CN106093138B - Pass through the manufacturing method and sensor of the sensor of metal oxide detection gas - Google Patents

Pass through the manufacturing method and sensor of the sensor of metal oxide detection gas Download PDF

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CN106093138B
CN106093138B CN201610453753.7A CN201610453753A CN106093138B CN 106093138 B CN106093138 B CN 106093138B CN 201610453753 A CN201610453753 A CN 201610453753A CN 106093138 B CN106093138 B CN 106093138B
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film layer
metal film
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CN106093138A (en
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赖建文
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Shanghai Shenxiling Microelectronics Technology Co Ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12Investigating 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
    • G01N27/128Microapparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00206Processes for functionalising a surface, e.g. provide the surface with specific mechanical, chemical or biological properties

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Abstract

The manufacturing method and sensor of a kind of sensor by metal oxide detection gas provided by the invention, include the following steps:Include the following steps:In silicon chip substrate the first silicon oxide film layer is deposited with plasma enhanced chemical vapor deposition method;Dry etching is carried out to the first metal film layer, adding thermal resistance layer pattern is carved on the first metal film layer;Third metal film layer is deposited with physical vaporous deposition on the second metal film layer, and photoetching and dry etching are carried out to third metal film layer;It is located at the second silicon oxide film layer corresponding with the second contact hole below the second contact hole using dry or wet etch;On a photoresist and in the second contact hole metallic oxide film is deposited with physical vaporous deposition.Beneficial effects of the present invention are as follows:The ingredient and concentration of environmental gas can accurately be detected.Therefore manufacturing cost can be reduced, reduces the volume and power consumption of product, increased reliability and consistency, improve sensitivity and the precision of product.

Description

Pass through the manufacturing method and sensor of the sensor of metal oxide detection gas
Technical field
The present invention relates to a kind of manufacturing methods of sensor, especially a kind of to detect gas by PULSE HEATING metal oxide The manufacturing method of the sensor of body and the sensor manufactured using this method.
Background technology
The quality of environment and people’s lives and work comfort degree, health are closely bound up.In recent years, as people are to ring The requirement in border is higher and higher, simple and reliable it is desirable to have, the quality of cheap method and product testing surrounding air, Such as carbon monoxide, imflammable gas, ethyl alcohol, the aerial content of discomfort or toxic gas of NO2 etc..But it is traditional Gas sensor, volume is larger, and power consumption is higher, and cost is higher, and reliability and consistency are poor, it is difficult in popular market such as hand It is promoted on machine, housed device and wearable device.It is related when being studied more with the sensor of metal oxide detection gas Patent also have application and authorize.However, it is possible to be accepted by the public seldom with widely applied product, such as in mobile phone, household is set It is promoted on standby and wearable device and is difficult to realize.There are two its reasons:One is that some sensors are manufactured with thick-film technique Metal-oxide gas transducer, complex process, consistency is poor, and volume is larger, and cost is higher.Another reason is some sensings Device is manufactured with unconventional semiconductor fabrication process such as MEMS technology, and complex process is of high cost, and consistency and reliability are poor.
Such as the patent application of application number 200710054450.9, it is that metal oxide is made of thick-film technique about one The manufacturing method of sensor on potsherd, the disadvantage is that volume is big, power consumption is high, it is difficult to produces in enormous quantities, it is of high cost, unanimously Property and poor repeatability.
The for another example patent application of application number CN201410397034.9 is to manufacture metal with the technique of MEMS about one The manufacturing method of oxide sensor.The disadvantage is that its MEMS technology used is non-standard semiconductor technology, technology difficulty is big, Consistency and poor reliability, cost are higher, it is difficult to for producing in enormous quantities.
Invention content
For the defects in the prior art, the object of the present invention is to provide a kind of volume and power consumption reducing product, increase Reliability and consistency improve the system of the measurement sensitivity of product and the sensor by metal oxide detection gas of precision Make method and sensor.
In order to solve the above technical problems, the present invention provides a kind of manufacture of the sensor by metal oxide detection gas Method includes the following steps:
Step 1, in silicon chip substrate the first silicon oxide film layer is deposited with plasma enhanced chemical vapor deposition method;
Step 2, on the first silicon oxide film layer the first metal film layer is deposited using physical vaporous deposition;
Step 3, dry etching is carried out to the first metal film layer, heating resistor layer figure is carved on the first metal film layer Shape;
Step 4, using plasma enhanced chemical vapor deposition method on the first metal film layer deposition silicon nitride film Layer, and output on silicon nitride film layer the first contact hole through silicon nitride film;
Step 5, the second metal film layer is deposited with physical vaporous deposition on silicon nitride film layer, in the first contact hole Interior filling contact, contact connects the first metal film layer and the second metal film layer, and is carried out to the second metal film layer Photoetching and dry etching;
Step 6, third metal film layer is deposited with physical vaporous deposition on the second metal film layer, and to third Metal film layer carries out photoetching and dry etching;
Step 7, it is thin that the second silica is deposited on third metal film layer with plasma enhanced chemical vapor deposition method Film layer;
Step 8, the coating photoresist on the second silicon oxide film layer, and second through photoresist is outputed on a photoresist Contact hole;
Step 9, it is located at the second oxidation corresponding with the second contact hole below the second contact hole using dry or wet etch Silicon membrane layer;
Step 10, metallic oxide film is deposited with physical vaporous deposition on a photoresist and in the second contact hole;
Step 11, photoresist is removed;
Step 12, vacuum bakeout is carried out to entire device;
Step 13, photoetching is carried out to the second silicon oxide film layer, is outputed on silica membrane layer through the second oxidation The third contact hole of silicon membrane layer;
Step 14, one end of connecting line is stretched into third contact hole, and one end of connecting line is connect with third metal film layer.
Preferably, the thickness of the first silicon oxide film layer is 200 nanometers~2 microns.
Preferably, the thickness of the first metal film layer is 200 nanometers~1 micron, and the material of the first metal film layer is gold Belong to tungsten or tungsten-titanium alloy.
Preferably, the thickness of silicon nitride film layer is 10 nanometers~200 nanometers.
Preferably, the thickness of the second metal film layer is 100 nanometers~1 micron, and the material of the second metal film layer is gold Belong to tungsten or tungsten-titanium alloy.
Preferably, the thickness of third metal film layer is 200 nanometers~3 microns, and the material of third metal film layer is gold Belong to tungsten or tungsten-titanium alloy.
Preferably, the thickness of the second silicon oxide film layer is 100 nanometers~500 nanometers.
Preferably, the thickness of metallic oxide film is 100 nanometers~800 nanometers.
Preferably, the temperature of baking is 300 DEG C~500 DEG C, and the time of baking is 10 minutes~4 hours.
A kind of sensor, the sensor use manufacturer's legal system of the sensor by metal oxide detection gas It makes.
Compared with prior art, beneficial effects of the present invention are as follows:It can be the film heating resistance of nanometer scale, film Heat sink and thin-film metallic oxide gas sensing resistance are made on silicon chip simultaneously, quick by the pulse for being applied to heating film resistor Metal oxide gas sensing resistance near heating, encourages the resistance of the oxide to change, then fast further through heat dissipation film The quickly cooling but resistance makes resistance value restore initial value, forms resistance value pulse signal.The shape of the resistance value pulse signal, amplitude, Response characteristic is influenced by its environmental gas.The ingredient and concentration of environmental gas can accurately be detected.The method uses integrated electricity Standard technology in the manufacture of road avoids using unconventional MEMS technology, therefore can reduce manufacturing cost, reduces the body of product Product and power consumption increase reliability and consistency, improve sensitivity and the precision of product.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature mesh of the invention And advantage will become more apparent upon.
Fig. 1 is manufacturing method schematic diagram one of the present invention by the sensor of metal oxide detection gas;
Fig. 2 is manufacturing method schematic diagram two of the present invention by the sensor of metal oxide detection gas;
Fig. 3 is manufacturing method schematic diagram three of the present invention by the sensor of metal oxide detection gas;
Fig. 4 is manufacturing method schematic diagram four of the present invention by the sensor of metal oxide detection gas;
Fig. 5 is manufacturing method schematic diagram five of the present invention by the sensor of metal oxide detection gas;
Fig. 6 is manufacturing method schematic diagram six of the present invention by the sensor of metal oxide detection gas;
Fig. 7 is manufacturing method schematic diagram seven of the present invention by the sensor of metal oxide detection gas;
Fig. 8 is manufacturing method schematic diagram eight of the present invention by the sensor of metal oxide detection gas;
Fig. 9 is manufacturing method schematic diagram nine of the present invention by the sensor of metal oxide detection gas;
Figure 10 is manufacturing method schematic diagram ten of the present invention by the sensor of metal oxide detection gas;
Figure 11 is manufacturing method schematic diagram ten one of the present invention by the sensor of metal oxide detection gas;
Figure 12 is manufacturing method schematic diagram ten two of the present invention by the sensor of metal oxide detection gas;
Figure 13 is structural schematic diagram one of the present invention by the sensor of metal oxide detection gas;
Figure 14 is structural schematic diagram two of the present invention by the sensor of metal oxide detection gas;
Figure 15 is structural schematic diagram three of the present invention by the sensor of metal oxide detection gas;
Figure 16 is schematic diagram of the present invention by the sensor of metal oxide detection gas;
Figure 17 is signal graph of the present invention by the sensor of metal oxide detection gas.
In figure:
1- silicon chips 2- the first silicon oxide film layer the first metal film layers of 3-
4- silicon nitride film layers 5- the second metal film layer 6- third metal film layers
7- the first contact hole 8- third layer metallic pattern 9- second layer metal figures
10- the second silicon oxide film layer 11- photoresists the second contact holes of 12-
13- metallic oxide film 14- third contact hole 15- connecting lines
16- contacts
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention Protection domain.
Step 1:Can be 6 inches, 8 inches or 12 inch silicon wafers 1, Ke Yishi using the industrial silicon chip 1 of standard semiconductor P-shaped can also be N shapes.
Step 2:The first silicon oxide film layer 2 is deposited with the method for the semiconductor technology PECVD of standard, thickness is received 200 Rice is between 2 microns.
Step 3:On the first silicon oxide film layer 2 the first metallic film is deposited with the method for standard semi-conductor processes PVD Layer 3, for thickness between 200 nanometers to 1 micron, material can be tungsten or tungsten-titanium alloy or other refractory metals.
Step 4:Do first time photoetching.
Step 5:First time dry etching is done, the first metal film layer 3 is carved adding thermal resistance layer pattern.This figure is in electricity It can be strip to hinder region or heating region, can also be simple single shape.First metal film layer 3 is in non-resistive region Or non-heated region area is larger, and with the second metal film layer of top layer 5, third metal film layer 6 connects, and plays heat dissipation work( Energy.When heating driving pulse application, resistance region resistance is larger to be brought rapidly up.After heating driving pulse disappearance, heat is logical The metal for crossing peripheral non-resistive region distributes rapidly, and temperature is made to restore room temperature as early as possible.
Step 6:One layer of silicon nitride film layer 4 is deposited on the first metal film layer 3 with standard PECVD process, thickness exists Between 10 nanometers to 200 nanometers.The thickness of this film is thin enough, enhances heating effect.
Step 7:Do second of photoetching.
Step 8:With standard semiconductor dry etching silicon nitride film layer 4, the first contact hole 7 is outputed.First contact hole 7 Following.First metal film layer 3 is exposed.
Step 9:Deposit the second metal film layer 5 with the method for PVD on silicon nitride film layer 4, thickness at 100 nanometers extremely Between 1 micron, in the place for having the first contact hole 7, contact 16 fill the first contact hole 7, and with the first metal of its bottom Film layer 3 connects, and the material of the second metal film layer 5 and contact 16 can be tungsten or tungsten-titanium alloy or other resistance to height Warm metal.
Step 10:It is thick with standard semiconductor PVD process deposit third metal film layer 6 on the second metal film layer 5 For degree between 200 nanometers to 3 microns, material can be metallic aluminium or aluminium copper.The third metal film layer 6 is completely covered The second following metal film layer 5, and the second metal film layer 5 is connected in electricity meaning.When applying heating pumping signal, Second metal film layer 5, third metal film layer 6 play the role of low-resistance line so that and adding thermal resistance obtains most of energy, And it is rapidly heated.
Step 11:Do third time photoetching.
Step 12:With standard semiconductor dry etching, third metal film layer 6 is etched third layer metallic pattern 8, is carved Erosion stops on the second metal film layer 5.So etching needs have preferable selectivity to the second metal film layer 5.
Step 13:Do four mask.
Step 14:With standard semiconductor dry etching, the second metal film layer 5 is etched second layer metal figure 9, is carved Erosion stops on silicon nitride film layer 4.Portion of second layer metal 5 and whole third layer metals 6 expose.Second layer metal figure Shape 9 can be interdigitated, can also be simple figure.Left and right side figure is not connected to, will be respectively as subsequent metal oxide The two end electrodes of resistance.
Step 15:It is deposited on the second metal film layer 5 and third metal film layer 6 with standard semiconductor PECVD methods Second silicon oxide film layer 10, thickness is between 50 nanometers to 500 nanometers.Third is completely covered in this second silicon oxide film layer 10 Metal film layer 6 prevents from improving the reliability of device by environmental attack in the application of metal afterwards as passivation protection layer.
Step 16:Coating photoresist 11 does the 5th photoetching, makes the second contact hole 12.
Step 17:Using standard semiconductor dry or wet technique, the second silica etched under the second contact hole 12 is thin Film layer 10 is prepared for the deposit of subsequent metal oxide and stripping technology.11 thickness of photoresist 500 nanometers to 2 microns it Between.Etching stopping is on silicon nitride film layer 4.
Step 18:Metallic oxide film 13 is deposited with the method for PVD on photoresist 11, thickness is at 100 nanometers To between 800 nanometers, material can be SnO2, ZnO, TiO2Equal gas sensitives, or pass through Fe, Zn, Pt, the elements such as Pd mix Such gas sensitive.
Step 19 removes photoresist 11 using solvent, and the covering of gas-sensitive metal oxide film layer 13 second stayed connects Contact hole 12, forms a gas sensing resistance, and the both ends of gas sensing resistance connect the two poles of the earth of the second metal film layer 5, are then connected to Third metal film layer 6.
Step 20:Vacuum bakeout is done at a certain temperature, and the crystallization of metallic oxide film 13 is made to form required stablize The gas sensing resistance of characteristic.For baking temperature between 300 DEG C to 500 DEG C, the time is between 10 minutes to 4 hours.During baking, the Protection of three metal film layers 6 by the second silicon oxide film layer 10.
Step 21:Do the 6th photoetching.
Step 22:With the second silicon oxide film layer of standard semiconductor dry etching 10, third contact hole 14 is obtained, third gold Belong to film layer 6 to be exposed.Third contact hole 14 corresponds to two electrodes of two electrodes and metal heating thin films of gas sensing resistance.
Step 23:It is with the standard metal copper of semiconductor-sealing-purpose or the connecting line 15 of gold solder that the both ends of gas sensing resistance are electric The two end electrodes of pole and micro metal adding thermal resistance are connected in encapsulation, and entire four end sensor device is completed.
Rh is equivalent adding thermal resistance, and Rg is equivalent gas sensing resistance.This structure is as the upper outer connecting resistance R appropriate of connection and fits When supply voltage Vdd after, the resistance value of output voltage Vg reflection gas sensing resistance.Vh is applied to the pulse voltage of adding thermal resistance Signal.Vh is as a pumping signal, and when applying a short pulse, adding thermal resistance is generated heat rapidly.On it because of gas sensing resistance Face, centre is only separated by very thin silicon nitride film layer 4, therefore gas sensing resistance also follows heating.As temperature increases, it is adsorbed on gas The negative oxygen ion on sensitized metal oxide resistor surface increases sharply, and oxide surface formed depletion layer, make its resistivity with Temperature rise and rise.After the driving voltage pulse for heating metallic resistance disappears, temperature declines, and the negative oxygen ion of absorption subtracts Few, the resistivity of gas-sensitive metal oxide restores initial value.Therefore, Vh may be considered driving source, Vg (Rg) pulse in response. When fixing the amplitude of pumping signal and time, if air is pure without other pernicious gases, the amplitude of this response impulse It is fixed with shape.The figure referred to such as the A in Figure 17.
But when containing a certain amount of reducibility gas in air, such as CO, H2With other volatile organic matter gases Such as ethyl alcohol, negative oxygen ion lower in the adsorption capacity of gas-sensitive metal oxide, and depletion layer is reduced so that gas sensing resistance is with temperature The amplitude of rising is reduced, and the peak value of response signal Vg (Rg) becomes smaller, and the shape of signal changes.As the B in Figure 17 is referred to Figure.
On the contrary, when containing a certain amount of oxidizing gas in air, such as NO2, negative oxygen ion is in gas-sensitive metal oxide Adsorption capacity enhancing, depletion layer increase so that gas sensing resistance also increases with the amplitude of temperature rise, response signal Vg's (Rg) Peak value becomes larger, and signal shape changes.The figure referred to such as the C in Figure 17.
By the variation of the method analysis response signal Vg (Rg) with software, the signal of pure air is compared, it can be accurate Detect the ingredient and concentration of environmental gas.
In addition, adding thermal resistance is larger in non-heated region area, cooling effect can be played.When heating pulse disappear with Afterwards, the heat of adding thermal resistance is distributed rapidly by the metal in non-heated region so that and the temperature of gas sensing resistance comparatively fast restores room temperature, Then second of pulse excitation can be carried out.By the test of multiple Challenge-response, gained information can eliminate noise, improve The precision and consistency of measurement.
The present invention also provides a kind of manufacturing method manufactures using the sensor by metal oxide detection gas Sensor.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make a variety of changes or change within the scope of the claims, this not shadow Ring the substantive content of the present invention.In the absence of conflict, the feature in embodiments herein and embodiment can arbitrary phase Mutually combination.

Claims (10)

1. a kind of manufacturing method of sensor by metal oxide detection gas, includes the following steps:
Step 1, in silicon chip substrate the first silicon oxide film layer is deposited with plasma enhanced chemical vapor deposition method;
It is characterized in that, further including:
Step 2, on the first silicon oxide film layer the first metal film layer is deposited using physical vaporous deposition;
Step 3, dry etching is carried out to the first metal film layer, adding thermal resistance layer pattern is carved on the first metal film layer;
Step 4, using plasma enhanced chemical vapor deposition method on the first metal film layer deposition silicon nitride film layer, and The first contact hole through silicon nitride film is outputed on silicon nitride film layer;
Step 5, the second metal film layer is deposited with physical vaporous deposition on silicon nitride film layer, is filled out in the first contact hole Contact is filled, contact connects the first metal film layer and the second metal film layer, and carries out photoetching to the second metal film layer And dry etching;
Step 6, third metal film layer is deposited with physical vaporous deposition on the second metal film layer, and to third metal Film layer carries out photoetching and dry etching;
Step 7, the second silicon oxide film layer is deposited on third metal film layer with plasma enhanced chemical vapor deposition method;
Step 8, the coating photoresist on the second silicon oxide film layer, and the second contact through photoresist is outputed on a photoresist Hole;
Step 9, to be located at the second silica corresponding with the second contact hole below the second contact hole using dry or wet etch thin Film layer;
Step 10, metallic oxide film is deposited with physical vaporous deposition on a photoresist and in the second contact hole;
Step 11, photoresist is removed;
Step 12, vacuum bakeout is carried out to entire device;
Step 13, photoetching is carried out to the second silicon oxide film layer, is outputed on silica membrane layer thin through the second silica The third contact hole of film layer;
Step 14, one end of connecting line is stretched into third contact hole, and one end of connecting line is connect with third metal film layer.
2. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of first silicon oxide film layer is 200 nanometers~2 microns.
3. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of first metal film layer is 200 nanometers~1 micron, and the material of the first metal film layer is tungsten or tungsten-titanium alloy.
4. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of silicon nitride film layer is 10 nanometers~200 nanometers.
5. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of second metal film layer is 100 nanometers~1 micron, and the material of the second metal film layer is tungsten or tungsten-titanium alloy.
6. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of third metal film layer is 200 nanometers~3 microns, and the material of third metal film layer is tungsten or tungsten-titanium alloy.
7. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of second silicon oxide film layer is 100 nanometers~500 nanometers.
8. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The thickness of metallic oxide film is 100 nanometers~800 nanometers.
9. the manufacturing method of the sensor according to claim 1 by metal oxide detection gas, which is characterized in that The temperature of baking is 300 DEG C~500 DEG C, and the time of baking is 10 minutes~4 hours.
10. a kind of sensor, which is characterized in that the sensor passes through metal using described in claim 1 to 9 any one The manufacturing method of the sensor of oxide detection gas manufactures.
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