CN101123135A - A low voltage/high non-linear index slice voltage sensitive resistor and its making method - Google Patents
A low voltage/high non-linear index slice voltage sensitive resistor and its making method Download PDFInfo
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- CN101123135A CN101123135A CNA2007101137707A CN200710113770A CN101123135A CN 101123135 A CN101123135 A CN 101123135A CN A2007101137707 A CNA2007101137707 A CN A2007101137707A CN 200710113770 A CN200710113770 A CN 200710113770A CN 101123135 A CN101123135 A CN 101123135A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 16
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004377 microelectronic Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a low voltage/high nonlinear index piece-type pressure-sensitive resistance and a producing method of the resistance, and belongs to the field of pressure-sensitive elements in sensor technologies in information field. Specialty of the low voltage/high nonlinear index piece-type pressure-sensitive resistance is that the resistance is made in following method: the pressure-sensitive chip is a composite structure consisting of two conductive films and a high nonlinear index pressure-sensitive film clipped in between; the conductive film, the pressure-sensitive film and the composite film are both made in film pricking process; the composite film is calcinated at a high temperature of 1000-1100 degrees to produce a pressure-sensitive chip; and the ends of the pressure-sensitive chip is encapsulated with Ni slurry and Sn slurry to produce a pressure-sensitive element. The invention meets the requirements in micro-electronic technologies, communication technologies and semiconductor technologies. Pressure-sensitive voltage of the piece-type pressure-sensitive element made through this technology is V1mA/mm=0.5-1.5V,Alpha=40-60, voltage dispersion is 3-5%, and Alpha value dispersion is plus or minus 8-plus or minus10. The method is characterized by simple process and low producing cost, overcomes the problems of general multi-layer structure process of inner electrode diffusion and end electrode extension, and applies to large scale production.
Description
(1) technical field
The present invention relates to a kind of type piezoresistor and manufacture method thereof of low-voltage/high non-linear index, belong to the pressure cell in the sensor technology of areas of information technology.
(2) background technology
Piezo-resistance is widely used in circuit, electronic devices and components, the overvoltage protection of equipment.Integrated circuit, rechargeable cellphone battery and computer system require the pressure cell of low-voltage/high non-linear index, and its pressure sensitive voltage is generally 0.5-10V, and nonlinear exponent is preferably in more than the 40-50.Character according to pressure sensitive---the high non-linearity index is followed high pressure sensitive voltage; Realize low pressure/high non-linearity index pressure cell so all adopt sandwich construction at present both at home and abroad.Yet the interior electrode metal ions diffusion of sandwich construction causes alpha index to descend, and the living pressure sensitive voltage dispersiveness that causes of prolonging of termination electrode increases.The pressure sensitive voltage of the piezo-resistance of 0402 chip component is 12-20V, α=30-40, and multi-layer structure process complexity, manufacturing cost height.
In recent years, doing big quantity research aspect low-voltage/high non-linearity index material, Zn-Bi-Sb based material pressure sensitive voltage can be accomplished 11V according to reports, and the α value is 12-15; TiO
2The pressure sensitive voltage of pressure sensitive can be accomplished 7-10V, and the α value is about 12-15.The type piezoresistor that research and development have low pressure/high non-linearity index is still current important topic.
(3) summary of the invention
The present invention is in order to remedy the deficiencies in the prior art, provides that a kind of technology is simple, the type piezoresistor and the manufacture method thereof of the low-voltage/high non-linear index of low cost of manufacture.
The present invention is achieved through the following technical solutions:
A kind of low-voltage/high non-linear index type piezoresistor, its special character is: make in the following way: the composite construction that chip varistor is made of the pressure sensitive film of pressing from both sides one deck high non-linear index between two conductive films; Conductive film and pressure sensitive film and compound film sheet are by pricking the membrane process preparation; Compound film sheet is made chip varistor through 1000--1100 ℃ of high-temperature calcination; Chip varistor is made pressure cell with Ni slurry and Sn slurry end-blocking.
Low-voltage of the present invention/high non-linear index type piezoresistor, the material of conductive film is the oxide that contains Mn-Ni-Cu-Ca, the mol ratio between it is: Mn: Ni: Cu: Ca=2.6: 1.3: 1.8: 0.3.Percentage by weight is MnO
2: NiO: CuO: CaO=43.845%: 18.834%: 34.058%: 3.263% composition also adds 0.3% ZnO.Pressure sensitive film is by ZnO, synthetic V, CoO and MnO
2Form, the ratio of its parts by weight is ZnO: V: CoO: MnO2=100: 5: 0.954: 0.414, synthetic V was by Bi
2O
3, TiO
2, Sb
2O
3And B
2O
3Constitute, the ratio of its percentage by weight is Bi
2O
3: TiO
2: Sb
2O
3: B
2O
3=88: 9: 2.0: 1.0.
The method of low-voltage of the present invention/high non-linear index type piezoresistor, its special character is: the composite construction that chip varistor is made of the pressure sensitive film of pressing from both sides one deck high non-linear index between two conductive films; Conductive film and pressure sensitive film and compound film sheet are by pricking the membrane process preparation; Compound film sheet is made chip varistor through 1000--1100 ℃ of high-temperature calcination; Chip varistor is made pressure cell with Ni slurry and Sn slurry end-blocking.
The method of low-voltage of the present invention/high non-linear index type piezoresistor, prick the film slurry weight proportion be: material: glue=(95-96): (4-5), used glue is polyvinyl alcohol.
The sintering temperature curve of high-temperature calcination is:
0.5 ℃/min of 300 ℃ of-500 ℃ of heating rates
500 ℃ of insulations (60-90) min
500 ℃ of-800 ℃ of heating rates (1.2-1.5) ℃/min
800 ℃ of insulation 60min
800 ℃ of-1000 ℃ of heating rate 3-4 ℃/min
1000 ℃ of insulations (150-180) min
0.6 ℃/min of 1000 ℃ of-800 ℃ of heating rates
800 ℃-300 ℃ are cooled off with stove.
Ni and Sn slurry end-blocking are: with Ni slurry dipping or be printed in the chip termination, at 560 ℃, reduce 30min in the air, the Sn slurry is used with quadrat method and is applied to the chip termination, toasts 40min in 350 ℃ of air atmospheres.
Principle of the present invention and concrete preparation method are as follows:
1, the preparation of conductive film
Conductive film adopts the Mn-Ni-Cu-Ca material system among the present invention, becomes porcelain to form spinelle (AB through high temperature
2O
4) structure, a large amount of Cu ions enter the B position, provide enough electronics to form high electricity and lead, and add the displacement of a small amount of Zn ion simultaneously, make lattice produce deformation, help forming firm combining with Zn pressure sensitive film coupling.Ca ion in the prescription reduces resistance on the one hand, reduces potential barrier between conductive layer and the varistor layer simultaneously.
Conductive film adopts ceramic process powder process, material prescription Mn
3O
4: NiO: CuO: CaO+ZnO=2.6: 1.3: 1.8: 0.3+0.5%wt, the ZnO conductive film is made the conducting film powder of 5-10um by following technology, powder at secondary ball milling adds adhesive (PVA) batching bundle film slurry, slurry ratio: material: adhesive=(95-96): (4-5), prick the thickness 5mm (for 0402) of film, 8mm (for 0603)
2, high non-linear index pressure sensitive film preparation
The pressure sensitive voltage of pressure sensitive film and nonlinear exponent (α) depend on prescription and the dopant species and the doping of material.Add synthetic (Bi-Ti-Sb-B) purpose among the present invention and be to reduce pressure sensitive voltage, improve nonlinear exponent.Add CoO and MnO simultaneously
2Help forming complete brilliant potential barrier, improve the uniformity of material.The pressure sensitive film preparation is identical with the conductive film preparation method, and diaphragm thickness is 0.1-0.3 (mm).
The relation of synthetic addition and pressure sensitive voltage and nonlinear exponent such as Fig. 1, the amount of synthetic only about 5%, helps obtaining than pressure sensitive voltage and higher non-linearity index.CoO and MnO
2Addition pressure sensitive voltage and nonlinear exponent are also had material impact (Fig. 2), measure (1.0-1.3) %, CoO: MnO general the adding
2=7: 3 (weight ratios).If in powder, add the praseodymium oxide (Pr6O11) of 0.1-0.15%wt, can improve nonlinear exponent.
3, sintering
The sintering of composite sheet must carry out in the atmosphere of semi-enclosed Zn pressure sensitive, normally be pressed into pad or do bedding and padding with synthetic powder with synthetic powder, cover plate and porcelain alms bowl should have certain slit, how much weight of briquetting decides according to lamination, and the effect of briquetting is to guarantee that sample is at high temperature indeformable.Sintering temperature is to the influence (as Fig. 3) of pressure sensitive voltage and nonlinear exponent (α) value.The sintering temperature height, pressure sensitive voltage descends, and the α value also reduces.Temperature pressure sensitive voltage on the low side raises rapidly.In the present invention, to the material prescription that is adopted, sintering temperature is taken as 1000-1100 ℃.
The pressure sensitive voltage V1mA/mm=0.5-1.5V of the chip pressure cell that the present invention makes, α=40-60, the voltage dispersiveness is 3-5%, the dispersiveness of α value is ± 8-± 10 to satisfy microelectric technique, mechanics of communication and semiconductor technology requirement.This method technology is simple, and low cost of manufacture has overcome the interior electrode diffusion that exists in the multi-layer structure process commonly used, the problem that termination electrode extends.This technology is applicable to production in enormous quantities.
(4) description of drawings
Fig. 1 is the graph of a relation of synthetic addition of the present invention and pressure sensitive voltage and nonlinear exponent;
Fig. 2 is CoO of the present invention and MnO
2Addition to the figure that influences of pressure sensitive voltage and nonlinear exponent;
Fig. 3 is the influence figure of sintering temperature of the present invention to pressure sensitive voltage and nonlinear exponent (α) value.
(5) embodiment
Embodiment 1:
1. the powder that conducts electricity preparation
Material prescription
MnO
2: NiO: CuO: CaO=43.845%: 18.834%: 34.058%: 3.263% (weight ratio)
Add the ZnO that accounts for total weight 0.3% in addition;
Ball milling: material: water: ball=1.0: 1.2: 1.5 (weight ratio);
The ball milling time first time: 8 hours;
Give and burning 700 ℃ of temperature, time: 2.5 hours;
Ball milling for the second time: time: 16 hours, cross 200 mesh sieves at last.
2. conductive film preparation
Slurrying: material: PVA=100: 40 (weight ratios), PVA concentration are 10%;
Fermentation: the slurry that fully stirs evenly was deposited 12 hours under the environment of wet relatively 95%RH.
Prick film: place in the roll forming roll forming repeatedly to roll (promptly material is sticking rolls) until taking off in slurry, adjust thickness then to 5mm.
3. pressure sensitive film preparation
The preparation of synthetic (V):
Batching: Bi
2O
3: TiO
2: Sb
2O
3: B
2O
3=88: 9.0: 2.0: 1.0 (weight ratio);
Through grinding (8 hours), 500 ℃ of synthesis temperatures, 2.5 hours time; And then ground 12 hours, as the synthetic powder
The pressure sensitive prescription:
Its parts by weight proportioning is: ZnO: V (synthetic): CoO: MnO
2=100: 5: 0.954: 0.414, can add that in addition parts by weight are 0.1 Pr6O11;
The pressure sensitive film preparation is identical with conductive film preparation technology, and the diaphragm thickness of compacting is 0.3mm.
4. lamination: pressure-sensitive film is clipped between two conducting films, and its bundle is ground into the compound film sheet that thickness is 1mm pricking on the film machine
5. sintering: compound film sheet is packed in the porcelain alms bowl, send into high temperature sintering.
6. element is made: will burned sheet be cut into the chip of 0402 size, the Ni slurry is soaked at 560 ℃ of reduction 30min in the chip two ends, and then soaks Sn and starch, and toasts 40min at 350 ℃, and 0402 chip component is finished.
7. test result (with 100 elements statistics)
| V1mA/mm | α | Ir/uA) | ΔV/v | Δα/α |
| 1.52V | 42 | 0.13mA | ±5％ | ±8％ |
Embodiment 2:
Change the thickness of conducting film into 8mm, pressure-sensitive film thickness is 0.3mm, makes 0603 chip pressure cell by the same method of embodiment, and test result (with 100 element statistics) is:
| V1mA/mm | α | Ir/(uA) | ΔV/v | Δα/α |
| 1.51V | 41.7 | 0.05 | ±4.2％ | ±7.1％ |
Embodiment 3:
The pressure sensitive film material prescription is taken as
ZnO: V: CoO: MnO2=99: (weight ratio) conductive film thickness was 5mm in 6.0: 0.78: 0.5, and pressure sensitive film thickness is 0.1mm, makes 0402 pressure cell by the method for embodiment, test result (with 100 element statistics)
| V1mA/mm | α | Ir/(uA) | ΔV/v | Δα/α |
| 0.72V | 54 | 0.58 | ±5％ | ±9.1％ |
Technology provided by the invention can realize low-voltage/high non-linearity index pressure cell, and technology is simple, low cost of manufacture, and can produce in enormous quantities.
Claims (8)
1. low-voltage/high non-linear index type piezoresistor is characterized in that: make in the following way: the composite construction that chip varistor is made of the pressure sensitive film of pressing from both sides one deck high non-linear index between two conductive films; Conductive film and pressure sensitive film and compound film sheet are by pricking the membrane process preparation; Compound film sheet is made chip varistor through 1000--1100 ℃ of high-temperature calcination; Chip varistor is made pressure cell with Ni slurry and Sn slurry end-blocking.
2. low-voltage according to claim 1/high non-linear index type piezoresistor is characterized in that: the material of conductive film is the oxide that contains Mn-Ni-Cu-Ca, and the mol ratio between it is: Mn: Ni: Cu: Ca=2.6: 1.3: 1.8: 0.3.
3. low-voltage according to claim 2/high non-linear index type piezoresistor is characterized in that: conductive film is to be MnO by percentage by weight
2: NiO: CuO: CaO=43.845%: 18.834%: 34.058%: 3.263% composition.
4. low-voltage according to claim 1/high non-linear index type piezoresistor is characterized in that: pressure sensitive film is by ZnO, synthetic V, CoO and MnO
2Form, the ratio of its parts by weight is ZnO: V: CoO: MnO2=100: 5: 0.954: 0.414, synthetic V was by Bi
2O
3, TiO
2, Sb
2O
3And B
2O
3Constitute, the ratio of its percentage by weight is Bi
2O
3: TiO
2: Sb
2O
3: B
2O
3=88: 9: 2.0: 1.0.
5. the method for low-voltage according to claim 1/high non-linear index type piezoresistor is characterized in that: the composite construction that chip varistor is made of the pressure sensitive film of pressing from both sides one deck high non-linear index between two conductive films; Conductive film and pressure sensitive film and compound film sheet are by pricking the membrane process preparation; Compound film sheet is made chip varistor through 1000--1100 ℃ of high-temperature calcination; Chip varistor is made pressure cell with Ni slurry and Sn slurry end-blocking.
6. the method for low-voltage according to claim 5/high non-linear index type piezoresistor is characterized in that: prick the film slurry weight proportion be: material: glue=(95-96): (4-5), used glue is polyvinyl alcohol.
7. the method for low-voltage according to claim 5/high non-linear index type piezoresistor is characterized in that:
The sintering temperature curve of high-temperature calcination is:
0.5 ℃/min of 300 ℃ of-500 ℃ of heating rates
500 ℃ of insulations (60-90) min
500 ℃ of-800 ℃ of heating rates (1.2-1.5) ℃/min
800 ℃ of insulation 60min
800 ℃ of-1000 ℃ of heating rate 3-4 ℃/min
1000 ℃ of insulations (150-180) min
0.6 ℃/min of 1000 ℃ of-800 ℃ of heating rates
800 ℃-300 ℃ are cooled off with stove.
8. the method for low-voltage according to claim 5/high non-linear index type piezoresistor, it is characterized in that: Ni and Sn slurry end-blocking are: Ni is starched dipping or is printed in the chip termination, at 560 ℃, reduce 30min in the air, the Sn slurry is used with quadrat method and is applied to the chip termination, toasts 40min in 350 ℃ of air atmospheres.
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|---|---|---|---|
| CN200710113770A CN100595849C (en) | 2007-09-12 | 2007-09-12 | A low voltage/high non-linear index slice voltage sensitive resistor and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710113770A CN100595849C (en) | 2007-09-12 | 2007-09-12 | A low voltage/high non-linear index slice voltage sensitive resistor and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN101123135A true CN101123135A (en) | 2008-02-13 |
| CN100595849C CN100595849C (en) | 2010-03-24 |
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ID=39085419
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|---|---|---|---|
| CN200710113770A Expired - Fee Related CN100595849C (en) | 2007-09-12 | 2007-09-12 | A low voltage/high non-linear index slice voltage sensitive resistor and its making method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633498A (en) * | 2012-03-31 | 2012-08-15 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered zinc oxide voltage-sensitive ceramic material and preparation method thereof |
| CN103021606A (en) * | 2012-12-26 | 2013-04-03 | 山东中厦电子科技有限公司 | Low-voltage/high-non-linear-coefficient ZnO pressure-sensitive element and manufacturing method thereof |
| CN107689277A (en) * | 2016-08-03 | 2018-02-13 | 东莞市仙桥电子科技有限公司 | A kind of sintering process of thermistor |
-
2007
- 2007-09-12 CN CN200710113770A patent/CN100595849C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633498A (en) * | 2012-03-31 | 2012-08-15 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered zinc oxide voltage-sensitive ceramic material and preparation method thereof |
| CN103021606A (en) * | 2012-12-26 | 2013-04-03 | 山东中厦电子科技有限公司 | Low-voltage/high-non-linear-coefficient ZnO pressure-sensitive element and manufacturing method thereof |
| CN107689277A (en) * | 2016-08-03 | 2018-02-13 | 东莞市仙桥电子科技有限公司 | A kind of sintering process of thermistor |
| CN107689277B (en) * | 2016-08-03 | 2019-02-22 | 东莞市仙桥电子科技有限公司 | A kind of sintering process of thermistor |
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| Publication number | Publication date |
|---|---|
| CN100595849C (en) | 2010-03-24 |
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