CN101447265A - Method for fabricating zinc oxide multilayer chip piezoresistor - Google Patents
Method for fabricating zinc oxide multilayer chip piezoresistor Download PDFInfo
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- CN101447265A CN101447265A CNA2007101934691A CN200710193469A CN101447265A CN 101447265 A CN101447265 A CN 101447265A CN A2007101934691 A CNA2007101934691 A CN A2007101934691A CN 200710193469 A CN200710193469 A CN 200710193469A CN 101447265 A CN101447265 A CN 101447265A
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Abstract
The invention provides a method for manufacturing a zinc oxide multilayer chip piezoresistor with a laminated multilayer sheet structure with good voltage limiting characteristic and good pulse tolerance characteristic. The manufacturing method is characterized in that raw materials are prepared according to 100 mol percent of ZnO, 0.1-1.5 mol percent of Bi2O3, 0.01-2.0 mol percent of Sb2O3, 0.1-1.5 mol percent of more than one of CoO and MnO2, 0.01-2 mol percent of Cr2O3, 0.01-2 mol percent of H3BO3 and Al2O3 with the concentration of 10-1000ppm. In the materials, calcining material containing all Bi2O3 and Sb2O3 and 0.1-1.0 mol percent of ZnO is subject to heat treatment within the temperature range of 700 DEG C and 1000 DEG C. The calcining material and other raw materials are added to form blank sheet material which is laminated and cut, so as to form a blank chip to be calcined.
Description
Technical field
The present invention relates to be used in various electric and electronics to protect semiconductor element etc. to avoid being subjected to load rejection impacts and (piezoresistive element when ロ-De ダ Application プ サ-ジ), igniter shock, lightning impulse, Electrostatic Discharge, switching surge etc., particularly relates to the manufacture method of small-sized zinc oxide multilayer chip piezoresistor that can the real dress in surface.
Background technology
In the electric and electronic of portable phone etc.; follow rapid in recent years high frequencyization, high capacity; guarantee the stability of moving and corresponding with pulsive noise, Electrostatic Discharge etc. for protective circuit avoids being subjected to various impacts, the needs as the piezo-resistance of more high performance overvoltage protection element are increased with the noise regulation.In addition, from the machine miniaturization, what the disc piezo-resistance of using the ratio band to go between mostly was more small-sized can the real zinc oxide multilayer chip piezoresistor of adorning in surface.
Usually, Zinc-oxide piezoresistor as principal component, adds the bismuth oxide (Bi of accelerating oxidation zinc grain growth with zinc oxide (ZnO)
2O
3) and suppress the antimony oxide (Sb of grain growth
2O
3).Perhaps add various glass etc. as sintering aid.
The basic additive of piezo-resistance has changed the electrical characteristics of piezo-resistance greatly according to the combination of its addition.That is to say, mixed proportion according to the raw material that adds, the fluctuation of two Schottky barriers (グ Block Le シ ヨ Star ト キ-barrier) of unbalanced, the so-called crystal boundary energy level of grain growth can take place during sintering, it found that, the pulse tolerance the during impact of the leakage current during as the applied voltage of piezo-resistance fundamental characteristics, the nonlinear α value of expression, piezo-resistance voltage, deboost, particularly outer increasing has big difference.
As the desirable form of piezo-resistance sintered body as following.
Crystal grain (ZnO crystal grain) is uniform.
Space between the crystal grain (ZnO crystal grain) is little.
Form crystal boundary energy level (Schottky barrier), its fluctuation is little.
The ratio resistance of crystal grain (ZnO crystal grain) is little.
Disclose in the patent documentation 1 in advance with 3 moles of zinc oxide (ZnO), 0.025 mole of bismuth oxide (Bi that % is above more than the %
2O
3), the above antimony oxide (Sb of 0.025 mole of %
2O
3) mix, in roasting more than 700 ℃, will join in this roasting raw material as the zinc oxide (ZnO) of main material, formally burn till, form piezo-resistance.The document has been put down in writing by forming the pyrochlore phase by roasting, and the fluctuation of piezo-resistance voltage reduces, and the deboost characteristic is also good in addition.
But, the grain growth of ZnO has directivity, because of crystal grain is grown up along the C direction of principal axis, the inhomogeneities that causes crystal grain, this becomes the reason of deterioration in characteristics, can think, even as patent documentation 1, the very small amount of pyrochlore that is formed by roasting is added to mutually with in zinc oxide (ZnO) remaining raw material as main body, can not fully control the grain growth of whole ZnO.In addition, as prerequisite, this is owing to comparing with multilayer sheet type, and is especially big as the live part of the piezoresistive element between pair of electrodes, can think, can improve according to patent documentation 1 characteristic with the disc piezo-resistance for patent documentation 1.As the occasion of the multilayer sheet type type piezo-resistance of object of the present invention, owing to be the structure of lamination multi-layer thin sheet material,,, can not obtain effect of sufficient by constituting of patent documentation 1 so can think because of the particle state of crystal grain has appreciable impact to characteristic.
[patent documentation 1] spy opens flat 3-211705 communique
Summary of the invention
The present invention finishes in view of above-mentioned situation, the objective of the invention is to, the manufacture method of all good zinc oxide multilayer chip piezoresistor of the deboost characteristic of zinc oxide multilayer chip piezoresistor of lamination composite wafer equipment structure and pulse tolerance characteristic can be provided.
The manufacture method of zinc oxide multilayer chip piezoresistor of the present invention is characterised in that, according to zinc oxide (ZnO) be 100 moles of % with in the other addition relative, bismuth oxide (Bi with it
2O
3) be 0.1～1.5 mole of %, antimony oxide (Sb
2O
3) be 0.01～2.0 mole of %, cobalt oxide (CoO) and manganese oxide (MnO
2) in be 0.1～1.5 mole of %, chromium oxide (Cr more than a kind
2O
3) be 0.01～2 mole of %, boric acid (H
3BO
3) be 0.01～2 mole of %, other aluminium oxide (Al
2O
3) concentration be that 10～1000ppm prepares these raw materials like that, in these raw materials, to containing the bismuth oxide (Bi of whole amounts
2O
3) and antimony oxide (Sb
2O
3) and the roasting raw material of the zinc oxide (ZnO) of 0.1～1.0 mole of % in 700～1000 ℃ temperature range, heat-treat, add this roasting raw material and other raw material, form blank sheet, on this blank sheet, form electric conducting material and stick with paste pattern, with this blank sheet lamination, cut-out, after forming chips, burn till.By this, can make deboost characteristic and all good zinc oxide multilayer chip piezoresistor of pulse tolerance characteristic.
Description of drawings
Fig. 1 is the profile of zinc oxide multilayer chip piezoresistor.
Fig. 2 is the flow chart of manufacture method of the zinc oxide multilayer chip piezoresistor of one embodiment of the present invention.
Symbol description
10 zinc oxide multilayer chip piezoresistors
11 piezo-resistance sintered bodies
12a, 12b internal electrode
13a, 13b outer electrode
Embodiment
Below, with reference to the description of drawings embodiments of the present invention.
Fig. 1 represents the component structure example of zinc oxide multilayer chip piezoresistor.This zinc oxide multilayer chip piezoresistor 10 be with become the raw-material zinc oxide of piezo-resistance as principal component, contain the electric conducting material that disposes platinum (Pt) or palladium (Pd) etc. on the blank sheet 11 of additive of antimony oxide, bismuth oxide etc. and stick with paste pattern (internal electrode pattern), make its lamination, burn till and the lamination-type sintered body element made.With zinc oxide as principal component, contain the inside of sintered body 11 of the additive of antimony, bismuth etc., with internal electrode 12a, the 12b of the mutual stacked arrangement electric conducting material of parallel flat shape, become the electrode configuration same with stacked capacitor.
And, a plurality of internal electrode 12a, 12b respectively with about outer electrode 13a, 13b be connected.Thereby, be applied to voltage between left and right sides outer electrode 13a, 13b and also just be applied to inside at piezo-resistance sintered body 11 with the piezo-resistance sintered body part between electrode 12a, the 12b of the configuration of parallel flat shape.In this embodiment, by the quick electrical resistance sintering body of 4 laminations layer, formed piezoresistive element.On the electrode of silver etc., implement nickel plating, solder or zinc-plated, can make outer electrode 13a, 13b have good real equipment.In addition, zinc oxide multilayer chip piezoresistor 10 for example is the parts that have as the surperficial real dress type of the size of the standard chips parts of 3.2mm * 1.6mm (3216 type) etc.
Piezo-resistance be applied voltage reach certain certain value when above electric current can flow out rapidly to limit the voltage limit function element of the voltage more than it.Utilize the voltage limit function of piezo-resistance, can protect the circuit of electric and electronic and semiconductor element to avoid being subjected to various abnormal voltages.Following explanation earlier is as 3 specific characters (leakage current, deboost, pulse tolerance) and the α value of the essential characteristic of piezo-resistance.
(leakage current)
Usually, leakage current is represented the electric current that flows through when adding maximum allows circuit voltage.That is, when being expression use piezo-resistance, under the voltage environment that can be applied to outer electrode continuously, can only flow through the index of much electric currents, wish little.On the other hand, when it was estimated, the electric current that flows through when adding as 0.9 times of the piezo-resistance voltage of harsh conditions more voltage was estimated.In embodiments of the invention described later, the leakage current during also with the voltage that adds 0.9 times of piezo-resistance voltage is estimated.In order to suppress leakage current it is diminished, the uniformity of the two Schottky barriers that form at the crystal boundary place of zinc oxide grain is important with its thickness is thickened.When forming crystal boundary, can obtain simultaneously liquid phase when brilliant, can high resistanceization, leakage current is diminished.
(deboost)
The voltage V that the piezo-resistance two ends were represented when usually, so-called piezo-resistance voltage was meant the electric current that flows through 1 (mA)
1mARelative therewith, so-called piezo-resistance deboost is meant the voltage V that the piezo-resistance two ends are represented when flowing through electric current bigger about 1 (A), 2 (A), 10 (A)
1A, V
2A, V
10AWill be with respect to piezo-resistance voltage (V
1mA) deboost (V
2A, 10A) ratio (deboost/piezo-resistance voltage) be called limit voltage ratio.Piezo-resistance and the parts that will protect also connect; show as the characteristic of piezo-resistance non-linear for the abnormal current utilization of Electrostatic Discharge etc. circuit voltage is suppressed function for low-voltage; this deboost is low more, and indication circuit voltage, the abnormal electrical pressure drop that is added on the guard block must be low more.To suppress the characteristic that this deboost makes its step-down in order showing, must to improve the uniformity of zinc oxide (ZnO) crystal grain of sintered body.By this, electric field disperses, and the nonlinear characteristic that is manifested by crystal boundary increases, and deboost reduces.
(pulse tolerance)
The tolerance of the piezo-resistance when so-called pulse tolerance is illustrated in the big electric current of pulse feature that flows into as lightning impulse, igniter shock, load rejection are impacted.This tolerance in order to surge waveform add 500 (A) etc. big electric current, estimate by the rate of change of the piezo-resistance voltage before the applied shock and behind the applied shock.In order to improve this pulse tolerance, crystal grain (zinc oxide grain) and grain boundary (crystal boundary) as the piezo-resistance basic comprising are adapted both ways.At first, seek the crystal grain low resistanceization, the big electric current that wish to flow into becomes Joule heat in the grain boundary heat is as soon as possible to all diffusions of main body, to prevent the destruction of 1 crystal boundary.On the other hand, for the grain boundary, the thickness of Schottky barrier is thickened, it is important not causing destroying for the big electric current of charging into.
(α value)
In piezo-resistance, be configured in interelectrode sintered body and sharply change because of voltage makes resistance value, reach to a certain voltage when above, the electric current that flows through hardly before this flows out sharp.The variation a little of piezo-resistance voltage can make electric current with 10 times unit change.This moment non-linear (that is, though electric current and voltage are linear relations in ohm's law) is called the α value, and non-linear good more, the α value is big more.The α value is big more, and expression standby action leakage current is more little, and power consumption is low, is difficult to take place out of control by oneself simultaneously and heating destruction that cause.
Below, the manufacturing process of piezo-resistance of the present invention is described with reference to Fig. 2.
At first, according to zinc oxide (ZnO) be 100 moles of % with in the other addition relative, bismuth oxide (Bi with it
2O
3) be 0.1～1.5 mole of %, antimony oxide (Sb
2O
3) be 0.01～2.0 mole of %, cobalt oxide (CoO) and manganese oxide (MnO
2) in be 0.1～1.5 mole of %, chromium oxide (Cr more than a kind
2O
3) be 0.01～2 mole of %, boric acid (H
3BO
3) be 0.01～2 mole of %, in addition, aluminium oxide (Al
2O
3) concentration be that 10～1000ppm prepares these raw materials like that, in these raw materials, mix all bismuth oxide (Bi of amount
2O
3) and antimony oxide (Sb
2O
3) and 0.1～1.0 mole of % zinc oxide (ZnO) (step 100) as the roasting raw material, with ball mill etc. it is pulverized and adjust particle diameter (step 101), under oxidizing atmosphere, carry out roasting (step 102) 700～1000 ℃ temperature ranges, adjust particle diameter (step 103) with pulverizing such as ball mills.In addition, for convenience, so-called roasting raw material is represented any or both sides of state before the heat treatment of step 102 and the state after the heat treatment.
Then, add this roasting raw material and other raw material, promptly as the remainder of the zinc oxide (ZnO) of main material with according to cobalt oxide (CoO) and manganese oxide (MnO
2) in be 0.1～1.5 mole of %, chromium oxide (Cr more than a kind
2O
3) be 0.01～2 mole of %, boric acid (H
3BO
3) be 0.01～2 mole of %, aluminium oxide (Al
2O
3) concentration be the such various additives of 10～1000ppm, carry out the mixing (step 104) of raw material.Then, make particle neat (step 105), add PVB, plasticizer, dispersant, release agent, retarder thinner, make slurry (step 106) with pulverizing such as ball mills.
Then, use the scraper film forming, make the blank sheet (step 107) about thickness 10～100 μ m.On this blank sheet, print the pattern that platinum (Pt) or palladium (Pd) are stuck with paste, form internal electrode pattern, with laminations (step 108) such as hot pressing.Then, contrast product size (3216 size) is cut off, and forms chips (step 109), carries out 500 ℃ of removal binding agents (step 110) of 10 hours, burns till (step 111) under 950～1300 ℃.
Then, under 700 ℃, anneal (step 112),, burn till and form terminal electrode (outer electrode) (step 113) by the paste of silver coating (Ag) or silver/palladium (Ag/Pd).Then, terminal electrode is implemented plating (step 114), detect the electrical characteristics (step 115) of piezo-resistance voltage, leakage current etc., become the product of finishing with the order of nickel (Ni) layer, tin (Sn) layer.
The piezo-resistance of being made by above-mentioned manufacturing process particularly can reach low restriction voltageization and high impulse toleranceization.That is to say, in outer dosage, to containing the bismuth oxide (Bi of 0.1～1.5 mole of % with respect to 100 moles of % zinc oxide (ZnO)
2O
3), the antimony oxide (Sb of 0.01～2.0 mole of %
2O
3), the roasting raw material in zinc oxide (ZnO) scope of 0.1～1.0 mole of % carries out roasting in advance in 700～1000 ℃ temperature range, in this roasting raw material, add zinc oxide (ZnO) as main material, by burning till, can reach the low restriction voltageization of piezo-resistance.This point below is described.
In general, antimony oxide becomes Sb under the lower temperature in the stage of burning till
2O
4, physically be adsorbed on the surface of zinc oxide (ZnO) crystal grain, hinder its grain growth, in addition, at high temperature form pyrochlore mutually with spinelle mutually, equally also hinder its grain growth.But, because the grain growth of zinc oxide (ZnO) is since about 900 ℃, so can envision, in fact why make grain growth become unbalanced problem be because, forming pyrochlore mutually and the spinelle phase time, just in time and the crystal grain that just will begin the zinc oxide (ZnO) of grain growth influence each other.Thereby, can envision, as long as the grain growth of zinc oxide (ZnO) and pyrochlore can be separated separately with the formation of spinelle phase mutually, just can be to not influence of grain growth, can obtain the uniformity of the crystal grain of zinc oxide (ZnO), to realize low restriction voltageization.
That is to say, though since only roasting in advance have the Bi that grain growth promote to suppress effect
2O
3, Sb
2O
3, also can not get the good piezo-resistance of deboost, so anticipation is by grain growth and ZnO-Bi with zinc oxide (ZnO)
2O
3-Sb
2O
3The reaction of the formation pyrochlore phase spinelle phase that takes place in the system separately can obtain the uniformity of zinc oxide (ZnO) crystal grain, seeks low restriction voltageization.
Can think that the present invention is in the roasting stage, by Sb
2O
3Oxidation reaction form Sb
2O
4, with the compound that forms stratiform between the Bi that changes mutually, a part is as Sb
2O
4Monomer exists, perhaps as Bi
2O
3Monomer exists, but by carry out roasting under the temperature more than 700 ℃, part suppresses the Sb of grain growth
2O
3Disappeared, this moment, Zn also entered as Bi glass.When adding this roasting raw material and formally burning till zinc oxide (main material), form the pyrochlore phase, form the spinelle phase, the control grain growth.Can think, because pyrochlore is not mutually and in spinelle enters zinc oxide grain (ZnO) mutually, so, can realize hanging down and limit voltageization by promoting the uniformity of crystal grain.That is to say, can think, make the unbalanced Sb of grain growth
2O
3In the oxidation of roasting stage, form Sb
2O
4, and by the roasting raw material form pyrochlore mutually with spinelle mutually, obtain the uniformity of grain growth.
Below, expression forms the pyrochlore phase and forms spinelle general reaction equation mutually.
2Sb
2O
3+O
2→2Sb
2O
4
(condensing and on the surface attached to ZnO crystal grain) (1) by the evaporation that produces by oxidation
15ZnO+20Bi
2O
3+20Sb
2O
4+42O
2→30Zn
2Bi
3Sb
3O
14
(forming the pyrochlore phase) (2)
2Zn
2Bi
3Sb
3O
14+17ZnO→3Zn
7Sb
2O
12+3Bi
2O
3
(form spinelle and reach formation bismuth liquid phase mutually) (3)
Therefore, can think, until a series of formation spinelle mutually before, at the Bi for preparing to help to react
2O
3-Sb
2O
3The reaction of (1) when making its roasting, does not take place in the mixture of-ZnO system under the low temperature that formally burns till the stage, can obtain reaction selectivity thereafter, makes to hang down restriction voltageization.
That is to say, in method in the past, Sb
2O
3Fierce oxidation reaction takes place about 500 ℃, physically be adsorbed on the surface of ZnO, by Sb
2O
3Become Sb
2O
4Oxidizing process in the evaporation absorption of a part takes place.The Sb of this absorption
2O
3Can all not adsorb equably, this causes growing up of crystal grain inhomogeneous, makes deterioration in characteristics.Thereby, to prevent Sb
2O
3Be adsorbed on ZnO and upward be purpose, roasting in advance is by the Bi that forms liquid phase in the element that adds
2O
3And Sb
2O
3, form compound.By this, Bi
2O
3And Sb
2O
3Can not become the mutually such crystallization of pyrochlore fully, can get rid of and make the unbalanced essential factor of ZnO grain growth.
But this compound finally can only be got rid of by Sb
2O
3Become Sb
2O
4The time make the unbalanced essential factor of grain growth, can not represent that but ZnO can keep uniformity in grain growth thereafter, ZnO is necessary here.Contain in the compound trace Zn the time, compound thereafter will with the big quantitative response of ZnO as main material.In this course of reaction, because originally Zn-Bi, Zn-Sb form compound, promptly reactive just high, so when surpassing sintering temperature, owing to its reaction begins to react sharp.Therefore can think,, can relax above-mentioned rapid reaction, suppress growing up of abnormal grain by add Zn in advance micro-ly.
Even Bi and ZnO do not react, also forming liquid phase in the sintering process thereafter.We can say that in piezo-resistance that form crystal boundary is Bi, that is to say, add Bi from the viewpoint of what is called control grain growth, not equal to add Bi in order to form crystal boundary.But, owing to only add, not only form crystal boundary, but also influential to the crystal grain inhomogeneities, be important so grain growth can balancedly be added.Equally, though Sb is particularly influential to grain growth, by be added on and Zn between the The Uniform Control of the spinelle that the forms grain growth during with respect to high temperature show important effect.In the crystallization of spinelle phase, do not have Bi, but since the pyrochlore of the presoma that is called the spinelle phase mutually in Bi be necessary, so also together roasting of Bi.When excessively adding Zn, be adsorbed on the Zn though want the Sb that suppresses by Bi-Sb produces, the karyomorphism of Zn and Sb becomes a star, and has finally formed the crystal seed of exaggerated grain growth.Few just because of amount, account for major part according to the compound of probability theory Bi-Sb, on its part, adsorb zinc, just can control above-mentioned reaction, volume adds, and after mainly having formed the Bi-Zn compound, finally in sintering process thereafter exaggerated grain growth takes place.Thereby, the roasting stage with bismuth oxide (Bi
2O
3) be set at 0.1～1.5 mole of %, with antimony oxide (Sb
2O
3) be set at 0.01～2.0 mole of %, zinc oxide (ZnO) is set at 0.1～1.0 mole of %.
Below, research is by the high impulse toleranceization of adding the piezo-resistance that donor element causes.As described above, for the high impulse toleranceization 2 kinds of methods are arranged.A kind of method is that the thickness of two Schottky barriers of crystal boundary is thickened, and when strengthening electric current outward, the electron avalanche formula that can suppress to be caused by tunnel effect leaps the phenomenon of crystal boundary.Another kind method is by reducing the ratio resistance of zinc oxide (ZnO) crystal grain, improve thermal diffusion efficient, and it is all to make the Joule heat of generation be diffused into element as soon as possible, to prevent the destruction of crystal boundary part.
But, even the thickness of Schottky barrier is thickened, form the crystal boundary of the big electric current of tolerance, if but the Joule heat that produces Joule heat big or that produce when concentrating on the crystal boundary partly is difficult to obtain good tolerance.Thereby in order to improve the pulse tolerance, the ratio resistance of the latter's reduction zinc oxide (ZnO) crystal grain, raising thermal diffusion efficient are important.By adding aluminium (Al) in forming at this, can improve the pulse tolerance significantly as donor element.
In addition, the titanium (Ti) by will similarly forming the spinelle phase and be that glass joins above-mentioned Bi as rare earth element and Si that crystal boundary forms material
2O
3-Sb
2O
3-ZnO is in the mixture, adds in the roasting raw material, can further improve the characteristic of piezo-resistance.Simultaneously, by making the addition optimization of cobalt oxide, manganese oxide, chromium oxide, boric acid, can obtain high performance piezo-resistance characteristic.
Below, the evaluation result of manufacturing experimently is described.In all trial-production evaluation results, firing temperature is 1100 ℃ and kept 5 hours down that article shape is 3216 sizes, makes the internal electrode number of plies with 4 layers laminated construction, and the electric conducting material of the platinum (Pt) of electrode material use 100% is stuck with paste.
At first, as a comparative example, will be shown in table 1 with the evaluation result of the piezo-resistance of the trial-production of manufacturing process in the past.This preproduction is with respect to 100 moles of % of zinc oxide (ZnO), by other adding bismuth oxide (Bi
2O
3) 0.5 mole of %, antimony oxide (Sb
2O
3) 1.0 moles of %, 1.0 moles of % of cobalt oxide (CoO), manganese oxide (MnO
2) 1.0 moles of %, chromium oxide (Cr
2O
3) 0.5 mole of %, boric acid (H
3BO
3) 0.5 mole of %, aluminium oxide (Al
2O
3) 0.0001 mole of %, titanium oxide (TiO
2) 0.1 mole of %, silica (SiO
2) 0.5 mole of %, carry out raw material and mix, make according to step 104～115 of manufacturing process shown in Figure 2.In addition, with bismuth oxide (Bi
2O
3) and antimony oxide (Sb
2O
3) add after the roasting in 1 hour carrying out under 800 ℃ in advance.The thickness of change blank sheet is made 3 kinds of low voltage varistors, middle pressure piezo-resistance, high voltage varistor.Numerical value represents that with the σ of mean value and expression deviation the sample number is 20.
Table 1
| The electrical characteristics assessment item | Low voltage varistor | The middle piezo-resistance of pressing | High voltage varistor |
| Piezo-resistance voltage (1mA) | 12.1V(σ＝2.2) | 46.8V(σ＝1.6) | 84.3V(σ＝2.6) |
| Leakage current (V 1mA* 0.8 adds) | 5μA(σ＝1.1) | 3μA(σ＝1.0) | 2μA(σ＝0.8) |
| α value (between the 0.01-1mA) | 21(σ＝2.2) | 23(σ＝1.3) | 23(σ＝1.1) |
| Deboost (2A) | 23V(σ＝2.1) | 75V(σ＝2.3) | 135V(σ＝2.1) |
| Impact tolerance (8/20 μ s waveform 160A adds) | 30A(σ＝4.5) | 60A(σ＝5.8) | 83A(σ＝8.8) |
It is such that result as shown in table 1 shows, even a roasting in advance has the bismuth oxide (Bi that grain growth promotes to suppress effect
2O
3), antimony oxide (Sb
2O
3), can not obtain the good piezo-resistance of deboost.Therefore anticipation is by grain growth and the ZnO-Bi with ZnO
2O
3-Sb
2O
3The reaction of the formation pyrochlore spinelle phase that takes place in the system separately can obtain the uniformity of ZnO, seeks low restriction voltageization.Therefore, by adding zinc oxide (ZnO) to Bi
2O
3-Sb
2O
3In the mixture, change the addition of zinc oxide (ZnO), carry out roasting in advance, the affirmation how deboost is changed the results are shown in table 2.In addition, addition is represented with the addition that adds with respect to the zinc oxide (ZnO) of 100 moles of %.As long as Bi/Sb is than want piezo-resistance voltage Gao Shixiao greatly when wanting piezo-resistance voltage low.In this trial result, the Bi/Sb ratio is taken as 1, in the mixture of 0.5 mole of % of each interpolation, change the ZnO addition, test.Other composition is identical with the composition of the piezo-resistance shown in the table 1.
Table 2
This result can confirm, adds zinc oxide (ZnO) and Bi in the scope of 0.1～1 mole of %
2O
3-Sb
2O
3Mixture is roasting together, and its limit voltage ratio becomes 1.5, and the deboost characteristic improves.
Studied the aluminium (Al) that adds as donor element, to seek the high impulse toleranceization.In order to improve the pulse tolerance, the ratio resistance, the raising thermal diffusion efficient that reduce zinc oxide (ZnO) crystal grain are important.Therefore, making changes the Al that becomes donor element with respect to ZnO
2O
3The preproduction of addition, add 500 (A) with 8/20 μ s surge waveform, the rate of change before and after the impact of having measured piezo-resistance voltage adds.It the results are shown in table 3.Al
2O
3The Al of addition to contain in the raw material
2O
3Concentration (ppm) expression.Other additive, addition are identical with the trial result shown in the table 2, and the addition of ZnO is 0.5 mole of %.This result can confirm, by add Al in 10～1000ppm scope
2O
3, can seek the high impulse toleranceization.
Table 3
Can confirm low restriction voltageization, the high impulse toleranceization of zinc oxide multilayer chip piezoresistor by above-mentioned trial-production evaluation result.But, also must study other characteristic as above-mentioned piezo-resistance.Therefore, studied and other the correlation of additive addition, verified the composition of piezo-resistance and the relation of piezo-resistance characteristic.
The research of forming is divided into following 7 projects and manufactures experimently evaluation.
(a) with zinc oxide (ZnO) Bi of roasting together
2O
3-Sb
2O
3The research of ratio of components
(b) crystal boundary forms the research (CoO, MnO) of basic additive
(c) research (Cr of reliability stabilisation material
2O
3)
(d) glass and have the research (H of the additive of alms giver's effect
3BO
3)
(e) high performance 1 of roasting raw material composition, the research (TiO of titanium oxide
2)
(f) high performance 2 of roasting raw material composition, the research (Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) that terres rares adds
(g) high performance 3 of roasting raw material composition, the research (SiO of silicon dioxide
2)
(a) with zinc oxide (ZnO) Bi of roasting together
2O
3-Sb
2O
3The research of ratio of components
As the roasting raw material, studied Bi as basic composition
2O
3-Sb
2O
3Ratio of components combination.The α value that is used as the nonlinear evaluation index of piezo-resistance is estimated.The metewand of α value is considered practicality, is estimated as lower limit with 20 between piezo-resistance electric current 0.01mA～1mA.Evaluation result is shown in table 4.Can distinguish by this result,, wish the Bi that adds in addition with respect to 100 moles of % of zinc oxide (ZnO)
2O
3Addition be 0.1～1.5 mole of %, Sb
2O
3Addition be 0.01～2.0 mole of %.In addition, the addition of ZnO is 0.5 mole of %.
Table 4
Below, to studying for the sintering temperature that obtains low restriction voltageization.In the trial result shown in the table 4, for making 0.5 mole of %Bi
2O
3, 0.5 mole of %Sb
2O
3The sintering temperature of the roasting raw material of addition changes the preproduction of making, and the relation of its limit voltage ratio and sintering temperature is shown in table 5.The composition of preproduction is: the Bi of the ZnO of 100 moles of %, 0.5 mole of %
2O
3, 0.5 mole of % Sb
2O
3, 0.5 mole of % Cr
2O
3, 0.5 mole of % H
3BO
3, 0.5 mole of % CoO, MnO, the Al of 0.5 mole of %
2O
3Concentration 20ppm.Can confirm by this trial-production evaluation result, wish that sintering temperature is in 700～1000 ℃ scope.
Table 5
(b) crystal boundary forms the research (CoO, MnO) of basic additive
As the basic additive that crystal boundary forms, studied the addition of cobalt oxide (CoO) and manganese oxide (MnO).Estimate with the α value equally with the evaluation result of table 4 expression.The metewand of α value is considered practicality, is estimated as lower limit with 20 between 0.01mA～1mA.In addition, the roasting raw material with respect to ZnO100 mole %, adds 0.5Bi in addition
2O
3-0.5Sb
2O
3Composition condition beyond the-0.5ZnO, CoO, MnO is identical with the evaluation test shown in table 1 and the table 2.Evaluation result is shown in table 6, table 7.This result can confirm that when the addition of cobalt (CoO) and manganese (MnO) was 0.1～1.5 mole of % respectively, the α value reached more than 20.
Table 6
Table 7
Below, same cobalt and manganese as transition metal is added in combination, carries out the evaluation of α value.It the results are shown in table 8.The composition of the preproduction except that cobalt and manganese is: the Bi of the ZnO of 100 moles of %, 0.5 mole of %
2O
3, 0.5 mole of % Sb
2O
3, 0.5 mole of % Cr
2O
3, 0.5 mole of % H
2BO
3, Al
2O
3Concentration 20ppm.Can confirm that by this result the addition of cobalt oxide (CoO) and manganese oxide (MnO) is to add up to when adding 0.1～1.5 mole of % more than a kind, can obtain the α value more than 20.
Table 8
(c) research (Cr of reliability stabilisation material
2O
3)
As reliability stabilisation material, studied chromium oxide (Cr
2O
3) addition.Estimate with the rate of change that adds the piezo-resistance voltage before and after the impulse current.The impulse current that adds is taken as 300A without exception, and the judgement of good product is set at the piezo-resistance voltage change ratio in 10%.In addition, the roasting raw material is for being 0.5Bi in addition with respect to 100 moles of % of ZnO
2O
3-0.5Sb
2O
3-0.5ZnO is with respect to the other cobalt oxide that adds 0.5 mole of % of 100 moles of % of ZnO.The results are shown in table 9.This result can confirm, by add the chromium oxide (Cr of 0.01～2 mole of % with respect to 100 moles of % of ZnO
2O
3) addition, can obtain the high piezo-resistance of reliability.
Table 9
(d) research (H of glass additive
3BO
3, SiO
2)
For the optimization of glass additive addition, the research of 2 kinds of tests of the leakage current when having carried out so-called impact energy tolerance and high temperature.The impact energy tolerance is big more, and the tolerance during big electric current is good more, because the leakage current during high temperature is the leakage current that flows through when standby, so more little good more.
To boric acid (H
3BO
3) the research of addition.
The roasting raw material adds 0.5Bi in addition with respect to 100 moles of % of ZnO
2O
3-0.5Sb
2O
3-0.5ZnO with respect to 100 moles of % of ZnO, adds the cobalt oxide of 0.5 mole of % in addition, with respect to 100 moles of % of ZnO, adds the chromium oxide of 0.3 mole of % in addition.Table 10 expression impact tolerance (ampere: A), table 11 expression energy tolerance (joule: J), the leakage current (microampere: μ A) during table 12 expression high temperature.These results can confirm, with respect to 100 moles of % of ZnO, add the boric acid (H of 0.01～2.0 mole of % in addition
3BO
3), can seek high performance.
Table 10
Table 11
Table 12
(e) high performance 1 of roasting raw material composition, the research (TiO of titanium oxide
2)
Can confirm according to The above results,, add the roasting raw material in addition, to become (0.1～1.5 mole of %) Bi by with respect to 100 moles of % of ZnO
2O
3-(0.01～2 mole of %) Sb
2O
3-(0.1～1 mole of %) ZnO is such, can obtain hanging down restriction voltageization and α value in the high-performance piezo-resistance more than 20.As further improvement, studied by titanium oxide being joined in the roasting raw material composition high performance of impact energy tolerance.Its evaluation result is impacted tolerance and is shown in table 13, and the energy tolerance is shown in table 14.In addition, accept above-mentioned result of the test, composition is with respect to 100 moles of % of ZnO, to add the CoO of 0.5 mole of %, the Cr of 0.3 mole of % in addition
2O
3, 0.3 mole of % H
3BO
3, studied the roasting raw material.Its result can confirm, by at the Bi as the roasting raw material
2O
3-Sb
2O
3Among-the ZnO, add the titanium oxide (TiO of 0.01～0.5 mole of % in addition with respect to ZnO100 mole %
2), can further improve the impact energy tolerance.
Table 13
Table 14
(f) research (Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) of the high performance 2 of roasting raw material composition, terres rares interpolation
Can confirm according to The above results,, add the roasting raw material in addition, to become (0.1～1.5 mole of %) Bi by with respect to 100 moles of % of ZnO
2O
3-(0.01～2 mole of %) Sb
2O
3-(0.1～1 mole of %) ZnO is such, can obtain hanging down restriction voltageization and α value in the high-performance piezo-resistance more than 20.As further improvement, studied by rare earth element being joined in the roasting raw material composition high performance of impact energy tolerance.Its evaluation result is impacted tolerance and is shown in table 15, and the energy tolerance is shown in table 16.In addition, accept above-mentioned result of the test, composition is with respect to 100 moles of % of ZnO, to add the CoO of 0.5 mole of %, the Cr of 0.3 mole of % in addition
2O
3, 0.3 mole of % H
3BO
3, studied the roasting raw material.Its result can confirm, by at the Bi as the roasting raw material
2O
3-Sb
2O
3Among-the ZnO,, add the rare-earth oxide (A of 0.01～0.5 mole of % in addition with respect to 100 moles of % of ZnO
2B
3), can further improve and impact tolerance, energy tolerance.
Table 15
Table 16
(g) high performance 3 of roasting raw material composition, the research (SiO of silicon dioxide
2)
Can confirm according to The above results,, add the roasting raw material in addition, to become (0.1～1.5 mole of %) Bi by with respect to 100 moles of % of ZnO
2O
3-(0.01～2 mole of %) Sb
2O
3-(0.1～1 mole of %) ZnO is such, can obtain hanging down restriction voltageization and α value in the high-performance piezo-resistance more than 20.As further improvement, studied and passed through silicon dioxide (SiO
2) join in the roasting raw material composition, impact the high performance of tolerance energy tolerance.Its evaluation result is impacted tolerance and is shown in table 17, and the energy tolerance is shown in table 18.In addition, accept above-mentioned result,, add the CoO of 0.5 mole of %, the H of 0.3 mole of % in addition with respect to 100 moles of % of ZnO
3BO
3, 0.3 mole of % Cr
2O
3On the basis as basic composition, studied the partial roasting raw material.Its result can confirm, by at the Bi as the roasting raw material
2O
3-Sb
2O
3Among-the ZnO,, add the silica (SiO of 0.01～0.5 mole of % in addition with respect to 100 moles of % of ZnO
2), can further improve and impact tolerance, energy tolerance.
Table 17
Table 18
By above result, will contain the bismuth oxide (Bi of 0.1～1.5 mole of % in addition with respect to 100 moles of % of zinc oxide (ZnO)
2O
3), the antimony oxide (Sb of 0.01～2.0 mole of %
2O
3), the raw material of the zinc oxide (ZnO) of 0.1～1.0 mole of % carries out roasting in advance as the roasting raw material in 700～1000 ℃ temperature range, in this roasting raw material according to the roasting raw material in the zinc oxide (ZnO) that contains add up to and become 100 moles of % and add zinc oxide (ZnO) like that as main material, in addition, the cobalt oxide (CoO), the manganese oxide (MnO that add 0.1～1.5 mole of %
2) in more than a kind, the chromium oxide (Cr of 0.01～2 mole of %
2O
3), the boric acid (H of 0.01～2 mole of %
3BO
3), the aluminium oxide (Al of 10～1000ppm
2O
3), formally burn till, by this, can obtain the high-performance multilayer type piezoresistor.In addition, as the roasting raw material, also contain the titanium oxide (TiO of 0.01～0.5 mole of %
2), also contain with A
2B
3(A: rare earth element, B: oxygen element) rare earth element of 0.01～0.5 of form mole of % (Pr, Y, Nb etc.), also contain the silica (SiO of 0.01～0.5 mole of %
2), also be effective obtaining aspect the high-performance multilayer type piezoresistor.
So far, one embodiment of the present invention have been described, but the present invention is not limited to above-mentioned execution mode, self-evident, in its technological thought scope, can various mode implement.
Claims (4)
1. the manufacture method of a zinc oxide multilayer chip piezoresistor is characterized in that, according to zinc oxide (ZnO) be 100 moles of % with in the other addition relative, bismuth oxide (Bi with it
2O
3) be 0.1～1.5 mole of %, antimony oxide (Sb
2O
3) be 0.01～2.0 mole of %, cobalt oxide (CoO) and manganese oxide (MnO
2) in be 0.1～1.5 mole of %, chromium oxide (Cr more than a kind
2O
3) be 0.01～2 mole of %, boric acid (H
3BO
3) be 0.01～2 mole of %, in addition, aluminium oxide (Al
2O
3) concentration be that 10～1000ppm prepares these raw materials like that,
In these raw materials, to containing the bismuth oxide (Bi of whole amounts
2O
3) and antimony oxide (Sb
2O
3) and the roasting raw material of the zinc oxide (ZnO) of 0.1～1.0 mole of % in 700～1000 ℃ temperature range, heat-treat,
Add this roasting raw material and other raw material, form blank sheet,
On this blank sheet, form electric conducting material and stick with paste pattern,, after the formation chips, burn till this blank sheet lamination, cut-out.
2. the manufacture method of zinc oxide multilayer chip piezoresistor according to claim 1 is characterized in that, in the other addition with respect to 100 moles of % of zinc oxide (ZnO), the roasting raw material also contains the titanium oxide (TiO of 0.01～0.5 mole of %
2).
3. the manufacture method of zinc oxide multilayer chip piezoresistor according to claim 1 is characterized in that, in the other addition with respect to 100 moles of % of zinc oxide (ZnO), the roasting raw material also contains with A
2B
3(A: rare earth element, B: the rare earth element of 0.01～0.5 of form mole of % (Pr, Y, Nb etc.) oxygen element).
4. the manufacture method of zinc oxide multilayer chip piezoresistor according to claim 1 is characterized in that, in the other addition with respect to 100 moles of % of zinc oxide (ZnO), the roasting raw material also contains the silica (SiO of 0.01～0.5 mole of %
2).
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| CNA2007101934691A CN101447265A (en) | 2007-11-27 | 2007-11-27 | Method for fabricating zinc oxide multilayer chip piezoresistor |
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| CNA2007101934691A CN101447265A (en) | 2007-11-27 | 2007-11-27 | Method for fabricating zinc oxide multilayer chip piezoresistor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126852A (en) * | 2011-03-22 | 2011-07-20 | 襄樊市三三电气有限公司 | Method for preparing zinc oxide piezoresistor ceramic |
| CN102424576A (en) * | 2011-08-31 | 2012-04-25 | 清华大学 | Preparation method of non-linear composite material having adaptive uniform electric field |
| CN105084885A (en) * | 2014-05-06 | 2015-11-25 | 游钦禄 | Zinc oxide piezoresistor medium material and chip resistor preparation method |
| CN106252006A (en) * | 2016-09-22 | 2016-12-21 | 蚌埠万科电子科技有限公司 | The resistor sintered bar of Fast Installation |
| CN104867638B (en) * | 2014-02-26 | 2018-09-14 | 兴亚株式会社 | The rheostatic manufacturing method of Zinc oxide |
| CN111816398A (en) * | 2020-06-23 | 2020-10-23 | 上海大学 | Resistor disc preparation method capable of improving high-current impact stability |
| CN112236834A (en) * | 2018-06-06 | 2021-01-15 | 兴亚株式会社 | Zinc oxide piezoresistor |
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2007
- 2007-11-27 CN CNA2007101934691A patent/CN101447265A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126852A (en) * | 2011-03-22 | 2011-07-20 | 襄樊市三三电气有限公司 | Method for preparing zinc oxide piezoresistor ceramic |
| CN102126852B (en) * | 2011-03-22 | 2013-06-05 | 襄樊市三三电气有限公司 | Method for preparing zinc oxide piezoresistor ceramic |
| CN102424576A (en) * | 2011-08-31 | 2012-04-25 | 清华大学 | Preparation method of non-linear composite material having adaptive uniform electric field |
| CN102424576B (en) * | 2011-08-31 | 2013-03-06 | 清华大学 | Preparation method of non-linear composite material having adaptive uniform electric field |
| CN104867638B (en) * | 2014-02-26 | 2018-09-14 | 兴亚株式会社 | The rheostatic manufacturing method of Zinc oxide |
| CN105084885A (en) * | 2014-05-06 | 2015-11-25 | 游钦禄 | Zinc oxide piezoresistor medium material and chip resistor preparation method |
| CN106252006A (en) * | 2016-09-22 | 2016-12-21 | 蚌埠万科电子科技有限公司 | The resistor sintered bar of Fast Installation |
| CN112236834A (en) * | 2018-06-06 | 2021-01-15 | 兴亚株式会社 | Zinc oxide piezoresistor |
| CN111816398A (en) * | 2020-06-23 | 2020-10-23 | 上海大学 | Resistor disc preparation method capable of improving high-current impact stability |
| CN111816398B (en) * | 2020-06-23 | 2022-01-07 | 上海大学 | Resistor disc preparation method capable of improving high-current impact stability |
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