CN102176365A - Method for manufacturing piezoresistor thick film - Google Patents
Method for manufacturing piezoresistor thick film Download PDFInfo
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- CN102176365A CN102176365A CN 201110051455 CN201110051455A CN102176365A CN 102176365 A CN102176365 A CN 102176365A CN 201110051455 CN201110051455 CN 201110051455 CN 201110051455 A CN201110051455 A CN 201110051455A CN 102176365 A CN102176365 A CN 102176365A
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Abstract
The invention relates to a method for manufacturing a piezoresistor thick film used for high voltage electrostatic discharge protection, belonging to the technical field of piezoresistor material manufacture. The method comprises the following steps of: mixing a rare earth oxide Y2O3 with traditional ZnO voltage-sensitive material hexabasic-formula power; performing high-energy ball milling to obtain resistor slurry with a certain viscosity; and performing screen printing and low-temperature sintering to finally obtain the piezoresistor thick film with high voltage electrostatic discharge protection property. After being connected with a circuit to be protected, the piezoresistor thick film can inhibit transient overvoltage in the circuit, thereby reducing the damage of high voltage electrostatic discharge to the circuit; in addition, the piezoresistor thick film also can be used for the forestage voltage stabilization of a high voltage circuit and the reference voltage output of a high voltage power supply. The method has the advantages of simple process and good repeatability; and the prepared piezoresistor thick film product has higher voltage-sensitive voltage value and can meet the application requirement for high voltage electrostatic discharge protection.
Description
Technical field
The present invention relates to a kind of preparation method of piezo-resistance thick film, relate in particular to a kind of preparation method who is used for the piezo-resistance thick film of high-pressure electrostatic discharge prevention.
Background technology
Along with the high speed development of microelectric technique, computer technology, with the integrated circuit (IC)-components every field that various measurements, protection, supervisory circuit and computer network, the communication system of core has been widely used in the industries such as national defence, Aeronautics and Astronautics, finance, post and telecommunications, electric power, meteorology, petrochemical industry and the modern life.The components and parts integrated level of this class of electronic devices is more and more higher, and information storage is increasing, and speed and precision improve constantly, thereby disturbs sensitivity especially to external world, and is lower to superpotential tolerances such as thunder and lightning and static discharges.When this class overvoltage surpasses a certain threshold value, gently then cause system's misoperation, heavy then cause equipment or other components and parts permanent damage.
Static discharge is very common in daily life, because its phenomenon is faint, people almost do not perceive during generation, but may be fatal for electronic equipment.(as the inner electrostatic discharge (ESD) protection level of typical product is 1000～2000V) although our the daily electronic product its internal circuit that touches all is equipped with electrostatic discharge (ESD) protection measure on the sheet of certain grade; but owing to be subjected to the restriction in space on the sheet; it is too big that these protective circuits can not be done, therefore very limited to the protective capability of static discharge.Yet the static discharge voltage peak value that electronic product in use produces can rise to several thousand and even volt up to ten thousand in a short period of time, this head and shoulders above the scope of on-chip protection.According to Japanese parties concerned statistics, the damage of electronic component has 50% to be that static discharge causes; ESDA shows that to the assessment of the electronic product source of damage about 27～33% damage is caused by static discharge; The loss that China's communications industry every year is caused by static discharge is up to several hundred million yuans.This shows that the electrostatic discharge (ESD) protection measure is very necessary to the loss that minimizing high-pressure electrostatic discharge harm causes outside the sheet that introducing is assisted in electronic product.
Piezo-resistance is a kind of semiconductor ceramic material, because of its good electricity non-linear and preferably the surge absorbability be widely used in the power electronic system as voltage stabilizing element and over-voltage protection element.Because static discharge also is a kind of transient overvoltage surge, piezo-resistance naturally becomes the main candidate material of electric static discharge protector.Along with electronic product develops to miniature, light weight, multi-functional and highly reliable direction day by day, an urgent demand piezo-resistance is developed to novel small size membrane type by traditional large volume chip.The piezo-resistance thick film that is used for the high-pressure electrostatic discharge prevention has because of it that volume is little, pressure sensitive voltage is high and advantage such as suitable surface mounting technology is subjected to people and more and more pays close attention to, and becomes the first-selected element of novel electron product high-pressure electrostatic discharge prevention.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of piezo-resistance thick film.
A kind of preparation method of piezo-resistance thick film, after comprising the steps: to comprise the micron raw material mixing of yttria, adopt the method wet-milling of high-energy ball milling, then the mixed powder behind the ball milling is dried, adopt the method dry grinding of high-energy ball milling again, the dry powder of the nanoscale that obtains mixing; Join the dry powder of described nanoscale in the organic carrier and size mixing, obtain the piezo-resistance slurry; In the potsherd substrate, adopt the mode of silk screen printing to form hearth electrode, adopt the silk screen web plate that described piezo-resistance slurry substep repeatedly is printed on the described hearth electrode again, be completed for printing the back oven dry at every turn, form the thick film varistor layer, on described thick film varistor layer, adopt the mode of silk screen printing to form top electrode then; Resistance furnace is put in the substrate that will have described hearth electrode, described thick film varistor layer and described top electrode, carries out low-temperature sintering under 700～800 ℃ of conditions; On described hearth electrode and described top electrode end face, form electrode outlet line.
The preferred a kind of technical scheme of the present invention, described micron raw material is the mixture of zinc oxide, bismuth oxide, antimonous oxide, chrome green, cobalt sesquioxide, manganese dioxide, yttria, and the mol ratio of described zinc oxide, bismuth oxide, antimonous oxide, chrome green, cobalt sesquioxide, manganese dioxide, yttria is 96.42: 0.7: 1.0: 0.5: 0.8: 0.5: 0.08.
The preferred a kind of technical scheme of the present invention when adopting the high energy ball mill method wet-milling, adds the 15ml absolute ethyl alcohol, wet-milling 5～10 hours, and wherein, the scope of ratio of grinding media to material is 10～40: 1, the rotational speed of ball-mill scope is 300～600rpm.
The preferred a kind of technical scheme of the present invention when adopting the high energy ball mill method dry grinding, was dry grinded 1～2 hour, and wherein, the scope of ratio of grinding media to material is 10～40: 1, and the rotational speed of ball-mill scope is 300～600rpm.
The preferred a kind of technical scheme of the present invention, described organic carrier are 2～10% organic carrier for the concentration that ethyl cellulose is dissolved in terpinol preparation formation.
The preferred a kind of technical scheme of the present invention joins the dry powder of described nanoscale in the described organic carrier and in the step of sizing mixing, the mass ratio of dry powder of described nanoscale and described organic carrier is 1: (0.5～2).
The preferred a kind of technical scheme of the present invention, described substrate is the alumina ceramic plate substrate, the mode that adopts the silk screen printing conductive silver paste and dry under 100 ℃ temperature forms described hearth electrode and described top electrode.
The preferred a kind of technical scheme of the present invention, adopt the silk screen web plate of 6～60 μ m, divided for 2～10 steps with described piezo-resistance slurry, per step mode of 2～5 times is printed on the described hearth electrode, under 100 ℃ temperature, dry after each brush system is finished, form described thick film varistor layer.
The preferred a kind of technical scheme of the present invention, in described low sintering step, described resistance furnace is put in the substrate that will have described hearth electrode, described thick film varistor layer and described top electrode, is warming up to 700～800 ℃ gradually, is incubated and is cooled to room temperature with stove after 0.5～2 hour.
The preferred a kind of technical scheme of the present invention in the step that forms electrode outlet line, adopts the gluing system electrode outlet line of normal temperature quick-drying conductive silver on described hearth electrode and described top electrode end face.
The preferred a kind of technical scheme of the present invention, the wet-milling time is 5 hours, and ratio of grinding media to material is 40: 1, and rotational speed of ball-mill is 600rpm, and the dry grinding time is 2 hours, and ratio of grinding media to material is 40: 1, and rotational speed of ball-mill is 600rpm; The concentration of organic carrier is 2%, and the mass ratio of dry powder and organic carrier is 1: 0.5; The thickness of silk screen web plate is 60 μ m, and the silk screen printing step number was 10 steps, and per step divides 2 times; Slowly be warming up to 700 ℃, be incubated 2 hours.
The preferred a kind of technical scheme of the present invention, the wet-milling time is 5 hours, and ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm, and the dry grinding time is 2 hours, and ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm; The concentration of organic carrier is 5%, and the mass ratio of dry powder and organic carrier is 1: 1; The thickness of silk screen web plate is 30 μ m, and the silk screen printing step number was 6 steps, and per step divides 3 times; Slowly be warming up to 750 ℃, be incubated 1.5 hours.
The preferred a kind of technical scheme of the present invention, the wet-milling time is 10 hours, and ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm, and the dry grinding time is 1 hour, and ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm; The concentration of organic carrier is 5%, and the mass ratio of dry powder and organic carrier is 1: 1.5; The thickness of silk screen web plate is 10 μ m, and the silk screen printing step number was 4 steps, and per step divides 4 times; Slowly be warming up to 750 ℃, be incubated 1 hour.
Invent preferred a kind of technical scheme, the wet-milling time is 10 hours, and ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 300rpm, and the dry grinding time is 1 hour, and ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 300rpm; The concentration of organic carrier is 10%, and the mass ratio of dry powder and organic carrier is 1: 2; The thickness of silk screen web plate is 6 μ m, and the silk screen printing step number was 2 steps, and per step divides 5 times; Slowly be warming up to 800 ℃, be incubated 0.5 hour.
Compared with prior art, the preparation method of piezo-resistance thick film of the present invention improves the pressure sensitive voltage value of piezo-resistance thick film by rare-earth metal doped oxide yttria in the micron order raw material.Grind the micron order raw material by the employing high-energy ball-milling process, thus the dry powder of the nanoscale that acquisition mixes, particle is tiny.In filming technology, use silk screen print method, and repeatedly coating of substep, to prevent the film face checking and to guarantee the repeatability of technology.Under 700～800 ℃ of conditions, carry out low-temperature sintering, suppress too growing up and the volatilization of bismuth oxide of crystal grain, obtain the high voltage varistor thick film.Preparation method's technology of piezo-resistance thick film of the present invention is simple relatively, easy operating, and lower to equipment and cost requirement, the pressure sensitive voltage value and the high voltage protective level of the piezo-resistance thick film of gained meet and exceed the result that other method obtains.
Description of drawings
Fig. 1 is the preparation method's of a piezo-resistance thick film of the present invention flow chart.
Optical microstructure's photo after the piezo-resistance thick film that Fig. 2 prepares for the preparation method who adopts piezo-resistance thick film of the present invention corrodes.
The circuit theory diagrams that Fig. 3 carries out Hi-pot test for the piezo-resistance thick film that the preparation method who adopts piezo-resistance thick film of the present invention is prepared.
Fig. 4 is the high voltage stabilizing curve of the piezo-resistance thick film of preparation method's preparation of employing piezo-resistance thick film of the present invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing.
See also Fig. 1, Fig. 1 is the preparation method's of a piezo-resistance thick film of the present invention flow chart.The preparation method of piezo-resistance thick film of the present invention comprises the steps
(1) high-energy ball milling
With the micron order raw material: zinc oxide ZnO, bismuth oxide Bi
2O
3, antimonous oxide Sb
2O
3, chrome green Cr
2O
3, cobalt sesquioxide Co
2O
3, manganese dioxide MnO
2, yttria Y
2O
3, according to mol ratio ZnO: Bi
2O
3: Sb
2O
3: Cr
2O
3: Co
2O
3: MnO
2: Y
2O
3=96.42: 0.7: 1.0: 0.5: after the mixing in 0.8: 0.5: 0.08, add the 15ml absolute ethyl alcohol, wet-milling 5～10 hours.Wherein, in the wet-milling process, ratio of grinding media to material is 10～40: 1, and rotational speed of ball-mill is 300～600rpm.With the mixed powder oven dry, under above-mentioned identical ball milling condition, dry grinded 1～2 hour the dry powder of the nanoscale that obtains mixing after the wet-milling again.
(2) preparation slurry
Ethyl cellulose is dissolved in terpinol, and to be mixed with concentration be 2～10% organic carrier, the dry powder that (1) step of weighing obtains, by dry powder: organic carrier=1: the mass ratio of (0.5～2) joins in the organic carrier and sizes mixing, and obtains having the piezo-resistance slurry of certain viscosity.
(3) silk screen printing
At Al
2O
3Silk screen printing conductive silver paste in the potsherd substrate is dried under 100 ℃ temperature, forms hearth electrode.Adopt the silk screen web plate of 6～60 μ m, the piezo-resistance slurry that (2) step was prepared divided for 2～10 steps, and per step mode of 2～5 times is printed on the hearth electrode, after each brush system is finished sample was dried under 100 ℃ temperature, formed the thick film varistor layer.At silk screen printing conductive silver paste on the thick film varistor layer and under 100 ℃ temperature, dry, form top electrode.
(4) low-temperature sintering
To put into the digit-control resistance stove through the substrate after (3) the step brush system, slowly be warming up to 700～800 ℃, and be incubated and be cooled to room temperature with stove after 0.5～2 hour, obtain the semi-finished product of sinter molding.
(5) sticking system electrode
On the end face of (4) the half-finished hearth electrode that obtains of step and top electrode, with the gluing system electrode outlet line of normal temperature quick-drying conductive silver, left standstill under the room temperature 0.5 hour, obtain being used for the piezo-resistance thick film of high-pressure electrostatic discharge prevention, as shown in Figure 2.
Provide embodiment 1 to embodiment 4 to further specify the preparation method of piezo-resistance thick film of the present invention below.The specific compound that uses among the embodiment, method and condition are as illustration of the present invention and also unrestricted the present invention.
Embodiment 1:
With the micron order raw material: zinc oxide ZnO, bismuth oxide Bi
2O
3, antimonous oxide Sb
2O
3, chrome green Cr
2O
3, cobalt sesquioxide Co
2O
3, manganese dioxide MnO
2, yttria Y
2O
3, according to mol ratio ZnO: Bi
2O
3: Sb
2O
3: Cr
2O
3: Co
2O
3: MnO
2: Y
2O
3=96.42: 0.7: 1.0: 0.5: after the mixing in 0.8: 0.5: 0.08, add the 15ml absolute ethyl alcohol, wet-milling 5 hours.Wherein, ratio of grinding media to material is 40: 1, and rotational speed of ball-mill is 600rpm.With the mixed powder oven dry, under above-mentioned identical ball milling condition, dry grinded 2 hours the dry powder of the nanoscale that obtains mixing after the wet-milling again.
Ethyl cellulose is dissolved in terpinol, and to be mixed with concentration be 2% organic carrier, the dry powder that weighing obtains above, by dry powder: the mass ratio of organic carrier=1: 0.5 joins in the organic carrier and sizes mixing, and obtains having the piezo-resistance slurry of certain viscosity.
At Al
2O
3Silk screen printing conductive silver paste in the potsherd substrate is dried under 100 ℃ temperature, forms hearth electrode.Adopt the silk screen web plate of 60 μ m, divided for 10 steps with the piezo-resistance slurry for preparing, per step mode of 2 times is printed on the hearth electrode, after each brush system is finished sample is dried under 100 ℃ temperature, forms the thick film varistor layer.At silk screen printing conductive silver paste on the thick film varistor layer and under 100 ℃ temperature, dry, form top electrode.
The digit-control resistance stove is put in the substrate of finishing after the silk screen printing, slowly be warming up to 700 ℃, be incubated and be cooled to room temperature with stove after 2 hours, obtain the semi-finished product of sinter molding.
On the end face of half-finished hearth electrode that obtains and top electrode, with the gluing system electrode outlet line of normal temperature quick-drying conductive silver, left standstill under the room temperature 0.5 hour, obtain being used for the piezo-resistance thick film products of high-pressure electrostatic discharge prevention.
The electric property index of the piezo-resistance thick film of preparation method's preparation of the piezo-resistance thick film of employing present embodiment is: electric potential gradient 3260V/mm; Non linear coefficient 8.9; Leakage current 89.6 μ A.
See also Fig. 3, the circuit theory diagrams that the piezo-resistance thick film that the preparation method who adopts piezo-resistance thick film of the present invention is prepared carries out Hi-pot test.Wherein, R1 is a current-limiting resistance, and R2 is the piezo-resistance thick film that is used for the high-pressure electrostatic discharge prevention, and R3 is a load resistance, promptly desires protective circuit, and U1 is an input voltage, and U0 is for desiring the protective circuit two ends to output voltage.The piezo-resistance thick film R2 that will be used for the high-pressure electrostatic discharge prevention is in parallel with the desire protective circuit, carry out Hi-pot test, output voltage and power output are carried out record desiring the protective circuit two ends, obtain the relevant parameter index and be: unit thickness maximum output voltage 3181V; Unit thickness peak power output 1.69W; Regulation factor 0.414.
Embodiment 2:
With the micron order raw material: zinc oxide ZnO, bismuth oxide Bi
2O
3, antimonous oxide Sb
2O
3, chrome green Cr
2O
3, cobalt sesquioxide Co
2O
3, manganese dioxide MnO
2, yttria Y
2O
3, according to mol ratio ZnO: Bi
2O
3: Sb
2O
3: Cr
2O
3: Co
2O
3: MnO
2: Y
2O
3=96.42: 0.7: 1.0: 0.5: after the mixing in 0.8: 0.5: 0.08, add the 15ml absolute ethyl alcohol, wet-milling 5 hours.Wherein, ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm.With the mixed powder oven dry, under above-mentioned identical ball milling condition, dry grinded 2 hours the dry powder of the nanoscale that obtains mixing after the wet-milling again.
Ethyl cellulose is dissolved in terpinol, and to be mixed with concentration be 5% organic carrier, the dry powder that weighing obtains above, by dry powder: the mass ratio of organic carrier=1: 1 joins in the organic carrier and sizes mixing, and obtains having the piezo-resistance slurry of certain viscosity.
At Al
2O
3Silk screen printing conductive silver paste in the potsherd substrate is dried under 100 ℃ temperature, forms hearth electrode.Adopt the silk screen web plate of 30 μ m, divided for 6 steps with the piezo-resistance slurry for preparing, per step mode of 3 times is printed on the hearth electrode, after each brush system is finished sample is dried under 100 ℃ temperature, forms the thick film varistor layer.At silk screen printing conductive silver paste on the thick film varistor layer and under 100 ℃ temperature, dry, form top electrode.
The digit-control resistance stove is put in the substrate of finishing after the silk screen printing, slowly be warming up to 750 ℃, be incubated and be cooled to room temperature with stove after 1.5 hours, obtain the semi-finished product of sinter molding.
On the end face of half-finished hearth electrode that obtains and top electrode, with the gluing system electrode outlet line of normal temperature quick-drying conductive silver, left standstill under the room temperature 0.5 hour, obtain being used for the piezo-resistance thick film products of high-pressure electrostatic discharge prevention.
The electric property index of the piezo-resistance thick film of preparation method's preparation of the piezo-resistance thick film of employing present embodiment is: electric potential gradient 3112V/mm; Non linear coefficient 9.5; Leakage current 72.8 μ A.
Utilize circuit shown in Figure 3, piezo-resistance thick film to preparation method's preparation of the piezo-resistance thick film that adopts present embodiment carries out Hi-pot test, output voltage and power output are carried out record desiring the protective circuit two ends, obtain the relevant parameter index and be: unit thickness maximum output voltage 3048V; Unit thickness peak power output 1.55W; Regulation factor 0.199.
Embodiment 3:
With the micron order raw material: zinc oxide ZnO, bismuth oxide Bi
2O
3, antimonous oxide Sb
2O
3, chrome green Cr
2O
3, cobalt sesquioxide Co
2O
3, manganese dioxide MnO
2, yttria Y
2O
3, according to mol ratio ZnO: Bi
2O
3: Sb
2O
3: Cr
2O
3: Co
2O
3: MnO
2: Y
2O
3=96.42: 0.7: 1.0: 0.5: after the mixing in 0.8: 0.5: 0.08, add the 15ml absolute ethyl alcohol, wet-milling 10 hours.Wherein, ratio of grinding media to material is 20: 1, and rotational speed of ball-mill is 450rpm.With the mixed powder oven dry, under above-mentioned identical ball milling condition, dry grinded 1 hour the dry powder of the nanoscale that obtains mixing after the wet-milling again.
Ethyl cellulose is dissolved in terpinol, and to be mixed with concentration be 5% organic carrier, the dry powder that weighing obtains above, by dry powder: the mass ratio of organic carrier=1: 1.5 joins in the organic carrier and sizes mixing, and obtains having the piezo-resistance slurry of certain viscosity.
At Al
2O
3Silk screen printing conductive silver paste in the potsherd substrate is dried under 100 ℃ temperature, forms hearth electrode.Adopt the silk screen web plate of 10 μ m, divided for 4 steps with the piezo-resistance slurry for preparing, per step mode of 4 times is printed on the hearth electrode, after each brush system is finished sample is dried under 100 ℃ temperature, forms the thick film varistor layer.At silk screen printing conductive silver paste on the thick film varistor layer and under 100 ℃ temperature, dry, form top electrode.
The digit-control resistance stove is put in the substrate of finishing after the silk screen printing, slowly be warming up to 750 ℃, be incubated and be cooled to room temperature with stove after 1 hour, obtain the semi-finished product of sinter molding.
On the end face of half-finished hearth electrode that obtains and top electrode, with the gluing system electrode outlet line of normal temperature quick-drying conductive silver, left standstill under the room temperature 0.5 hour, obtain being used for the piezo-resistance thick film products of high-pressure electrostatic discharge prevention.
The electric property index of the piezo-resistance thick film of preparation method's preparation of the piezo-resistance thick film of employing present embodiment is: electric potential gradient 2954V/mm; Non linear coefficient 9.8; Leakage current 92.6 μ A.
Utilize circuit shown in Figure 3, piezo-resistance thick film to preparation method's preparation of the piezo-resistance thick film that adopts present embodiment carries out Hi-pot test, output voltage and power output are carried out record desiring the protective circuit two ends, obtain the relevant parameter index and be: unit thickness maximum output voltage 2751V; Unit thickness peak power output 1.26W; Regulation factor 0.626.
Embodiment 4:
With the micron order raw material: zinc oxide ZnO, bismuth oxide Bi
2O
3, antimonous oxide Sb
2O
3, chrome green Cr
2O
3, cobalt sesquioxide Co
2O
3, manganese dioxide MnO
2, yttria Y
2O
3, according to mol ratio ZnO: Bi
2O
3: Sb
2O
3: Cr
2O
3: Co
2O
3: MnO
2: Y
2O
3=96.42: 0.7: 1.0: 0.5: after the mixing in 0.8: 0.5: 0.08, add the 15ml absolute ethyl alcohol, wet-milling 10 hours.Wherein, ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 300rpm.With the mixed powder oven dry, under above-mentioned identical ball milling condition, dry grinded 1 hour the dry powder of the nanoscale that obtains mixing after the wet-milling again.
Ethyl cellulose is dissolved in terpinol, and to be mixed with concentration be 10% organic carrier, the dry powder that weighing obtains above, by dry powder: the mass ratio of organic carrier=1: 2 joins in the organic carrier and sizes mixing, and obtains having the piezo-resistance slurry of certain viscosity.
At Al
2O
3Silk screen printing conductive silver paste in the potsherd substrate is dried under 100 ℃ temperature, forms hearth electrode.Adopt the silk screen web plate of 6 μ m, divided for 2 steps with the piezo-resistance slurry for preparing, per step mode of 5 times is printed on the hearth electrode, after each brush system is finished sample is dried under 100 ℃ temperature, forms the thick film varistor layer.At conductive silver paste that silk screen printing on the thick film varistor layer is purchased and under 100 ℃ temperature, dry, form top electrode.
The digit-control resistance stove is put in the substrate of finishing after the silk screen printing, slowly be warming up to 800 ℃, be incubated and be cooled to room temperature with stove after 0.5 hour, obtain the semi-finished product of sinter molding.
On the end face of half-finished top electrode that obtains and hearth electrode, with the gluing system electrode outlet line of normal temperature quick-drying conductive silver, left standstill under the room temperature 0.5 hour, obtain being used for the piezo-resistance thick film products of high-pressure electrostatic discharge prevention.
The electric property index of the piezo-resistance thick film of preparation method's preparation of the piezo-resistance thick film of employing present embodiment is: electric potential gradient 2936V/mm; Non linear coefficient 9.5; Leakage current 96.5 μ A.
Utilize circuit shown in Figure 3, piezo-resistance thick film to preparation method's preparation of the piezo-resistance thick film that adopts present embodiment carries out Hi-pot test, output voltage and power output are carried out record desiring the protective circuit two ends, obtain the relevant parameter index and be: unit thickness maximum output voltage 2724V; Unit thickness peak power output 1.24W; Regulation factor 0.587.
Compared with prior art, the preparation method of piezo-resistance thick film of the present invention improves the pressure sensitive voltage value of piezo-resistance thick film by rare-earth metal doped oxide yttria in the micron order raw material.Grind the micron order raw material by the employing high-energy ball-milling process, thus the dry powder of the nanoscale that acquisition mixes, particle is tiny.In filming technology, use silk screen print method, and repeatedly coating of substep, to prevent the film face checking and to guarantee the repeatability of technology.Under 700～800 ℃ of conditions, carry out low-temperature sintering, suppress too growing up and the volatilization of bismuth oxide of crystal grain, obtain the high voltage varistor thick film.Preparation method's technology of piezo-resistance thick film of the present invention is simple relatively, easy operating, and lower to equipment and cost requirement, the pressure sensitive voltage value and the high voltage protective level of the piezo-resistance thick film of gained meet and exceed the result that other method obtains.
Adopt the preparation method of piezo-resistance thick film of the present invention can prepare pressure sensitive voltage value height, well behaved piezo-resistance thick film, see also Fig. 4, Fig. 4 is the high voltage stabilizing curve of the piezo-resistance thick film of preparation method's preparation of employing piezo-resistance thick film of the present invention.The micro-parameter and the electric property index of the piezo-resistance thick film of preparation method's preparation of the piezo-resistance thick film of employing present embodiment are as shown in table 1.
Table 1
Under situation without departing from the spirit and scope of the present invention, can also constitute many very embodiment of big difference that have.Should be appreciated that except as defined by the appended claims, the invention is not restricted at the specific embodiment described in the specification.
Claims (10)
1. the preparation method of a piezo-resistance thick film is characterized in that, comprises the steps:
After will comprising the micron raw material mixing of yttria, adopt the method wet-milling of high-energy ball milling, then with the oven dry of the mixed powder behind the ball milling, adopt the method dry grinding of high-energy ball milling again, the dry powder of the nanoscale that obtains mixing;
Join the dry powder of described nanoscale in the organic carrier and size mixing, obtain the piezo-resistance slurry;
In the potsherd substrate, adopt the mode of silk screen printing to form hearth electrode, adopt the silk screen web plate that described piezo-resistance slurry substep repeatedly is printed on the described hearth electrode, be completed for printing the back oven dry at every turn, form the thick film varistor layer, on described thick film varistor layer, adopt the mode of silk screen printing to form top electrode then;
Resistance furnace is put in the substrate that will have described hearth electrode, described thick film varistor layer and described top electrode, carries out low-temperature sintering under 700～800 ℃ of conditions;
On described hearth electrode and described top electrode end face, form electrode outlet line.
2. the preparation method of piezo-resistance thick film as claimed in claim 1, it is characterized in that, described micron raw material is the mixture of zinc oxide, bismuth oxide, antimonous oxide, chrome green, cobalt sesquioxide, manganese dioxide, yttria, and the mol ratio of described zinc oxide, bismuth oxide, antimonous oxide, chrome green, cobalt sesquioxide, manganese dioxide, yttria is 96.42: 0.7: 1.0: 0.5: 0.8: 0.5: 0.08.
3. the preparation method of piezo-resistance thick film as claimed in claim 1 is characterized in that, when adopting the high energy ball mill method wet-milling, add the 15ml absolute ethyl alcohol, wet-milling 5～10 hours, wherein, the scope of ratio of grinding media to material is 10～40: 1, and the rotational speed of ball-mill scope is 300～600rpm.
4. the preparation method of piezo-resistance thick film as claimed in claim 1 is characterized in that, when adopting the high energy ball mill method dry grinding, dry grinds 1～2 hour, and wherein, the scope of ratio of grinding media to material is 10～40: 1, and the rotational speed of ball-mill scope is 300～600rpm.
5. the preparation method of piezo-resistance thick film as claimed in claim 1 is characterized in that, described organic carrier is 2～10% organic carrier for the concentration that ethyl cellulose is dissolved in terpinol preparation formation.
6. the preparation method of piezo-resistance thick film as claimed in claim 5, it is characterized in that, join the dry powder of described nanoscale in the described organic carrier and in the step of sizing mixing, the mass ratio of dry powder of described nanoscale and described organic carrier is 1: (0.5～2).
7. the preparation method of piezo-resistance thick film as claimed in claim 1 is characterized in that, described substrate is the alumina ceramic plate substrate, and the mode that adopts the silk screen printing conductive silver paste and dry under 100 ℃ temperature forms described hearth electrode and described top electrode.
8. the preparation method of piezo-resistance thick film as claimed in claim 1, it is characterized in that, adopt the silk screen web plate of 6～60 μ m, divided for 2～10 steps with described piezo-resistance slurry, per step mode of 2～5 times is printed on the described hearth electrode, under 100 ℃ temperature, dry after each brush system is finished, form described thick film varistor layer.
9. the preparation method of piezo-resistance thick film as claimed in claim 1, it is characterized in that, in described low sintering step, described resistance furnace is put in the substrate that will have described hearth electrode, described thick film varistor layer and described top electrode, be warming up to 700～800 ℃ gradually, be incubated and be cooled to room temperature with stove after 0.5～2 hour.
10. the preparation method of piezo-resistance thick film as claimed in claim 1 is characterized in that, in the step that forms electrode outlet line, adopts the gluing system electrode outlet line of normal temperature quick-drying conductive silver on described hearth electrode and described top electrode end face.
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| CN 201110051455 CN102176365A (en) | 2011-03-03 | 2011-03-03 | Method for manufacturing piezoresistor thick film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432281A (en) * | 2011-09-21 | 2012-05-02 | 江苏大学 | Method for improving electrical properties of zinc oxide-based low voltage-sensitive ceramic film |
| CN102856028A (en) * | 2012-09-10 | 2013-01-02 | 临安爱华电子有限公司 | Printed resistor bake-shaping method |
| CN107533892A (en) * | 2015-04-24 | 2018-01-02 | 斯坦雷电气株式会社 | Manufacture method, resistor and the electronic device of resistor |
-
2011
- 2011-03-03 CN CN 201110051455 patent/CN102176365A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《华东师范大学博士学位论文》 20100401 柯磊 高电位梯度片式/厚膜ZnO压敏电阻的研制 , 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432281A (en) * | 2011-09-21 | 2012-05-02 | 江苏大学 | Method for improving electrical properties of zinc oxide-based low voltage-sensitive ceramic film |
| CN102856028A (en) * | 2012-09-10 | 2013-01-02 | 临安爱华电子有限公司 | Printed resistor bake-shaping method |
| CN107533892A (en) * | 2015-04-24 | 2018-01-02 | 斯坦雷电气株式会社 | Manufacture method, resistor and the electronic device of resistor |
| CN107533892B (en) * | 2015-04-24 | 2019-12-03 | 斯坦雷电气株式会社 | Manufacturing method, resistor and the electronic device of resistor |
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Application publication date: 20110907 |