01) Silicon oxide film (02), the W film (03) being placed on described silicon oxide film (02), the WO that is formed on W film (03)₃Nano wire is thin Film (04), it is overlying on WO₃SnO on nano wire film (04)₂Nano thin-film (05), at SnO₂The two of the upper making of nano thin-film (05) Individual Pt electrode (06) and be positioned at the heating module (07) below described Si substrate；Described WO₃Nanowire length be 500～ 8000nm。

Preferably, the preparation method such as Fig. 2, CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 600nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 300nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.01wt%～ 0.1wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

Preferably, the test system of described CO sensor is made up of gas dilution system, electrochemical workstation, and it is right to realize The detection of minimum 1ppm gas, puts into test chamber the sample sensor made, and discharges chamber air, two electrodes and external electrical Chem workstation connects, and test voltage is 10V.Sensor response value is defined as: R=R0/Rg, wherein R0 be material in atmosphere Resistance, Rg is material resistance in certain concentration object gas, response time and recovery time is respectively response value and recovery Value reaches the time used during the 90% of balance.Found by test, CO concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 14,29,41,72, H2 concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 5,9,16,54, shows preferable CO selectivity；By the repeatability of 2000 times Test, under same concentrations CO, response value drops to original 93%, has good stability.

Test specification, this alarm is highly sensitive, repeated, have good stability, and has the biggest market application foreground.

Embodiment two:

Embodiments herein relates to alarm based on CO gas detection function, and this alarm includes alarm device and CO Gas sensor；As it is shown in figure 1, described CO gas sensor includes Si substrate (01), is formed on described Si substrate (01) Silicon oxide film (02), the W film (03) being placed on described silicon oxide film (02), the WO that is formed on W film (03)₃Nano wire is thin Film (04), it is overlying on WO₃SnO on nano wire film (04)₂Nano thin-film (05), at SnO₂The two of the upper making of nano thin-film (05) Individual Pt electrode (06) and be positioned at the heating module (07) below described Si substrate；Described WO₃Nanowire length be 500～ 7000nm。

Preferably, the preparation method such as Fig. 2, CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 900nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 300nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 3g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.01wt%～ 0.1wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

Preferably, the test system of described CO sensor is made up of gas dilution system, electrochemical workstation, and it is right to realize The detection of minimum 1ppm gas, puts into test chamber the sample sensor made, and discharges chamber air, two electrodes and external electrical Chem workstation connects, and test voltage is 10V.Sensor response value is defined as: R=R0/Rg, wherein R0 be material in atmosphere Resistance, Rg is material resistance in certain concentration object gas, response time and recovery time is respectively response value and recovery Value reaches the time used during the 90% of balance.Found by test, CO concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 14,29,41,72, H2 concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 5,9,16,45, shows preferable CO selectivity；By the repeatability of 2000 times Test, under same concentrations CO, response value drops to original 93%, has good stability.

Test specification, this alarm is highly sensitive, repeated, have good stability, and has the biggest market application foreground.

Embodiment three:

Embodiments herein relates to alarm based on CO gas detection function, and this alarm includes alarm device and CO Gas sensor；As it is shown in figure 1, described CO gas sensor includes Si substrate (01), is formed on described Si substrate (01) Silicon oxide film (02), the W film (03) being placed on described silicon oxide film (02), the WO that is formed on W film (03)₃Nano wire is thin Film (04), it is overlying on WO₃SnO on nano wire film (04)₂Nano thin-film (05), at SnO₂The two of the upper making of nano thin-film (05) Individual Pt electrode (06) and be positioned at the heating module (07) below described Si substrate；Described WO₃Nanowire length be 500～ 6000nm。

Preferably, the preparation method such as Fig. 2, CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 600nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 300nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.05wt%～ 0.5wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

Preferably, the test system of described CO sensor is made up of gas dilution system, electrochemical workstation, and it is right to realize The detection of minimum 1ppm gas, puts into test chamber the sample sensor made, and discharges chamber air, two electrodes and external electrical Chem workstation connects, and test voltage is 10V.Sensor response value is defined as: R=R0/Rg, wherein R0 be material in atmosphere Resistance, Rg is material resistance in certain concentration object gas, response time and recovery time is respectively response value and recovery Value reaches the time used during the 90% of balance.Found by test, CO concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 14,29,41,72, H2 concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 5,9,32,52, shows preferable CO selectivity；By the repeatability of 2000 times Test, under same concentrations CO, response value drops to original 93%, has good stability.

Test specification, this alarm is highly sensitive, repeated, have good stability, and has the biggest market application foreground.

Embodiment four:

Embodiments herein relates to alarm based on CO gas detection function, and this alarm includes alarm device and CO Gas sensor；As it is shown in figure 1, described CO gas sensor includes Si substrate (01), is formed on described Si substrate (01) Silicon oxide film (02), the W film (03) being placed on described silicon oxide film (02), the WO that is formed on W film (03)₃Nano wire is thin Film (04), it is overlying on WO₃SnO on nano wire film (04)₂Nano thin-film (05), at SnO₂The two of the upper making of nano thin-film (05) Individual Pt electrode (06) and be positioned at the heating module (07) below described Si substrate；Described WO₃Nanowire length be 500～ 5000nm。

Preferably, the preparation method such as Fig. 2, CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 600nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 600nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.51wt%～ 0.1wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

Preferably, the test system of described CO sensor is made up of gas dilution system, electrochemical workstation, and it is right to realize The detection of minimum 1ppm gas, puts into test chamber the sample sensor made, and discharges chamber air, two electrodes and external electrical Chem workstation connects, and test voltage is 10V.Sensor response value is defined as: R=R0/Rg, wherein R0 be material in atmosphere Resistance, Rg is material resistance in certain concentration object gas, response time and recovery time is respectively response value and recovery Value reaches the time used during the 90% of balance.Found by test, CO concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 14,29,41,72, H2 concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 5,9,25,38, shows preferable CO selectivity；By the repeatability of 2000 times Test, under same concentrations CO, response value drops to original 93%, has good stability.

Test specification, this alarm is highly sensitive, repeated, have good stability, and has the biggest market application foreground.

Embodiment five:

Embodiments herein relates to alarm based on CO gas detection function, and this alarm includes alarm device and CO Gas sensor；As it is shown in figure 1, described CO gas sensor includes Si substrate (01), is formed on described Si substrate (01) Silicon oxide film (02), the W film (03) being placed on described silicon oxide film (02), the WO that is formed on W film (03)₃Nano wire is thin Film (04), it is overlying on WO₃SnO on nano wire film (04)₂Nano thin-film (05), at SnO₂The two of the upper making of nano thin-film (05) Individual Pt electrode (06) and be positioned at the heating module (07) below described Si substrate；Described WO₃Nanowire length be 500～ 4000nm。

Preferably, the preparation method such as Fig. 2, CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Take the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, time ultrasonic Between be 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about at silicon chip surface The silicon oxide film of 600nm；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, then utilize Magnetron sputtering technique, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is The thickness of 300W, W film is 300nm, and size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge tube furnace In air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, be incubated complete allow its from So cooling, takes out silicon chip after dropping to room temperature, obtains one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g Fructus Citri Limoniae subsequently Acid, heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate, Precipitation stands 15h, removes removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, forms mixture precipitation, mixture precipitation is heated to 63 DEG C, adds back dissolving in saturated oxalic acid, until precipitation is the most molten Solve, obtain transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into 90 DEG C of baking oven dries 20h, obtains SnO₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is mixed Miscellaneous TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing to incite somebody to action SnO₂Slurry is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, is dried by silicon chip subsequently at 100 DEG C Dry 5min, at WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt Electrode；Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material be 0.01wt%～ 0.08wt%, described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.

Preferably, the test system of described CO sensor is made up of gas dilution system, electrochemical workstation, and it is right to realize The detection of minimum 1ppm gas, puts into test chamber the sample sensor made, and discharges chamber air, two electrodes and external electrical Chem workstation connects, and test voltage is 10V.Sensor response value is defined as: R=R0/Rg, wherein R0 be material in atmosphere Resistance, Rg is material resistance in certain concentration object gas, response time and recovery time is respectively response value and recovery Value reaches the time used during the 90% of balance.Found by test, CO concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 14,29,41,72, H2 concentration be respectively 200,500,1000, During 1500ppm, this sensor response value corresponds to 5,9,15,24, shows preferable CO selectivity；By the repeatability of 2000 times Test, under same concentrations CO, response value drops to original 93%, has good stability.

Test specification, this alarm is highly sensitive, repeated, have good stability, and has the biggest market application foreground.

Those skilled in the art, after considering description and putting into practice invention disclosed herein, will readily occur to its of the present invention Its embodiment.The application is intended to any modification, purposes or the adaptations of the present invention, these modification, purposes or Person's adaptations is followed the general principle of the present invention and includes the undocumented common knowledge in the art of the application Or conventional techniques means.Description and embodiments is considered only as exemplary, and true scope and spirit of the invention are by following Claim is pointed out.

It should be appreciated that the invention is not limited in precision architecture described above and illustrated in the accompanying drawings, and And various modifications and changes can carried out without departing from the scope.The scope of the present invention is only limited by appended claim.

Claims (2)

1. alarm based on CO gas detection function, this alarm includes alarm device and CO gas sensor；Described CO gas Body sensor include Si substrate, be formed at the suprabasil silicon oxide film of described Si, the W film that is placed on described silicon oxide film, It is formed at the WO on W film₃Nano wire film, it is overlying on WO₃SnO on nano wire film₂Nano thin-film, at SnO₂On nano thin-film Make two Pt electrodes and be positioned at the heating module below described Si substrate；Described WO₃Nanowire length be 500～ 8000nm。

Alarm the most according to claim 1, wherein, the preparation method of CO gas sensor comprises the steps:

Step one, preparation Si substrate:

Taking the silicon chip of certain size (5cm × 5cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning, ultrasonic time is equal For 30min, then silicon chip is being put in oxidation furnace, thermal oxide at 1100 DEG C, obtain a layer thickness about 600nm at silicon chip surface Silicon oxide film；

Step 2, prepares WO₃Nano wire film:

Silicon chip through step one thermal oxide is put in magnetic control sputtering device, is evacuated to 2.0 × 10^-3Hereinafter, magnetic control is then utilized Sputtering technology, plates one layer of W film at silicon oxide surface, using as WO₃The growth source of nano wire, magnetron sputtering power is 300W, W film Thickness be 300nm, size is 3cm × 3cm；

Then silicon chip is put in tube furnace, at ambient pressure, be passed through the Ar gas of 20sccm, first stablize 1h, discharge in tube furnace Air, following heated Tube-furnace to 380 DEG C, and is incubated 6h with the ramp of 10 DEG C/min, is incubated and complete makes it the coldest But, after dropping to room temperature, take out silicon chip, obtain one layer of WO on the W film surface of silicon chip₃Nano wire film；

Step 3, prepares SnO₂Nano thin-film:

First, prepare 100ml deionized water, weigh 5g SnCl₄·5H₂O is dissolved in deionized water, adds 0.3g citric acid subsequently, Heated solution to 53 DEG C, under magnetic stirring, ammonia to the pH value adding 0.5mol/L is 3, prepares Sn (OH)₄Precipitate is heavy Form sediment and stand 15h, remove removing chloride through repeatedly washing；Then 7g TiO is weighed₂Nanoparticle, with precipitation mixed grinding 0.5h, Form mixture precipitation, mixture precipitation is heated to 63 DEG C, add back dissolving in saturated oxalic acid, until precipitation is completely dissolved, To transparent SnO₂Colloidal sol, joins saturated for 10ml Polyethylene Glycol in vitreosol as surfactant, and puts into baking oven Dry 20h, obtain SnO for 90 DEG C₂Gel Precursor, by this SnO₂Gel Precursor is roasting 1.5h at 580 DEG C, is adulterated TiO₂The SnO of nanoparticle₂Nanometer powder；

Use terpineol and SnO₂Nanometer powder mixes, and preparation becomes SnO₂Slurry, and use the method for silk screen printing by SnO₂Slurry Material is coated in the WO of silicon chip₃Nano wire film region, SnO₂Slurry thickness is 2 μm, and silicon chip is dried at 100 DEG C 5min subsequently, At WO₃One layer of SnO of nano wire film area filling₂Nano thin-film；

Step 4, preparation pt electrode:

This sensor electrode uses Pt electrode, utilizes magnetron sputtering to combine template at SnO₂Pulp surface makes two Pt electrodes； Described Pt electrode is added with Bi₂O₃Material and MgB₂Material, described Bi₂O₃The addition of material is 0.01wt%～0.1wt%, Described MgB₂The addition of material is 0.005wt%～0.05wt%.

Step 5, assembling CO gas sensor:

Wire and two Pt electrodes are connected, at Si backside of substrate, heating module and the shell mechanism of sensor is installed.