CN1740113A - Electron emitter - Google Patents
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- CN1740113A CN1740113A CN 200510092938 CN200510092938A CN1740113A CN 1740113 A CN1740113 A CN 1740113A CN 200510092938 CN200510092938 CN 200510092938 CN 200510092938 A CN200510092938 A CN 200510092938A CN 1740113 A CN1740113 A CN 1740113A
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Abstract
Provided is a piezoelectric-film-type electron emitter which enables suppression of reduction of electron emission quantity due to repeated use thereof, and which exhibits high durability. The electron emitter includes a substrate (11); an emitter section (12) formed of a dielectric material; a first electrode (14) formed on the top surface(12a) of the emitter section; and a second electrode (16) formed on the bottom surface(12b) of the emitter section. The dielectric material forming the emitter section contains a dielectric composition having an electric-field-induced strain (i.e., percent deformation under application of an electric field of 4 kV/mm, as measured in a direction perpendicular to the electric field) of 0.07% or less.
Description
Technical field
The present invention relates in this wide variety of devices of utilizing electron rays of field-emitter display indicating meters such as (FED) or electron beam irradiation device, light source, electron device manufacturing installation, electronic circuit electronic emission element as electronic radial source.
Background technology
Constituting of above-mentioned electronic emission element as everyone knows, in the vacuum of specified vacuum degree, by emtting electrode portion (electron emission part) being applied the electric field of regulation, launched electronics from this emtting electrode portion.When this electronic emission element was applied to FED, several electronic emission elements were two-dimensionally arranged on matrixes such as glass or pottery.In addition, corresponding to these several electronic emission elements, several fluor are configured to respectively and each electronic emission element specified gap of being separated by.Like this, by the electronic emission element of the optional position in several electronic emission elements that optionally drive two-dimensional arrangements, launch electronics from the electronic emission element of optional position.Bump with fluor because this electronics that is launched out flies in above-mentioned gap, just the fluor from the optional position sends fluorescence, thereby can carry out desired demonstration.
In the past, among the above-mentioned electronic emission element, it was known constituting emtting electrode portion by dielectric medium (piezoelectrics).Such electronic emission element is called " piezoelectricity membranous type electronic emission element ".This piezoelectricity membranous type electronic emission element, cheap for manufacturing cost, therefore can be used for the FED that several electronic emission elements are as mentioned above disposed two-dimensionally with the area than broad aptly.As the prior art of this piezoelectricity membranous type electronic emission element, for example be disclosed in that the spy opens the 2004-146365 communique, the spy opens in the 2004-172087 communique.
In the such membranous type of piezoelectricity in the past electronic emission element, the part on the surface of the emtting electrode portion that is made of dielectric medium is covered by cathode electrode.In addition, on the inside of this emtting electrode portion or on the surface of emtting electrode portion and and cathode electrode be provided with the position configuration anode electrode of specified gap.Promptly, near the outer edge of the lip-deep cathode electrode of emtting electrode portion, form neither form cathode electrode do not form yet anode electrode emtting electrode portion surface exposed division (wherein, this exposed division forms the major portion of the electron emission effect in the emtting electrode portion, hereinafter referred to as " electron emission region ").
This electronic emission element is in the past worked as following.At first, as the fs, between cathode electrode and anode electrode, a side who applies cathode electrode becomes the voltage of noble potential.Utilization applies the electric field that voltage forms by this, the polarized state that the above-mentioned electron emission region in the emtting electrode portion is configured to stipulate.Then, as subordinate phase, between cathode electrode and anode electrode, a side who applies cathode electrode becomes the voltage of low potential.At this moment, in the outer edge emission primary electron of cathode electrode, the polarization of emtting electrode portion reverses.At the above-mentioned electron emission region of the emtting electrode portion that this polarization reverses, above-mentioned primary electron bumps, thus from this electron emission region emission secondary electron.This secondary electron flies to prescribed direction by the electric field from the regulation of outside, utilizes the electron emission of this electronic emission element thus.
Summary of the invention
But, in piezoelectricity membranous type electronic emission element in the past, existing owing to use repeatedly, electron emission amount reduces such problem significantly.And in the emtting electrode portion and electrode and matrix as the integrant of this piezoelectricity membranous type electronic emission element, the integrant that occurrence features changes owing to use repeatedly mainly is an emtting electrode portion.Therefore think that the major cause that the electron emission amount that is caused by using repeatedly of electronic emission element reduces is by the deterioration of using the emtting electrode portion that causes repeatedly.
This point is as constituting the dielectric substance (piezoelectric) of the emtting electrode portion of piezoelectricity membranous type electronic emission element in the past, main piezoelectric that is suitable for piezoelectric driving systens such as ink-jet printer and the piezoelectric that is used for strong dielectric memory of using.As the former piezoelectric driving systen piezoelectric, mainly use in the three component system solid solution compositions of PMN (magnesium lead niobate)-PZ (lead zirconates)-PT (lead titanate), consist of near the material of boundary line (so-called MPB (Morphotropic Phase Boundary)) in regular crystal zone and false cube crystalline substance and territory, rhombohedron crystalline region.In addition, strong dielectric memory piezoelectric as the latter, the main PZT based material that uses (consists of the summit (0 of PT in the PMN-PZ-PT three component system solid solution phasors, 1,0) and the summit (0 of PZ, 0,1) on the wire and near material) in, the ratio of PT is about 55% or its above material.
But the former piezoelectric driving systen and electronic emission element are said, the principle of work difference, and therefore the mechanism by the deterioration of using the piezoelectric that causes repeatedly is also certainly different.That is, in electronic emission element, the reverse of the direction of polarization by utilizing piezoelectric is from the surface emitting electronics of this piezoelectric.With respect to this, in piezoelectric driving systen, by the direction of polarization of the polarization processing predetermined fixed piezoelectric of stipulating, by applying the electric field of or vertical direction parallel with described immobilized direction of polarization, flexible or shearing strain take place in piezoelectric.In other words, the piezoelectric driving systen piezoelectric is that the reverse of the direction of polarization in the described piezoelectric is not preestablished.Therefore, the piezoelectric driving systen piezoelectric is not considered repeatedly to reverse the deterioration in characteristics cause by direction of polarization.
On the other hand, the latter's strong dielectric memory at this point of the reverse that utilizes direction of polarization, interosculates on principle of work with electronic emission element.But, in strong dielectric memory, be called as the good SrBi of weather resistance
2Ta
2O
9(SBT) or Bi
4Ti
3O
12(BIT), because remnant polarization Pr is little, so electron emission amount is few, is not suitable for FED.In addition, the ratio of PT lacks weather resistance, 10 roughly more than or equal to 55% PZT
6～10
7Inferior polarization reverses deterioration and just becomes remarkable.
Like this, in piezoelectricity membranous type electronic emission element in the past,, do not consider too much selection for it about the material of the emtting electrode portion that electronic emission element was fit to that can realize having desired weather resistance.
The present invention finishes in view of the above-mentioned problems, is purpose so that the piezoelectricity membranous type electronic emission element that can improve the electron emission amount reduction that causes by using repeatedly to be provided.
The matrix that electronic emission element of the present invention possesses the emtting electrode portion that is made of dielectric medium, the electrode that forms on the surface of this emtting electrode portion and supports described emtting electrode portion and electrode.
So to achieve the above object, electronic emission element of the present invention is characterised in that, the described dielectric electric field induction distortion that constitutes described emtting electrode portion is to be less than or equal to 0.07%.At this, described electric field induction distortion is when applying the electric field of 4kV/mm and the deformation rate on this electric field vertical direction.
That is, piezoelectric, in the process that forms the dielectric layer that constitutes emtting electrode portion (when for example burning till), crystalline structure is a cube crystalline substance when high temperature, and (temperature of Curie temperature) crystalline structure mainly changes to regular crystal in process of cooling after this.When this phase transformation, the inside of this piezoelectric forms many fine farmlands (refer to the zone that direction of polarization reaches unanimity, be also referred to as the territory).When forming this farmland, distortion at interface limitations (constraint) lattice on the farmland of adjacency, because lattice parameter can not be changed to the value of the regular crystal the steady state from the value of cube crystalline substance, so the lattice in this farmland becomes the shape of the distortion from steady state towards prescribed direction.Its result, emtting electrode portion form and are right after back (promptly make electronic emission element and be right after the back), and the inside of this emtting electrode portion will produce big unrelieved stress.
After this, to this emtting electrode portion, apply alternating electric field (by the electric field of driving voltage generation) for electron emission, when carrying out polar reverse and rotation repeatedly, owing to apply the electricapparatus transformation (promptly by the distortion that applies electric field induction) that electric field causes by this, the repeated stress that takes place to echo in the inside of this emtting electrode portion, mainly cause by the polar rotation with above-mentioned alternating electric field.Because at the inner repeated stress that takes place of this emtting electrode portion, generation can make the arrangement again on above-mentioned unrelieved stress demulcent farmland, the ordered state on farmland is from making the change of state after electronic emission element is right after.
Especially, under the situation that this emtting electrode portion is made of the big material of above-mentioned electric field induction distortion, become big as above-mentioned unrelieved stress.Therefore, in the case, further promote variation (arrangement again on farmland) as the ordered state on above-mentioned farmland.
In addition, emtting electrode portion is fixed on the matrix (directly or pass through electrode layer, below identical) under the situation about forming, fixed part between matrix and emtting electrode portion, distortion by matrix (perhaps described electrode layer) restriction (constraint) this emtting electrode portion, therefore not compared by the situation of shape constraining with emtting electrode portion, the above-mentioned basis that produces in this emtting electrode portion electron emission region of the surface of described fixed part opposing face (especially with) applies the degree that stress that alternating electric field causes takes place and becomes big.Therefore, in the case, further promote the arrangement again on above-mentioned farmland.
That this basis applies is that alternating electric field (and generation of the repeated stress that causes thus) produces, the arrangement again (variation of farmland state in the emtting electrode portion) on the unrelieved stress demulcent farmland when emtting electrode portion is formed, be considered to by using the reduction (being the deterioration of emtting electrode portion) of the electron emission amount that causes closely related repeatedly.
Therefore, in the present invention, utilize with above-mentioned electric field induction and be out of shape the dielectric medium formation emtting electrode portion of little dielectric composition as principal constituent.Thus, the stress that produces when the polarization rotation diminishes, therefore the mitigation and the farmland of the unrelieved stress when using the emtting electrode portion that causes to form are repeatedly arranged (variation of farmland state) again and are suppressed, thereby can suppress the reduction of the electron emission amount that caused by use repeatedly.That is, the weather resistance of this emtting electrode portion is improved.
At this, above-mentioned dielectric medium is suitable to be made of following the 1st to the 6th dielectric composition.
The 1st dielectric composition is as principal constituent and contain the dielectric composition of Ni with the composition of following general formula (1) expression, be the Ni content in this dielectric composition, be equivalent to the dielectric composition of 0.05～2.0 weight % when being converted into the content of the NiO in this dielectric composition.
General formula (1): Pb
xBi
p(Mg
Y/3Nb
2/3)
aTi
B-zM
zZr
cO
3
[in the above-mentioned general formula (1), 0.85≤x≤1.03,0.02≤p≤0.1,0.8≤y≤1.0, and a, b, c be with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), the decimal in the scope of (0.375,0.425,0.200) 5 encirclements.In addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.]
At this, described the 1st dielectric composition is suitable to constitute, in the dielectric composition of described composition with following general formula (1 ') expression as principal constituent, 2～10mol% of Pb atom is replaced by the Bi atom, and 2～10mol% of Ti atom is selected from least a replacement among Nb, Ta, Mo, the W, and this dielectric composition all contains the NiO of 0.05～2.0 weight % relatively.
General formula (1 '): Pb
x(Mg
Y/3Nb
2/3)
aTi
bZr
cO
3
[in the above-mentioned general formula (1 '), 0.95≤x≤1.05,0.8≤y≤0.1, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), the decimal in the scope of (0.375,0.425,0.200) 5 encirclements.]
Such dielectric composition for example obtains as following.At first, use the oxide compound of Pb, Mg, Nb, Ti, Zr, Ni, each element such as Bi, Ta or carbonate etc., obtain the mole fraction of each element is modulated at mixture in the described scope.Then, this mixture is packed in the encloses container, synthesize in the specified temperature pre-burning.Then, pulverize the pre-burning thing that obtains by pre-burning, make desired particle diameter, just can access above-mentioned dielectric composition.
Use the dielectric composition that obtains like this, (for example utilize general manufacturing process, silk screen print method, dip coating, coating method, electrophoretic method, aerosol sedimentation, ionic fluid method, sputtering method, vacuum vapour deposition, ion plating method, CVD (Chemical Vapor Deposition) method (CVD), plating or raw cook method) form dielectric layer, just can access emtting electrode of the present invention portion.Preferably again the dielectric layer that obtains is like this heat-treated or burnt till, improve the electrical characteristic of dielectric layer, improve density.
The 2nd dielectric composition is by constituting as principal constituent and the dielectric composition that contains Ni with the composition of following general formula (2) expression, be when the Ni content in this dielectric composition is converted into the content of the NiO in this dielectric composition, be equivalent to the dielectric composition of the amount of 0.05～2.0 weight %.
General formula (2): Pb
xBi
pSr
q(Mg
Y/3Nb
2/3)
aTi
B-zM
zZr
cO
3
[in the above-mentioned general formula (2), 0.65≤x≤1.01,0.02≤p≤0.1,0.02≤q≤0.20,0.8≤y≤1.0, and a, b, c be with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), the decimal in the scope of (0.375,0.425,0.200) 5 encirclements.In addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.]
In addition, described the 2nd dielectric composition is suitable to constitute, in the dielectric composition of described composition with described general formula (1 ') expression as principal constituent, 2～10mol% of Pb atom is replaced by the Bi atom, 2～20mol% of Pb atom is replaced by Sr, and 2～10mol% of Ti atom is selected from least a replacement among Nb, Ta, Mo, the W, and all contains the NiO of 0.05～2.0 weight % with respect to this dielectric composition.The preparation of such the present invention's the 2nd dielectric composition is also carried out in the same manner with above-mentioned the 1st dielectric composition.
At this, the described the 1st and the 2nd dielectric composition is being converted into MnO
2Containing ratio the time, the Mn that contains the amount that is equivalent to 0.05～1.0 weight % is suitable.
Like this, in the specified range of the invention described above, be more preferably the amount that replaces Pb by Bi and be 2～5mol% (be that x in the described general formula (1) is 0.90≤x≤1.03, p is 0.02≤p≤0.05).In addition, being more preferably the amount that replaces Pb by Sr and being 1～15mol% (is that x in the described general formula (2) is 0.70≤x≤1.02, p is that (being more preferably x is 0.75≤x≤1.02 in 0.02≤p≤0.10, p is 0.02≤p≤0.05), q is 0.01≤q≤0.15), more preferably 1～12mol% (is that x in the described general formula (2) is 0.73≤x≤1.02, p is that 0.02≤p≤0.10 (being more preferably x is 0.78≤x≤1.02, and p is 0.02≤p≤0.05), q are 0.01≤q≤0.12).In addition, being more preferably amount by replacement Ti such as Nb is 3～8mol% (be in described general formula (1) and (2) z be 0.03≤z≤0.08).In addition, being more preferably when the content of Ni is converted into the containing ratio of NiO, is the amount of 0.10～1.5 weight %.0.20～1.0 weight % more preferably.In addition, be more preferably the content of Mn is converted into MnO
2Containing ratio the time, be the amount of 0.1～1.0 weight %.The amount of 0.2～0.8 weight % more preferably.
If use electronic emission element of the present invention, just can improve the deterioration that causes by using repeatedly than in the past electronic emission element with this formation.Improve the weather resistance of electronic emission element thus.
The 3rd dielectric composition is that the dielectric composition of representing with following general formula (3) is the material of principal constituent.
General formula (3): Pb
x(Mg
Y/3Nb
2/3)
aTi
bZr
cO
3
[in the above-mentioned general formula (3), 0.95≤x≤1.05,0.90≤y≤1.10, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), the decimal in the scope of (0.250,0.360,0.390) 5 encirclements.]
The 4th dielectric composition is that the dielectric composition of representing with following general formula (4) is the material of principal constituent.
General formula (4): Pb
X-pMa
p(Mg
Y/3Nb
2/3)
aTi
bZr
cO
3
[in the above-mentioned general formula (4), the scope of x, y, a, b, c is identical with described general formula (3).In addition, Ma is selected from least a among Sr, La, the Bi.]
The 5th dielectric composition is that the dielectric composition of representing with following general formula (5) is the material of principal constituent.
General formula (5): Pb
x(Mg
Y/3Nb
2/3)
aTi
B-qMb
qZr
cO
3
[in the above-mentioned general formula (5), the scope of x, y, a, b, c is identical with described general formula (3).In addition, Mb is selected from least a among Nb, Ta, Mo, the W.]
The 6th dielectric composition is that the dielectric composition of representing with following general formula (6) is the material of principal constituent.
General formula (6): Pb
X-pMa
p(Mg
Y/3Nb
2/3)
aTi
B-qMb
qZr
cO
3
[in the above-mentioned general formula (6), the scope of x, y, a, b, c is identical with described general formula (3).In addition, Ma is identical with (5) with general formula (4) with Mb.]
Above-mentioned the 4th～the 6th dielectric composition, in other words, in the dielectric composition of described composition as principal constituent with described general formula (3) expression, can be with a part that is selected from least a replacement Pb atom among Sr, La, the Bi, and/or can be with a part that is selected from least a replacement Ti atom among Nb, Ta, Mo, the W.Because replace the part of Pb with Sr, thereby the electric field induction distortion is little, on the other hand, the reduction of remnant polarization Pr is little, that the electronics discharging amount is become more is possible while therefore improve weather resistance.In addition, owing to replace the part at the B position in the perovskite structures with La, Bi, Nb, W, Mo, Ta etc., thereby should become bigger by replacement valence mumber partly than the average valence mumber 4 at B position, in order to remedy this, in the positively charged ion position, produce the hole.Because this hole hinders the rotation on farmland, its weather resistance raising as a result.
In having the electronic emission element of the present invention of described formation, the electrode that forms on the surface of described emtting electrode portion is and for (the particularly described electron emission region) emitting electrons and the generation source of driving voltage that is used to produce electric field that need be applied near described emtting electrode portion (particularly its surperficial electron emission region) is electrically connected from above-mentioned surface.Specifically, for example on described surface, form in the 1st electrode, on described surface or the inside form the 2nd electrode, these the 1st are connected (in most cases, the 2nd electrode is a ground connection) with the 2nd electrode with the output terminal in described driving voltage generation source.Then, by this electrode is applied described driving voltage, at the electric field that applies regulation by the emtting electrode portion (particularly its surperficial electron emission region) that constitutes as the dielectric medium of principal constituent with described dielectric composition, just launch electronics from described electron emission region.
At this, from the viewpoint that weather resistance improves, described general formula (3) is in (6), described a, b, c preferably is in by (0.500,0.320 in described trigonometric coordinates, 0.180), (0.500,0.100,0.400), (0.300,0.100,0.600), (0.050,0.225,0.725), (0.050,0.425,0.525), (0.380,0.320,0.300) in the scope of 6 encirclements, more preferably be in by (0.500,0.320,0.180), (0.500,0.150,0.350), (0.350,0.150,0.500), (0.050,0.350,0.600), (0.050,0.425,0.525), in the scope of (0.380,0.320,0.300) 6 encirclements.
In addition, in described general formula (4) and (6), the described p value p (Sr) when Ma is Sr suits in 0.03～0.15 scope, and is preferably in 0.03～0.10 scope, further suits in 0.05～0.07 scope.
In addition, in described general formula (4) and (6), the described p value p (La+Bi) when Ma is La/ or Bi suits in 0.002～0.015 scope, and is preferably in 0.003～0.10 scope, further suits in 0.005～0.009 scope.
Especially preferably contain 0.05～0.07 Sr, and contain the formation of 0.005～0.009 La with mole fraction with mole fraction.
In addition, in described general formula (5) and (6), described q value suits in 0.01～0.15 scope, and is preferably in 0.02～0.10 scope, further suits in 0.02～0.08 scope.
The the 3rd to the 6th dielectric composition so also can prepare in the same manner with the 1st and the 2nd above-mentioned dielectric composition.Then, use the dielectric composition obtain and the above-mentioned described emtting electrode portion that similarly forms.
At this, described dielectric medium is suitable to be principal phase with false cube crystalline substance or rhombohedron crystalline substance.Moreover as mentioned above, described dielectric medium is to constitute, when applying the electric field of 4kV/mm and the described electric field induction distortion of the deformation rate on this electric field vertical direction be less than or equal to 0.07%.
That is, as mentioned above, piezoelectric, in the process that forms the dielectric layer that constitutes emtting electrode portion, crystalline structure is a cube crystalline substance when high temperature, and in process of cooling after this, crystalline structure mainly changes to regular crystal.When this phase transformation, form many fine farmlands in the inside of this piezoelectric.When forming this farmland, interface on the farmland of adjacency, the distortion of lattice is restricted (constraint), and lattice parameter can not be changed to the value of the regular crystal of steady state from the value of cube crystalline substance, and therefore the lattice in this farmland becomes the shape of the distortion of the direction towards regulation from steady state.Its result, (after promptly just having made electronic emission element) produces big unrelieved stress in the inside of this emtting electrode portion after just forming emtting electrode portion.
After this, this emtting electrode portion is being applied the alternating electric field that is used for electron emission, polar reverses or during rotation repeatedly, apply the electricapparatus transformation (i.e. the induced distortion owing to apply electric field) that electric field causes according to this, the repeated stress that is mainly caused by the polar rotation that echoes mutually with above-mentioned alternating electric field takes place in the inside of this emtting electrode portion.Because at the inner repeated stress that takes place of this emtting electrode portion, generation can make the arrangement again on described unrelieved stress demulcent farmland, the state of the ordered state on farmland behind the firm manufacturing electronic emission element changes.
Especially, emtting electrode portion is fixed on the matrix and when forming, fixed part between matrix and emtting electrode portion, the distortion of this emtting electrode portion is by matrix (perhaps described electrode layer) restriction (constraint), therefore not compared by the situation of shape constraining with emtting electrode portion, the degree that takes place in applying of producing of this emtting electrode portion (electron emission region on the surface of particularly opposite with the described fixed part face) unrelieved stress that above-mentioned alternating electric field causes becomes big.Therefore, in the case, promoted the arrangement again on above-mentioned farmland more.
Think this arrangement again (variation of the state on the farmland in the emtting electrode portion) by the applying of alternating electric field (and generation of the repeated stress that causes thus) unrelieved stress demulcent farmland that produce, when emtting electrode portion is formed, closely related with the reduction (being the deterioration of emtting electrode portion) of the electron emission amount that causes by use repeatedly.
Therefore, among the present invention, by with aforesaid the 3rd～the 6th dielectric composition as principal constituent, to constitute emtting electrode portion with false cube crystalline substance or rhombohedron crystalline substance as the dielectric medium of principal phase be suitable.Thus, when polar rotates, the stress that produces according to the axial ratio (c/a) of lattice parameter diminishes, and the mitigation and the farmland of the unrelieved stress when therefore the emtting electrode portion that causes by using repeatedly forms are arranged (variation of the state on farmland) again and be suppressed, so the weather resistance of emtting electrode portion can improve.
In addition, described emtting electrode portion is suitable is arranged to be fixed on the surface of described matrix.And then, described electrode suitable by the face side that is arranged on described emtting electrode portion the 1st electrode and the 2nd electrode that is arranged on the inside side of described emtting electrode portion constitute, described the 2nd electrode is arranged to be fixed on the surface of described matrix, and described emtting electrode portion is arranged to be fixed on described the 2nd electrode.
That is, in such formation, the 2nd electrode is fixed on the surface of matrix and is provided with, and emtting electrode portion is fixed on the 2nd electrode and is provided with, and the 1st electrode is arranged on the face side of this emtting electrode portion.According to such formation, compare with the formation that the 2nd electrode is arranged on the face side of emtting electrode portion simultaneously with the 1st electrode, being used to constitute the necessary area of single electronic emission element diminishes, can improve the real dress density of electronic emission element on matrix, therefore particularly when this electronic emission element is applied to FED, realize high definition easily.In addition, according to such formation, the 1st electrode is separately positioned on the different face side (face side and the inside side) of the dielectric layer that constitutes emtting electrode portion with the 2nd electrode, so becomes the formation of dielectric layer between the 1st electrode and the 2nd electrode.Thus, compare, between two electrodes, can apply higher voltage with the formation that two electrodes are arranged on the face side of emtting electrode portion simultaneously.Therefore, the suitable electronic emission element that provides weather resistance not only but also electron emission amount itself also to improve becomes possibility.
In addition, be fixed on the matrix and under the situation about forming, the thermal expansivity of the matrix preferably thermal expansivity than the dielectric layer that constitutes emtting electrode portion is big in emtting electrode portion.
That is, form in the process of described dielectric layer (when for example burning till), during by densification, special stress does not take place at this dielectric layer at this dielectric layer of high temperature.On the other hand, in the process of cooling after described dielectric layer is by densification, the thermal expansivity of matrix is bigger than dielectric layer, thereby the contraction of this dielectric layer of contraction ratio of matrix wants big.Therefore the stress under compression of direction that is parallel to the interface of this dielectric layer and matrix at this dielectric layer.
Because this stress under compression that is parallel to described interface direction that takes place at described dielectric layer, the farmland in this dielectric layer are just easily towards the direction perpendicular to described interface.That is, when forming described dielectric layer on matrix, compare with situation about not being formed on the matrix, the farmland is easily towards the direction perpendicular to the interface of dielectric layer and matrix.Therefore, the reverse on farmland (180 ° of reverses) becomes and takes place easily than the rotation on farmland (90 ° of rotations during regular crystal, 71 ° of rotations when rhombohedron is brilliant, 109 ° of rotations), and the farmland of reversing without rotation is also many than rotating the farmland of afterwards reversing earlier.Thus, when this dielectric layer is applied alternating electric field, can cause promptly that the polar of the emtting electrode portion that is made of this dielectric layer switches, so the electronic transmitting efficiency of this dielectric layer when using as electronic emission element uprises.
In addition, the thickness of described emtting electrode portion, it is suitable being made of 1～300 μ m.
If it is just many that the thickness of emtting electrode portion, constitutes the subsurface defect of dielectric layer of this emtting electrode portion less than 1 μ m, the densification of this emtting electrode portion becomes insufficient.And the specific inductivity of this defect part is much smaller than the dielectric medium that constitutes emtting electrode portion.Therefore, major part in the driving voltage is not applied to described electron emission region in fact but is applied to the defect part of this dielectric layer inside, its result, the driving voltage that is applied to described electron emission region effectively diminishes, and is difficult to the electron emission characteristic that obtains suiting.
On the other hand, if the thickness of emtting electrode portion surpasses 300 μ m, (when particularly having fixed the formation of emtting electrode portion and matrix) just becomes big by the stress that produces in the described dielectric layer of being applied to of driving voltage.And, even under the situation that produces big stress like this,, also need to make the thickness of matrix quite thick in order to accomplish to support emtting electrode portion well by matrix.So because the increase of the thickness of this emtting electrode portion and matrix, it is difficult that the miniaturization of electronic emission element and slimming just become, and especially is difficult to be applied to FED.Have again, the emtting electrode portion of surface, while the 2nd electrode be arranged on to(for) the 1st electrode are arranged on the electronic emission element of this formation in the inside of emtting electrode portion, the driving voltage that is used for obtaining in the necessary regulation strength of electric field of electron emission work can become excessive, therefore need be corresponding to high-tension drive IC etc., the manufacturing cost of electronic emission element rises.
In addition, for densification, the miniaturization that prevents insulation breakdown, electronic emission element and the slimming of the tissue of the dielectric layer of realizing constituting emtting electrode portion, and the lower voltage of driving voltage, simultaneously to make qualification rate good and obtain stable electron emission capability in order to make, and constitutes that the electrode layer of emtting electrode portion is suitable more to be constituted with 5～100 μ m thickness.
At this, electronic emission element of the present invention, suitable especially constituting can be carried out following work.At first,, can make described the 1st electrode become current potential, carry out the emission (supply) of electronics to the surface of described emtting electrode portion (electron emission region) from described the 1st electrode than the low driving voltage of described the 2nd electrode by applying as the 1st stage.That is, go up accumulated electrons (charged) on the surface of this emtting electrode portion (electron emission region).Then, as the 2nd stage, can make described the 1st electrode become current potential than the high driving voltage of described the 2nd electrode by applying, the electronics that is accumulated in described surface is launched.According to such formation, the control of the carried charge on the surface (electron emission region) of the described emtting electrode portion in described the 1st stage is to be relatively easy to, therefore with the high controlled stable electron emission amount that obtains.
Suit especially on the 1st electrode, to form peristome, expose the outside and constitute electronic emission element corresponding to the surface of the emtting electrode portion of this peristome.According to such formation, in the electron emission amount in improving single electronic emission element, the electronics of described peristome to going out from described surface emitting can play the function as gate electrode or focused electron lens.Therefore, according to such formation, can improve the rectilinear propagation of the electronics of launching.Thus, be arranged in when plane at several electronic emission elements, the crosstalk between the electronic emission element of adjacency reduces.Especially, when this electronic emission element was applied to FED, sharpness improved.
The invention effect
According to electronic emission element of the present invention with above-mentioned formation, also can suppress electron emission amount and reduce significantly even use repeatedly, the weather resistance of piezoelectricity membranous type electronic emission element is improved.
Description of drawings
Fig. 1 is the sectional view that part is elliptically represented the electronic emission element of relevant one embodiment of the present invention.
Fig. 2 is the sectional view that amplifies the major portion of the above-mentioned electronic emission element of expression.
Fig. 3 is the figure of voltage waveform that expression is applicable to the driving voltage of above-mentioned electronic emission element.
Fig. 4 is the explanatory view of the mode of operation of the above-mentioned electronic emission element of expression.
Fig. 5 is the explanatory view of the mode of operation of the above-mentioned electronic emission element of expression.
Fig. 6 is used to illustrate the interelectrode electric field of the 1st electrode-the 2nd owing to form the gap and affected equivalent-circuit diagram between the 1st electrode and emtting electrode portion.
Fig. 7 is used to illustrate the interelectrode electric field of the 1st electrode-the 2nd owing to form the gap and affected equivalent-circuit diagram between the 1st electrode and emtting electrode portion.
Fig. 8 is the PMN-PZ-PT three component system solid solution phasors of expression embodiment and Comparative Examples.
Among the figure, the 10th, electronic emission element, the 11st, substrate, the 12nd, emtting electrode portion, 12a are that surface, 12b are that the inside, 14 is that the 1st electrode, 16 is the 2nd electrodes.
Embodiment
Below, with reference to accompanying drawing and table explanation suitable embodiment of the present invention.
＜use the summary of the FED of electronic emission element to constitute 〉
Fig. 1 represents to use the electronic emission element of relevant present embodiment fragmentary cross-sectional view 10 that constitute, that constitute as the summary of the indicating meter 100 of FED.
Indicating meter 100 possesses electronic emission element 10, is configured in the transparent panel 130 of the top of this electronic emission element 10, (promptly relative with electronic emission element 10 face) collector electrode 132 that forms, the luminescent coating 134 that (the same) forms below this collector electrode 132, the grid bias power supply 136 that is connected with collector electrode 132 through resistance and the pulsing source 18 that is connected with electronic emission element 10 below this transparent panel 130.
At the matrix that is made of pottery is to form several electronic emission elements 10 on the substrate 11 two-dimensionally.This electronic emission element 10 possesses emtting electrode portion 12, the 2nd electrode 16 that form at the 1st electrode 14 that forms on the surperficial 12a of this emtting electrode portion 12 and on above-mentioned substrate 11, that dispose with the inside 12b of above-mentioned emtting electrode portion 12 with being connected.In addition, be used in the pulsing source 18 that applies driving voltage Va between these two electrodes in connection on the 1st electrode 14 and the 2nd electrode 16.Moreover, illustrate in the electronic emission element 10 that on substrate 11, forms several two-dimensionally among Fig. 1.In addition, the right-hand member among Fig. 1 illustrates i.e. the 1st electrode 14 of a part of another electronic emission element 10 of adjacency.
The 1st electrode 14 is made of metallic membrane, metallics, nonmetal conductive film (carbon film or nonmetal electroconductive oxide film etc.) or non-metallic conductive particles (carbon particles or electroconductive oxide particle etc.), utilizes coating or evaporation etc. to form 0.1～20 μ m thickness on described surperficial 12a.As the material of above-mentioned metallic membrane or metallics, preferred platinum, gold and silver, indium, palladium, rhodium, molybdenum, tungsten and their alloy.In addition, as the above-mentioned nonmetal conductive film or the material of non-metallic conductive particles, preferred graphite, ITO (indium tin oxide), LSCO (lanthanum strontium copper oxide).Particle shape when the 1st electrode 14 is formed by metallics or non-metallic conductive particles, preferred flakey, tabular, paper tinsel shape, needle-like, bar-shaped, web-like.
Be formed with several peristomes 20 on the 1st electrode 14.This peristome 20 forms, and the surperficial 12a of emtting electrode portion 12 is exposed to the outside (being above-mentioned vacuum: following identical) of electronic emission element 10.In addition, in the outer edge 21 of the periphery of the 1st electrode 14, the surperficial 12a of emtting electrode portion 12 also is exposed to the outside of electronic emission element 10.In addition, peristome 20 suitable forming, the summation of the port area of several peristomes 20 that form on the 1st electrode 14 is with respect to becoming 5～80% to the ratio of the full surface-area (summation that comprises the port area of this peristome 20) of the contributive emtting electrode of electron emission portion 12.At this, above-mentioned can be to the full surface-area of the contributive emtting electrode of electron emission portion 12, be equivalent to outer edge 21 that the periphery at the 1st electrode 14 forms near the surface (peripheral part of the 1st electrode 14 under the surface of emtting electrode portion 12) of the emtting electrode portion 12 of exposing and the total area of the standard-sized sheet open area in the peristome 20.
The 2nd electrode 16 is made of metallic membrane, forms thickness and is less than or equal to 20 μ m, is more preferably less than or equals 5 μ m.The 2nd electrode 16 also utilizes coating or evaporation to form on substrate 11 with the 1st electrode in the same manner.
That is, in this electronic emission element 10, the 2nd electrode 16 is fixed on the top of substrate 11 and is provided with.In addition and the 2nd electrode 16 top fixing and emtting electrode portion 12 is set.And then, the 1st electrode 14 is set on the surperficial 12a of this emtting electrode portion 12.Here said " fixing " is meant and do not use organic class or mineral-type tackiness agent, directly and closely engage.
So, as described in detail below, this electronic emission element 10 constitutes, electronics from 14 supplies of the 1st electrode, after the surperficial 12a that is accumulated in peristome 20 and outer edge 21 pairing emtting electrode portion 12 went up, the electronics that is accumulated on the 12a of this surface was launched to the outside of this electronic emission element 10 (promptly to luminescent coating 134).
The details of the formation of＜electronic emission element 〉
Fig. 2 is the sectional view that the major portion of electronic emission element shown in Figure 1 10 is amplified.As mentioned above, emtting electrode portion 12 is made of polycrystal.Therefore, on the surperficial 12a of emtting electrode portion 12, as depicted in figs. 1 and 2, form the concavo-convex of microcosmic, form recess 24 by this concavo-convex surperficial 12a in emtting electrode portion 12 by crystal boundary etc.And, form the peristome 20 of the 1st electrode 14 in part corresponding to above-mentioned recess 24.Moreover, forming a peristome 20 corresponding to a recess 24 shown in the example of Fig. 1 and Fig. 2, but also can form a peristome 20 corresponding to several recesses 24.
In addition, as shown in Figure 2, peristome 20 by with the edge of opening (inner edge 26b described later) of this peristome 20 the communicating pores 20a that constitutes of the space that surrounds and the part of the 1st electrode 14 around this communicating pores 20a be that perimembranous 26 constitutes.And the 1st electrode 14 forms, separating from emtting electrode portion 12 with the 12 relative face 26a of emtting electrode portion in the perimembranous 26 of peristome 20.That is, in the 1st electrode 14, form gap 28 between face 26a relative in the perimembranous 26 of peristome 20 and the emtting electrode portion 12 with emtting electrode portion 12.And the perimembranous 26 of the 1st electrode 14 split shed portions 20 forms from side section to see it is that cap shape (bead shape) (therefore, in the following description, is designated as " the cap portion 26 of the 1st electrode 14 " with " perimembranous 26 of the peristome 20 of the 1st electrode 14 ".In addition, " in the 1st electrode 14, the face 26a relative with emtting electrode portion 12 of the perimembranous 26 of peristome 20 " is designated as " the following 26a of cap portion 26 ".)。
In addition, this electronic emission element 10 constitutes, and the maximum angle θ at the formed angle of following 26a of the cap portion 26 of near surperficial 12a of emtting electrode portion 12 (summit of the protuberance in the concaveconvex shape face) and the 1st electrode 14 is 1 °≤θ≤60 °.
In addition, in this electronic emission element 10, emtting electrode portion 12 and the 1st electrode 14 form, vertically maximum clearance d is 0 μ m＜d≤10 μ m between the following 26a of the cap portion 26 of the surperficial 12a of emtting electrode portion 12 and the 1st electrode 14, meanwhile, the surfaceness of this surface 12a is according to Ra (center line average roughness: be 0.005～0.5 the μ m of unit).
And, form triple junctures (3 emphasis that form by the 1st electrode 14 and emtting electrode portion 12 and contacting of vacuum) 26c in the place of external agency (air) contact of the surperficial 12a of emtting electrode portion 12, the 1st electrode 14, this electronic emission element 10.These triple juncture 26c are when applying driving voltage Va between the 1st electrode 14 and the 2nd electrode 16, to produce the place (electric field is concentrated portion) that power line is concentrated (electric field is concentrated)." power line is concentrated " is meant in that this is said, when suppose that the 1st electrode 14, emtting electrode portion 12 and the 2nd electrode 16 drawn power line as seeing the flat board of endless from side section, from downside electrode 16 with the equal power line of generation places of being concentrated uniformly-spaced.Concentrate the power line of portion to concentrate (electric field is concentrated) state at this electric field, can simulate and affirmation simply by the numerical analysis that utilizes limited factors method.
Have, in the present embodiment, the shape that peristome 20 is had is that the inner edge 26b of this peristome 20 becomes described electric field and concentrates portion again.Specifically, the cap portion 26 of described peristome 20 being shaped as when side section is seen is that described inner edge 26b acutangulates (thickness is attenuation little by little) towards the tip of this cap portion 26.Moreover, as mentioned above, concentrate portion and described triple juncture 26c at the described electric field of the inner edge 26b of peristome 20, also be formed on position corresponding to the outer edge 21 of the 1st electrode 14 peripheries.
Here, peristome 20 can form circle, ellipse, Polygons, various shapes such as unsetting when overlooking.In addition, this peristome 20 forms, under the situation of the area circle of the same area of the communicating pores 20a when overlooking, average (below, be called " mean diameter of communicating pores 20a ") of the diameter that this is circular is in the size of 0.1 μ m～20 μ m the shape approximation of this communicating pores 20a.It is the reasons are as follows.
As shown in Figure 2, the polarization according to driving voltage Va in the emtting electrode portion 12 takes a turn for the worse or the part that changes is, be formed with the 1st electrode 14 under part (part 1) 40 and corresponding to from the inner edge 26b (interior week) of peristome 20 part (part 2) 42 to the interior side's of peristome 20 zone.Especially, the occurrence scope of part 2 42 can change according to the level of driving voltage Va or the electric field intensity of this part.At this, the mean diameter of the communicating pores 20a in the present embodiment just obtains the emission measure in peristome 20 ejected electron fully if above-mentioned scope (0.1 μ m～20 μ m), meanwhile can efficient emitting electrons well.
On the other hand, during less than 0.1 μ m, the area of described part 2 42 just diminishes in the mean diameter of communicating pores 20a.This part 2 42 constitutes the major portion of accumulating among the zone (electron emission region) of the surperficial 12a of the contributive emtting electrode of the electron pair electron emission portion 12 that the 1st electrode 14 is supplied with.Therefore, the area of this part 1 42 diminishes, and amount of electrons emitted just tails off.In addition, when the mean diameter of communicating pores 20a surpassed 20 μ m, the part that the described peristome 20 from emtting electrode portion 12 exposes, the ratio of part 2 42 (occupation rate) diminished.Therefore the reflection efficiency of electronics reduces.
The electron emission principle of＜electronic emission element 〉
Then, use Fig. 3～Fig. 5 that the electron emission principle of electronic emission element 10 is described.In the present embodiment, as the driving voltage Va that between the 1st electrode 14 and the 2nd electrode 16, applies, use the alternating voltage of the square wave in cycle (T1+T2) as shown in Figure 3.In this driving voltage Va, votage reference (corresponding to the voltage at fluctuation center) is 0V.In addition, in driving voltage Va, become the V2 of current potential, then become the V1 of current potential than the 2nd electrode 16 height (positive voltage) at time T 2, the 1 electrodes 14 as the 2nd stage than the 2nd electrode 16 low (negative voltages) at time T 1, the 1 electrode 14 as the 1st stage.
In addition, state in the early stage, the direction of polarization of emtting electrode portion 12 is tending towards a direction, imagines that for example dipolar negative pole describes towards the situation of the state (with reference to Fig. 4 A) of the surperficial 12a of emtting electrode portion 12.
At first, apply the A-stage of votage reference, shown in Fig. 4 A, become the state of dipolar negative pole, thereby become on the surperficial 12a of emtting electrode portion 12 state of accumulated electrons hardly towards the surperficial 12a of emtting electrode portion 12.
After this, apply negative voltage V2, polarization just reverses (with reference to Fig. 4 B).Because this polarization reverses, concentrating portion at described electric field is that inner edge 26b and triple juncture 26c electric field just takes place concentrate.The above-mentioned electric field that takes place thus from the 1st electrode 14 is concentrated the electron emission (supply) of portion to the surperficial 12a of emtting electrode portion 12.For example, in surperficial 12a, near the part the cap portion 26 of part that the peristome 20 from the 1st electrode 14 exposes and the 1st electrode 14, accumulated electrons (with reference to Fig. 4 C).That is, surperficial 12a is charged.This is charged, according to the sheet resistance value of emtting electrode portion 12, is possible until becoming certain state of saturation, and can control carried charge by the control voltage application time.Like this, the 1st electrode 14 (particularly described electric field is concentrated portion) plays the function to the electronics supply source of emtting electrode portion 12 (surperficial 12a).
After this, driving voltage Va is re-used as driving voltage Va and applies positive voltage V1 after becoming votage reference earlier from negative voltage V2 such as Fig. 5 A, and polarization just reverses (with reference to Fig. 5 B) once more.So, the coulombic repulsion of utilization and dipolar negative pole, the electronics that is accumulated in surperficial 12a just passes through communicating pores 20a to external emission (with reference to Fig. 5 C).
Moreover also carry out and above-mentioned identical electron emission the outer edge 21 of the peripheral part that does not have peristome 20 in the 1st electrode 14.
The equivalent electrical circuit that＜electronic emission element constitutes 〉
In addition, the formation of present embodiment as shown in Figure 6, as the characteristic of circuit, can be similar between the 1st electrode 14 and the 2nd electrode 16 and to form by the electrical condenser C1 of emtting electrode portion 12 and constituting by the aggregate of several electrical condensers Ca in each gap 28.That is, several electrical condensers Ca that is formed by each gap 28 can reconstruct an electrical condenser C2 who connects side by side into mutually.Like this, can constitute the electrical condenser C2 that forms by above-mentioned aggregate and by the be connected in series equivalent electrical circuit of this form of the electrical condenser C1 that emtting electrode portion 12 forms.
But, electrical condenser C2 that is formed by aggregate and the equivalent electrical circuit that merely is connected in series by the electrical condenser C1 that emtting electrode portion 12 forms are unpractiaca.That is, according to the formation number of the peristome 20 of the 1st electrode 14 and all formation areas etc., ratio among the electrical condenser C1 that is formed by emtting electrode portion 12 and that be connected in series by the electrical condenser C2 that aggregate forms changes.
At this, as shown in Figure 7, among the electrical condenser C1 that for example supposes to form by emtting electrode portion 12, its 25% and by the situation that the electrical condenser C2 that aggregate forms is connected in series, come rated capacity.
Gap 28 is vacuum, thereby relative permittivity is 1.Then, the largest interval d that sets gap 28 is 0.1 μ m, and the area S of the part in a gap 28 is 1 μ m * 1 μ m, and the number in gap 28 is 10000.In addition, the relative permittivity of setting emtting electrode portion 12 is 2000, and the thickness of emtting electrode portion 12 is 20 μ m, and the opposed area of the 1st electrode 14 and the 2nd electrode 16 is 200 μ m * 200 μ m.
Under above hypothesis, the capability value of the electrical condenser C2 that is formed by aggregate becomes 0.885pF, and the capability value of the electrical condenser C1 that is formed by emtting electrode portion 12 becomes 35.4pF.And, among the electrical condenser C1 that forms by emtting electrode portion 12, the part that is connected in series with the electrical condenser C2 that is formed by aggregate is defined as at all 25% o'clock, capability value in this part that is connected in series (capability value that comprises the capability value of the electrical condenser C2 that is formed by aggregate) becomes 0.805pF, and residual capability value becomes 26.6pF.
Lingering section and this part that is connected in series beyond the part that is connected in series among the electrical condenser C1 that is formed by above-mentioned emtting electrode portion 12 and by the electrical condenser C2 that aggregate forms are connected in parallel.Therefore, all joint capacity values between the 1st electrode 14 and the 2nd electrode 16 become 27.5pF.This joint capacity value be the electrical condenser C1 that forms by emtting electrode portion 12 capability value 35.4pF 78%.That is to say that all joint capacity values are littler than the capability value of the electrical condenser C1 that is formed by emtting electrode portion 12.
Like this, the joint capacity C2 of the capability value of the electrical condenser Ca that is formed by gap 28 and the aggregate in this gap 28 becomes little more than the electrical condenser C1 that is formed by the emtting electrode portion 12 that is connected in series.Therefore, be applied on the series circuit of this electrical condenser Ca (C2) and C1 apply voltage Va the time the major part of dividing potential drop, on the little electrical condenser Ca (C2) of the capacity that just is applied to.In other words, the major part that applies voltage Va is applied on the gap 28.Therefore, in each gap 28, apply voltage with high-level efficiency, its result obtains more electron emission amount.That is, realize the height outputization of electronic emission element.
In addition, the electrical condenser C2 that forms by the aggregate structure that becomes and be connected in series by the electrical condenser C1 that emtting electrode portion 12 forms.Therefore, all joint capacity values are littler than the capability value of the electrical condenser C1 that is formed by emtting electrode portion 12.Thereby, can access all electricity that disappears so good characteristic that diminishes.
The summary of the dielectric composition of the emtting electrode portion of＜formation the 1st embodiment 〉
The emtting electrode portion 12 that uses in the present embodiment specifically, is by the dielectric composition formation that contains NiO with the composition of following general formula (1) expression as principal constituent, with specific ratio.
Pb
xBi
p(Mg
y/3Nb
2/3)
aTi
b-zM
zZr
cO
3 …(1)
[in the above-mentioned general formula (1), 0.85≤x≤1.03,0.02≤p≤0.1,0.8≤y≤1.0, and a, b, c be with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), the decimal in the scope of (0.375,0.425,0.200) 5 encirclements.In addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.]
Thus, the densification of the dielectric layer of emtting electrode portion 12 can be realized constituting, electron emission characteristic can be improved.That is,, can access the few dielectric layer of defective by making the dielectric layer densification that constitutes emtting electrode portion 12.Therefore, can improve the strength of electric field in the above-mentioned gap 28 when applying driving voltage, thereby can improve electron emission amount.Have, even use this electronic emission element 10 for a long time, the electron emission capability that also can make emtting electrode portion 12 is by using the deterioration that causes to diminish repeatedly again.Thus, the weather resistance of electronic emission element 10 is improved.
With respect to this, as using embodiment 1 and Comparative Examples 1 to describe in the back, if a, b in the above-mentioned general formula (1), c or replace the amount of Pb or Ti, or the content of NiO is outside above-mentioned specified range just become big by the deterioration that causes of using repeatedly of the electron emission capability of emtting electrode portion 12.
In addition, less than 0.05%, it is insufficient that the densification of dielectric layer just becomes if the containing ratio of NiO is too small, and electron emissivity reduces.That is, the defective (pore etc.) that constitutes the dielectric layer of emtting electrode portion 12 becomes many, and electric field just concentrates on the low defective part of this specific inductivity.Therefore, reduce corresponding to the strength of electric field at the electron emission position in gap 28, electron emission amount itself is reduction just.
And, from suppressing emtting electrode portion 12 by the viewpoint of using the deterioration that causes repeatedly, within the specified range of the invention described above, the amount that is replaced Pb by Bi is that 2～5mol% is more suitably, amount by replacement Ti such as Nb is that 3～8mol% is more suitably, and the containing ratio of NiO is that 0.50～1.0 weight % is more suitably.
The manufacture method of the electronic emission element of＜the 1 embodiment 〉
At first, by the Y that utilizes 3mol%
2O
3Carry out the ZrO of the thick 0.5mm of stabilization
2On the substrate 11 that constitutes, use silk screen print method to form the 2nd electrode 16 that the Pt by thick 3 μ m constitutes with the size of 1mm * 0.5mm.Then, the temperature about 1000～1400 ℃ is heat-treated the substrate 11 that forms the 2nd electrode 16, makes the 2nd electrode 16 and substrate 11 fixing and integrated thus.The thickness of Pt after fixedly becoming one is 1.5 μ m.
Then, on the 2nd electrode 16, use silk screen print method to make and form thick film with the size of 1.1mm * 0.6mm, make coating thickness become 40 μ m as principal constituent, the dielectric composition that contains the NiO of definite quality % with the composition of above-mentioned general formula (1) expression.
At this,, can use oxide compound (for example PbO, the Pb of each element such as Pb, Mg, Nb, Zr, Ti, Ni as the raw material of above-mentioned dielectric composition
3O
4, MgO, Nb
2O
5, TiO
2, ZrO
2, NiO etc.), the carbonate of these each elements, contain the compound (MgNb for example of several these each elements
2O) or the elemental metals of these each elements and alloy etc.These raw materials can be used alone, and perhaps are used in combination two kinds or more than it.
And the preparation method about dielectric composition has no particular limits, but can use following method to prepare dielectric composition.
At first, use the above-mentioned raw materials of common mixing device mixing such as ball mill, make the containing ratio of each element become desired ratio.Then, resulting mixing raw material carries out pre-burning at 750～1300 ℃, obtains dielectric composition.Dielectric composition after this pre-burning, with regard to the diffracted intensity that utilizes the X-ray diffraction device to obtain, pyrrhite equates the ratio of the strongest out of phase diffracted ray intensity for the strongest diffracted ray intensity of uhligite phase, preferably is less than or equal to 5%, is more preferably less than or equals 2%.At last, use ball mill etc. is pulverized the dielectric composition after the pre-burning that obtains, and obtains the dielectric medium powder of regulation particle diameter (for example obtaining median size 0.1～1 μ m according to laser diffractometry) thus.
Moreover, also can heat-treat at the powder of 400～750 ℃ of dielectric compositions that pulverizing is obtained as required, carry out the adjustment of particle diameter.That is, under heating condition, other particles that fine more particle is easy and adjacent more become one.Therefore, promote the integrated of minuteness particle by above-mentioned thermal treatment, the dielectric medium powder after the thermal treatment becomes the powder that particle diameter reaches unanimity.Therefore, can access the dielectric film that particle diameter reaches unanimity.
The powder of the dielectric composition that obtains like this is dispersed in the tackiness agent of regulation and preparation is stuck with paste, uses this paste, utilize above-mentioned silk screen print method on the 2nd electrode 16, to form thick film.
And thermal treatment should form the dielectric composition of thick film, when making evaporate, made the dielectric layer densification.Form emtting electrode portion 12 thus.
And then, in established emtting electrode portion 12, use silk screen print method to form the presoma that constitutes by resinous acid platinum with the size of 0.95mm * 0.45mm after, heat-treat, form the 1st electrode 14 that constitutes by the Pt electrode thus.As above, just can make the electronic emission element 10 of dielectric medium membranous type.
Use aforesaid manufacture method, make the dielectric medium membranous type electronic emission element of embodiment 1-1～1-8 as described below and Comparative Examples 1-1～1-9.Then, constitute indicating meter as shown in Figure 1, by using the degradation that causes repeatedly, each embodiment and Comparative Examples are estimated as metewand with the brightness of this indicating meter.Specifically, measure the brightness and 10 at initial stage
9Brightness after the inferior electron emission work (durable back brightness), as 100%, the brightness of obtaining the durable back relative initial stage of brightness keeps the how brightness of degree with the brightness at initial stage.The thickness of the emtting electrode portion 12 after the thermal treatment all is 24 μ m.
＜＜embodiment 1-1〉〉
With the principal constituent is Pb
0.96Bi
0.04(Mg
1/3Nb
2/3)
0.20Ti
0.38Nb
0.05Zr
0.37O
3, and the material that contains 1.0 quality %NiO as embodiment 1-1.For this embodiment 1-1, a, b in (1) formula, c are changed beyond scope of the present invention, that is, the embodiment 1-1 that to make Bi replacement amount, Nb replacement amount, NiO addition interior with being in the scope of the invention is identical, and makes (Mg
1/3Nb
2/3) and the material that beyond scope of the present invention, changes of the ratio of Ti and Zr 1-1～1-3 as a comparison case.This results are shown in the table 1.
Table 1
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Nb measures (mol%) | NiO measures (wt%) | Durable back brightness | |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | 5 | 1.00 | 77％ |
| Comparative Examples 1-1 | 4 | 60 | 25 | 10 | 5 | 1.00 | 19％ |
| Comparative Examples 1-2 | 4 | 30 | 50 | 15 | 5 | 1.00 | 33％ |
| Comparative Examples 1-3 | 4 | 0 | 45 | 50 | 5 | 1.00 | 22％ |
As clear from the result of this table 1 institute, be among the embodiment 1-1 in the scope of the invention, durable back brightness is 77%, with respect to this, among Comparative Examples 1-1～1-3, durable back brightness is all below half of embodiment 1-1.
＜＜embodiment 1-2,1-3〉〉
For embodiment 1-1, make (Mg
1/3Nb
2/3) and ratio, Nb replacement amount, the NiO addition of Ti and Zr certain, and the material that changes Bi replacement amount is as embodiment 1-2,1-3 and Comparative Examples 1-4,1-5.The results are shown in the table 2.
Table 2
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Nb measures (mol%) | NiO measures (wt%) | Durable back brightness | |
| Comparative Examples 1-4 | 1 | 20 | 38 | 37 | 5 | 1.00 | 25％ |
| Embodiment 1-2 | 2 | 20 | 38 | 37 | 5 | 1.00 | 73％ |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | 5 | 1.00 | 77％ |
| Embodiment 1-3 | 8 | 20 | 38 | 37 | 5 | 1.00 | 59％ |
| Comparative Examples 1-5 | 12 | 20 | 38 | 37 | 5 | 1.00 | 38％ |
Clear as result institute from this table 2, be among the embodiment 1-1～1-3 in the scope of the invention, durable back brightness with respect to this, is among the scope of the invention outer Comparative Examples 1-4, the 1-5 about 60%, and durable back brightness is then less than 40%.Especially can estimate that the amount that replaces Pb by Bi is in 2～5mol% scope the time, durable back brightness can be embodiment 1-1 and the 1-2 of 2～4mol% with the replacement amount more than or equal to 70%, and durable back brightness is very good.
＜＜embodiment 1-4,1-5〉〉
For embodiment 1-1, make (Mg
1/3Nb
2/3) and ratio, Bi replacement amount, the NiO addition of Ti and Zr certain, and the material that changes Nb replacement amount is as embodiment 1-4,1-5 and Comparative Examples 1-6,1-7.This results are shown in the table 3.
Table 3
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Nb measures (mol%) | NiO measures (wt%) | Durable back brightness | |
| Comparative Examples 1-6 | 4 | 20 | 42 | 37 | 1 | 1.00 | 47％ |
| Embodiment 1-4 | 4 | 20 | 41 | 37 | 2 | 1.00 | 66％ |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | 5 | 1.00 | 77％ |
| Embodiment 1-5 | 4 | 20 | 35 | 37 | 8 | 1.00 | 70％ |
| Comparative Examples 1-7 | 4 | 20 | 33 | 37 | 12 | 1.00 | 44％ |
Clear as result institute from this table 3, be among the scope of the invention interior embodiment 1-1,1-4, the 1-5, durable back brightness surpasses 60%, with respect to this, is among the scope of the invention outer Comparative Examples 1-6, the 1-7, and durable back brightness is but less than 50%.Especially can estimate that when the replacement amount of the Ti of Nb was in the scope of 3～8mol%, durable back brightness can be embodiment 1-1 and the 1-5 of 5～8mol% with the replacement amount more than or equal to 70%, durable back brightness is very good.
＜＜embodiment 1-6～1-8〉〉
For embodiment 1-1, make (Mg
1/3Nb
2/3) and ratio, Bi replacement amount, the Nb replacement amount of Ti and Zr certain, and the material that changes the NiO addition is as embodiment 1-6～1-8 and Comparative Examples 1-8,1-9.This results are shown in the table 4.
Table 4
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Nb measures (mol%) | NiO measures (wt%) | Durable back brightness | |
| Comparative Examples 1-8 | 4 | 20 | 38 | 37 | 5 | 0.00 | 38％ |
| Embodiment 1-6 | 4 | 20 | 38 | 37 | 5 | 0.10 | 55％ |
| Embodiment 1-7 | 4 | 20 | 38 | 37 | 5 | 0.50 | 69％ |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | 5 | 1.00 | 77％ |
| Embodiment 1-8 | 4 | 20 | 38 | 37 | 5 | 2.00 | 58％ |
| Comparative Examples 1-9 | 4 | 20 | 38 | 37 | 5 | 3.00 | 24％ |
Clear as result institute from this table 4, be among the scope of the invention interior embodiment 1-1,1-6,1-7, the 1-8, durable back brightness, is among the scope of the invention outer Comparative Examples 1-8, the 1-9 with respect to this greater than 55%, and durable back brightness is but less than 40%.Especially, embodiment 1-1 and the 1-7 of the containing ratio of NiO in 0.50～1.0 weight % scope, durable back brightness is very good about 70%.
＜＜embodiment 1-9～1-11〉〉
For embodiment 1-1, the element that is equivalent to M in the wushu (1) becomes the material of Ta, Mo, W respectively as embodiment 1-9,1-10,1-11 from Nb.Any embodiment among these each embodiment, durable back brightness all is good.This results are shown in the table 5.
Table 5
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Ti element kind | Replace Ti amount of element (mol%) | NiO measures (wt%) | Durable back brightness | |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | Nb | 5 | 1.00 | 77％ |
| Embodiment 1-9 | 4 | 20 | 38 | 37 | Ta | 5 | 1.00 | 71％ |
| Embodiment 1-10 | 4 | 20 | 40 | 37 | | 3 | 1.00 | 63％ |
| Embodiment 1-11 | 4 | 20 | 40 | 37 | | 3 | 1.00 | 65％ |
Like this, be in the interior embodiment of the scope of the invention 1 and be in the scope of the invention Comparative Examples 1 outward, durable back brightness has produced notable difference, according to the embodiment that is in the scope of the invention, can obtain favorable durability.And, if particularly with Pb
0.96Bi
0.04(Mg
1/3Nb
2/3)
0.20Ti
0.38Nb
0.05Zr
0.37O
3For principal constituent and NiO are that the embodiment 1-1 of 1.0 quality % is the center, be 2～5mol%, be the scope of the containing ratio of 3～8mol%, NiO by the replacement amount of the Pb of Bi at 0.50～1.0 weight % by the replacement amount of the Ti of Nb, durable back brightness just becomes more than or equal to 70%, is extremely suitable.
The summary of the dielectric composition of the emtting electrode portion of＜formation the 2nd embodiment 〉
NiO and MnO as principal constituent, are contained with specific ratio with the composition of identical, described general formula with described the 1st embodiment (1) expression in the emtting electrode portion 12 that uses in the present embodiment
2Dielectric composition constitute.That is, the dielectric composition that constitutes the emtting electrode portion of the 2nd embodiment is the dielectric composition for above-mentioned the 1st embodiment, further contains Mn (MnO with specific ratio
2).Such emtting electrode portion 12 and the electronic emission element 10 that possesses this emtting electrode portion 12 also can use the method manufacturing identical with above-mentioned the 1st embodiment.
＜＜embodiment 1-12～1-14〉〉
So, use the emtting electrode portion 12 of the 2nd such embodiment, constitute as shown in Figure 1 indicating meter in the same manner with the 1st above-mentioned embodiment, by using the degradation that causes repeatedly, carry out the evaluation of the emtting electrode portion 12 of present embodiment as metewand with the brightness of this indicating meter.That is, with MnO
2Content is the foregoing description 1-1 of 0 object as a comparison, contains MnO with different ratios
2Material as embodiment 1-12～1-14.This results are shown in the table 6.
Table 6
| Bi replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Ti element kind | Replace Ti amount of element (mol%) | NiO measures (wt%) | MnO 2Amount (wt%) | Durable back brightness | |
| Embodiment 1-1 | 4 | 20 | 38 | 37 | Nb | 5 | 1.00 | 0 | 77％ |
| Embodiment 1-12 | 4 | 20 | 38 | 37 | Nb | 5 | 1.00 | 0.05 | 78％ |
| Embodiment 1-13 | 4 | 20 | 38 | 37 | Nb | 5 | 1.00 | 0.2 | 76％ |
| Embodiment 1-14 | 4 | 20 | 38 | 37 | Nb | 5 | 1.00 | 1.00 | 69％ |
Clear as result institute from this table 6, MnO
2Content be 0.05 weight % embodiment 1-12, be the embodiment 1-13 of 0.2 weight %, be any among the embodiment 1-14 of 1.0 weight % with content that with content durable back brightness all is good.Especially, with embodiment 1-12 and the 1-13 of content in 0.01～0.2 weight % scope, durable back brightness is very good greater than 75%.
The summary of the dielectric composition of the emtting electrode portion of＜formation the 3rd enforcement formula 〉
The emtting electrode portion 12 of Shi Yonging in the present embodiment, by constituting with the dielectric composition of composition as principal constituent, specifically, by dielectric composition (above-mentioned the 2nd dielectric composition) formation that contains NiO with the composition of following general formula (2) expression as principal constituent, with the specified proportion identical with each above-mentioned embodiment.
Pb
xBi
pSr
q(Mg
y/3Nb
2/3)
aTi
b-zM
zZr
cO
3 …(2)
[in the above-mentioned general formula (2), 0.70≤x≤1.01,0.02≤p≤0.1,0.02≤q≤0.15,0.8≤y≤1.0, and a, b, c be with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), the decimal in the scope of (0.375,0.425,0.200) 5 encirclements.In addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.]
＜＜embodiment 1-15～1-17〉〉
That is, constituting the dielectric composition of the emtting electrode portion 12 of relevant the 3rd embodiment, is the dielectric composition for above-mentioned the 1st embodiment, further replaces the material of a part of Pb with Sr with specified proportion.Relevant emtting electrode portion 12 and the electronic emission element 10 that possesses this emtting electrode portion 12 can both use the method manufacturing identical with the respective embodiments described above.About the 3rd such embodiment, also carry out the evaluation identical with each above-mentioned embodiment.It the results are shown in the table 7.
Table 7
| Bi replacement amount (mol%) | Sr replacement amount (mol%) | (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Ti element kind | Replace Ti amount of element (mol%) | NiO measures (wt%) | Durable back brightness | |
| Embodiment 1-1 | 4 | 0 | 20 | 38 | 37 | Nb | 5 | 1.00 | 77％ |
| Embodiment 1-15 | 4 | 2 | 20 | 38 | 37 | Nb | 5 | 1.00 | 80％ |
| Embodiment 1-16 | 4 | 10 | 20 | 38 | 37 | Nb | 5 | 1.00 | 79％ |
| Embodiment 1-17 | 4 | 20 | 20 | 38 | 37 | Nb | 5 | 1.00 | 72％ |
As from this table 7 clear, the amount that replaces Pb by Sr be 2mol% embodiment 1-15, be the embodiment 1-16 of 10mol%, be any among the embodiment 1-17 of 20mol% with the replacement amount that with the replacement amount durable back brightness all is good.Especially can estimate, if with the replacement amount in 1～15mol% scope, the brightness of durable back can be more than or equal to 75%.Embodiment 1-15 and 1-16 in the scope of 1～12mol%, durable back brightness is about 80%, is very good.
＜the 4 implements the summary of the dielectric composition of formula 〉
The emtting electrode portion 12 of Shi Yonging is with described the 3rd composition in the present embodiment, promptly with the dielectric composition of following general formula (3) expression as principal constituent.
Pb
x(Mg
y/3Nb
2/3)
aTi
bZr
cO
3 …(3)
[in the above-mentioned general formula (3), 0.95≤x≤1.05,0.90≤y≤1.10, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), the decimal in the scope of (0.250,0.360,0.390) 5 encirclements.]
It is above-mentioned that (value c) is in the scope that the 5 limit shapes that formed by heavy line in the PMN-PZ-PT shown in Figure 8 three component system solid solution phasors surround for a, b.As clear from this Fig. 8 institute, the dielectric medium of forming shown in the above-mentioned general formula, with principal phase be regular crystal piezoelectric driving systen in the past with or the PZT of strong dielectric storage usefulness be representative to contain the piezoelectric that plumbous perovskite oxide constitutes different, principal phase is the brilliant or false cube crystalline substance of rhombohedron.
The manufacture method of the electronic emission element of＜the 4 embodiment 〉
At first, identical with the above-mentioned the 1st with the situation of the 2nd embodiment, by using Y
2O
3The ZrO of stabilization
2On the substrate 11 that constitutes, use silk screen print method to form the 2nd electrode 16, make the 2nd electrode 16 and substrate 11 fixing and integrated by thermal treatment.
Then, on the 2nd electrode 16, be the composition with above-mentioned general formula (3) expression the dielectric composition of principal constituent, use silk screen print method to form the thick film of coating thickness 40 μ m.After this, the dielectric film that obtains forming thick film and substrate 11 is heat-treated together and substrate 11 becomes one forms emtting electrode portion 12 thus.Preferred 1000～1400 ℃ of the thermal treatment temp of this moment, more preferably 1100～1350 ℃.The preparation of this dielectric composition can be carried out in the same manner with the situation of above-mentioned the 1st embodiment.
Moreover also the powder of the dielectric composition that can obtain pulverizing is as required heat-treated at 400～750 ℃, regulates particle diameter.That is, under heating condition, other particles that fine more particle is easy and adjacent more become one.Therefore, promoted that by the integrated of above-mentioned thermal treatment minuteness particle the dielectric medium powder after the thermal treatment becomes the powder that particle diameter reaches unanimity.Therefore, can access the dielectric film that particle diameter reaches unanimity.
Then and the situation of above-mentioned the 1st embodiment be identically formed the 1st electrode 14.As mentioned above, make the electronic emission element 10 of the piezoelectricity membranous type of present embodiment.
＜＜embodiment 2-1～2-2〉〉
Use aforesaid manufacture method, make the piezoelectricity membranous type electronic emission element of use at the dielectric composition of the embodiment 2 of following explanation and Comparative Examples 2.Then, constitute indicating meter shown in Figure 1, with the brightness of this indicating meter by the degree of using the deterioration that causes repeatedly as metewand, each embodiment and Comparative Examples are estimated.Specifically, measure the brightness and 10 at initial stage
9Brightness after the inferior electron emission work (durable back brightness) is 100% with the brightness at initial stage, obtains durable back brightness the brightness at initial stage is kept the how brightness of degree (in the following description and table, being called " weather resistance ").Moreover the thickness of the emtting electrode portion 12 after the thermal treatment all is 24 μ m.
With in the above-mentioned general formula (3) (a, b c) are that the dielectric composition of (0.375,0.25,0.375) is as embodiment 2-1, being that the dielectric composition of (0.10,0.36,0.54) is as embodiment 2-2.With respect to this, so that (a, b c) are (0.55,0.175,0.275) dielectric composition 2-1 as a comparison case, being (0.375,0.050,0.575) dielectric composition 2-2 as a comparison case, to be the dielectric composition 2-3 as a comparison case of (0.03,0.37,0.60).In addition, with Pb (Mg
1/3Nb
2/3)
0.20Ti
0.38Nb
0.05Zr
0.37O
3(be the material that replaces a part of Ti with Nb, (a, b c) are equivalent to (0.20,0.43,0.37)) be 2-4 as a comparison case for the dielectric composition of expression.Its evaluation result is shown in Table 8.In addition, in Fig. 8, use ● expression embodiment (has added " 1 " word in embodiment 2-1.Embodiment 2 is too), represent that with * Comparative Examples (added " 1 " word in Comparative Examples 2-1.Comparative Examples 2-2 later on too).
Table 8
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-2 | 10 | 36 | 54 | - | - | 68％ |
| Comparative Examples 2-1 | 55 | 17.5 | 27.5 | - | - | 43％ |
| Comparative Examples 2-2 | 37.5 | 5 | 57.5 | - | - | 38％ |
| Comparative Examples 2-3 | 3 | 37 | 60 | - | - | 47％ |
| Comparative Examples 2-4 | 20 | 38 | 37 | - | Nb/5 | 38％ |
Clear as result institute from table 8 and Fig. 8, be among the embodiment 2-1 and 2-2 in the scope of the invention, weather resistance is about 70%, and with respect to this, in Comparative Examples 2-1～2-3, weather resistance is less than 50%.And, in order to obtain higher weather resistance, preferred (a, b c) in above-mentioned trigonometric coordinates, is in by (0.500,0.320,0.180), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), (0.380,0.320,0.300) in the scope of 5 encirclements, more preferably be in by (0.500,0.320,0.180), (0.500,0.150,0.350), (0.350,0.150,0.500), (0.050,0.350,0.600), (0.050,0.420,0.525), (0.380,0.320,0.300) and in the scope of 6 encirclements.Optimum use be to be in by (0.500,0.320,0.180), (0.500,0.150,0.350), (0.350,0.150,0.500), (0.050,0.350,0.600), (0.050,0.385,0.565), (0.380,0.320,0.300) and the dielectric composition of composition in the scope of 6 encirclements.Moreover embodiment 2-1 is to be principal phase with false cube crystalline substance, and embodiment 2-2 is to be principal phase with the rhombohedron crystalline substance, and Comparative Examples 2-4 is to be principal phase with the regular crystal.
The summary of the dielectric composition of＜the 5 embodiment 〉
The emtting electrode portion 12 of Shi Yonging is with described the 4th dielectric composition in the present embodiment, and promptly the dielectric composition with following general formula (4) expression is the material of principal constituent.The dielectric medium of this composition is in described the 3rd dielectric composition, replaces the dielectric medium of Pb atom with other elements of regulation.The manufacture method of such dielectric composition is identical with described the 4th embodiment.
Pb
x-pMa
p(Mg
y/3Nb
2/3)
aTi
bZr
cO
3 …(4)
[in the above-mentioned general formula (4), the scope of x, y, a, b, c is identical with described general formula (3).In addition, Ma is select from Sr, La, Bi at least a.]
＜＜embodiment 2-3～2-5〉〉
Use the piezoelectricity membranous type electronic emission element of making the dielectric composition that uses embodiment 2-3～2-5 with the identical manufacture method of above-mentioned the 4th embodiment, estimate.That is, with (a, b in the above-mentioned general formula (4), c) be that (0.375,0.25,0.375) and Ma are that the dielectric composition of Sr and p=0.02 is as embodiment 2-3, with the dielectric composition of p=0.06 as embodiment 2-4, with the dielectric composition of p=0.12 as embodiment 2-5.These embodiment 2-3～2-5 can be described as the dielectric composition (false cube crystalline substance) for the foregoing description 2-1, only replace the dielectric composition of Pb with the Sr of specified amount.The evaluation result of these embodiment is shown in Table 9.Moreover as mentioned above, the foregoing description 2-1 is equivalent to the p=0 in the above-mentioned general formula (4) in fact, therefore is shown in the table to do reference.
Table 9
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-3 | 37.5 | 25 | 37.5 | Sr/2 | - | 73％ |
| Embodiment 2-4 | 37.5 | 25 | 37.5 | Sr/6 | - | 76％ |
| Embodiment 2-5 | 37.5 | 25 | 37.5 | Sr/12 | - | 69％ |
Clear as result institute from table 9, in the scope of p=0～0.12, obtain the favorable durability about 70%.But, between the embodiment of the embodiment of p=0 2-1 and p=0.02 2-3, almost there is not difference, almost can't see the additive effect of Sr, on the other hand, in the embodiment of p=0.06 2-4, see the raising of the weather resistance that the interpolation by Sr causes.And in the embodiment of p=0.12 2-5, weather resistance is than some reduction of embodiment 2-1 of not adding Sr.Therefore, Sr addition p value just can be expected sufficient weather resistance if in 0.03～0.15 scope, in order to obtain higher weather resistance, is suitable in 0.03～0.10 scope, is more suitably in 0.05～0.07 scope.
＜＜embodiment 2-6～2-9〉〉
In addition, with the Ma in the above-mentioned general formula (4) be the dielectric composition of La, p=0.002 as embodiment 2-6, with the dielectric composition of p=0.007 as embodiment 2-7, with the dielectric composition of p=0.012 as embodiment 2-8.In addition, be that the dielectric composition of Bi, p=0.007 is as embodiment 2-9 with Ma.The evaluation result of these embodiment is shown in Table 10.Moreover, identical with above-mentioned table 9, the table shown in (being equivalent to p=0) the foregoing description 2-1 to do reference.
Table 10
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-6 | 37.5 | 25 | 37.5 | La/0.2 | - | 75％ |
| Embodiment 2-7 | 37.5 | 25 | 37.5 | La/0.7 | - | 79％ |
| Embodiment 2-8 | 37.5 | 25 | 37.5 | La/1.2 | - | 72％ |
| Embodiment 2-9 | 37.5 | 25 | 37.5 | Bi/0.7 | - | 75％ |
Clear as result institute from table 10, in the scope of p=0～0.012, obtain surpassing 70% favorable durability.But, between the embodiment of the embodiment of the embodiment of p=0 2-1 and p=0.002 2-6 and p=0.012 2-8, almost there is not difference, almost can't see the additive effect of La, on the other hand, among the embodiment 2-7 of p=0.007 therebetween, can see significantly improving of weather resistance that the interpolation by La causes.In addition, as clear from embodiment 2-9 institute, not only Sr, La also obtain the effect that weather resistance improves even add Bi.Therefore, the addition p (La+Bi) of La and Bi value is if in 0.002～0.015 scope, just can expect sufficient weather resistance, in order to obtain higher weather resistance, in 0.003～0.010 scope, be suitable, in 0.005～0.009 scope, be more suitably.
＜＜embodiment 2-10〉〉
In addition, estimate as embodiment 2-10 with the material that has made up embodiment 2-4 that weather resistance is the highest among the foregoing description 2-3～5 (Ma in the above-mentioned general formula (4) is Sr, p=0.06) and the embodiment 2-7 (Ma in the general formula (4) is La, p=0.007) that weather resistance is the highest among the foregoing description 2-6～2-8.This results are shown in the table 11.Moreover and above-mentioned table 9 or table 10 in the same manner, at (being equivalent to p=0) the foregoing description 2-1 shown in the table to do reference.
Table 11
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-10 | 37.5 | 25 | 37.5 | Sr/6 La/0.7 | - | 80％ |
Clear as result institute from table 11, embodiment 2-10, weather resistance reaches 80%, demonstrates very favorable durability.Therefore, contain 0.05～0.07 Sr and contain the formation of 0.005～0.009 La by mole fraction,, can be described as best from the viewpoint of weather resistance by mole fraction.
The summary of the dielectric composition of＜the 6 embodiment 〉
The emtting electrode portion 12 of Shi Yonging is with described the 5th dielectric composition in the present embodiment, promptly with the dielectric composition of following general formula (5) expression as principal constituent.The manufacture method of such dielectric composition is identical with the 5th embodiment with the above-mentioned the 4th.
Pb
x(Mg
y/3Nb
2/3)
aTi
b-qMb
qZr
cO
3 …(5)
[in the above-mentioned general formula (5), the scope of x, y, a, b, c is identical with above-mentioned general formula (3).In addition, Mb is select from Nb, Ta, Mo, W at least a.]
＜＜embodiment 2-11～2-14〉〉
Use and the above-mentioned the 4th manufacture method identical, make the piezoelectricity membranous type electronic emission element of embodiment 2-11～2-14, estimate with the 5th embodiment.Promptly, with the Mb in the above-mentioned general formula (5) is that the dielectric composition of Nb and q=0.005 is as embodiment 2-11, with the dielectric composition of q=0.02 as embodiment 2-12, with the dielectric composition of q=0.05 as embodiment 2-13, with the dielectric composition of q=0.12 as embodiment 2-14.These embodiment 2-11～2-14 can be described as, for (a, b c) are the dielectric compositions of the foregoing description 2-1 of (0.375,0.25,0.375), only replace the material of Ti with specified amount Nb in above-mentioned general formula (3).The evaluation result of these embodiment is shown in Table 12.Moreover the foregoing description 2-1 is equivalent to the q=0 in the above-mentioned general formula (5) in fact, therefore is shown in the table to do reference.
Table 12
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-11 | 37.5 | 25 | 37.5 | - | Nb/0.5 | 74％ |
| Embodiment 2-12 | 37.5 | 25 | 37.5 | - | Nb/2 | 76％ |
| Embodiment 2-13 | 37.5 | 25 | 37.5 | - | Nb/5 | 77％ |
| Embodiment 2-14 | 37.5 | 25 | 37.5 | - | Nb/12 | 71％ |
Clear as result institute from table 12, in the scope of q=0～0.12, obtain surpassing 70% favorable durability.But, between the embodiment of the embodiment of q=0 2-1 and q=0.005 2-11, almost there is not difference, the embodiment 2-14 of q=0.12, weather resistance is on the contrary than some reduction of embodiment 2-1 of q=0, on the other hand, among the embodiment 2-12 of q=0.02 therebetween or the embodiment 2-13 of q=0.05, see the raising of the weather resistance that the interpolation by Nb causes.Therefore, the addition q value of Nb just can be expected sufficient weather resistance if in 0.01～0.15 scope, in order to obtain higher weather resistance, is more suitably in 0.02～0.10 scope, is only in 0.02～0.08 scope.
＜＜embodiment 2-15～2-17〉〉
Use and the above-mentioned the 4th manufacture method identical, make the piezoelectricity membranous type electronic emission element of embodiment 2-15～2-17, estimate with the 5th embodiment.Promptly, with weather resistance is the highest among the foregoing description 2-11～2-14 embodiment 2-13 (dielectric composition that the q=0.05 in the above-mentioned general formula (5), Mb are Nb) as the basis, replace the material of Nb as embodiment 2-15 as Mb with Ta, the material that replaces with Mo is as embodiment 2-16, and the material that replaces with W is as embodiment 2-17.The evaluation result of these embodiment is shown in Table 13.Moreover, with above-mentioned identical, the table shown in (being equivalent to q=0) the foregoing description 2-1 to do reference.
Table 13
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Replace Ti element/replacement amount (mol%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | - | 74％ |
| Embodiment 2-15 | 37.5 | 25 | 37.5 | - | Ta/5 | 70％ |
| Embodiment 2-16 | 37.5 | 25 | 37.5 | - | Mo/5 | 63％ |
| Embodiment 2-17 | 37.5 | 25 | 37.5 | - | W/5 | 61％ |
As clear from the result of table 13 institute, Nb not only is even add Ta, Mo, W also can access favorable durability.
Distortion of＜electric field induction and crystallographic system 〉
The best embodiment 2-10 of weather resistance in the foregoing description 2-1～2-17, about the composition in the above-mentioned PMN-PZ-PT three component system solid solution phasors, be identical with embodiment 2-1, with false cube crystalline substance as principal phase (become with Fig. 8 in the identical figure of embodiment 2-1).Here, from this embodiment 2-10, make the mole fraction of PMN certain, form to the material of regular crystal side displacement 2-5 as a comparison case.That is, embodiment 2-10 is in above-mentioned general formula (4), and (a, b c) are (0.375,0.25,0.375), and use Sr and La, the addition p (Sr)=0.06 of Sr, and the dielectric composition of the addition p (La)=0.007 of La as Ma.And Comparative Examples 2-5 is (a, b c) replace with the dielectric composition (composition of the Comparative Examples 2-5 on the above-mentioned ternary phase diagrams shown in Figure 8 is to do reference) of (0.375,0.375,0.25) among this embodiment 2-10.The evaluation result of these embodiment is shown in Table 14.Moreover embodiment 2-1 and 2-2 also are shown in Table 14 to do reference.
Table 14
| (Mg, Nb) measures (mol%) | Ti measures (mol%) | Zr measures (mol%) | Replace Pb element/replacement amount (mol%) | Crystallographic system | Electric field induction distortion (%) | Weather resistance | |
| Embodiment 2-1 | 37.5 | 25 | 37.5 | - | False cube crystalline substance | 0.06 | 74％ |
| Embodiment 2-2 | 10 | 36 | 54 | - | The rhombohedron crystalline substance | 0.056 | 68％ |
| Embodiment 2-10 | 37.5 | 25 | 37.5 | Sr/6 La/0.7 | False cube crystalline substance | 0.065 | 80％ |
| Comparative Examples 2-5 | 37.5 | 37.5 | 25 | Sr/6 La/0.7 | Regular crystal | 0.098 | 38％ |
Clear as result institute from table 14, be the Comparative Examples 2-5 of principal phase with the regular crystal, electric field induction is out of shape greatly to 0.098%, and it is quite low that weather resistance also becomes.With respect to this, the distortion of the electric field induction of embodiment 2 is 0.06% at embodiment 2-1 (false cube crystalline substance), is 0.056% at embodiment 2-2 (rhombohedron crystalline substance), is 0.065% at embodiment 2-10 (false cube crystalline substance), all is that the electric field induction distortion is below 0.07%.And the weather resistance of these embodiment all reaches about 70%.Like this, principal phase is false cube crystalline substance or rhombohedron crystalline substance, and electric field induction is out of shape in the embodiment 2-1,2,10 below 0.07%, has obtained favorable durability.
The explanation of＜variation 〉
The invention is not restricted to above-mentioned embodiment and embodiment, the distortion that can in the scope that does not change essence part of the present invention, suit.Illustration variation below, but this variation is not limited to following situation.
For example, as the raw material of each above-mentioned dielectric composition, except the oxide compound of each element such as Pb, Mg, Nb, Zr, Ti, Ni (for example PbO, Pb
3O
4, MgO, Nb
2O
5, TiO
2, ZrO
2Deng) in addition, can use these each elements carbonate, contain several compound (MgNb for example of these each elements
2O) or the elemental metals of these each elements and alloy etc.In addition, these raw materials can use separately, perhaps can be used in combination two kinds or more than it.
About the addition means of Ni, can use the addition of Ni to be converted into NiO content and be in any means in the above-mentioned scope.For example, also can use as NiO and be added on method in the ready-made dielectric composition.In addition, Ni (NiO) preferably is evenly dispersed in the emtting electrode portion 12.But, also can be dispersed into Ni (NiO) at thickness direction and have concentration gradient, so that Ni (NiO) concentration is that the inside 12b of emtting electrode portion 12 increases to surperficial 12a from the fixed face of emtting electrode portion 12 and substrate 11.
In addition, as the preparation method of the dielectric composition that constitutes emtting electrode portion 12, can use the whole bag of tricks in addition of the method shown in the foregoing description.For example, alkoxide process or coprecipitation method etc. can be used.And then after forming the 1st electrode 14 and the 2nd electrode 16, suitable heat-treating do not have no relations but do not carry out this thermal treatment yet.But,,, after forming the 2nd electrode 16 on the substrate 11, preferably heat-treat as the above embodiments in order to make the 2nd electrode 16 and substrate 11 fixing and integrated.
And then, about the formation of electronic emission element of the present invention, also be not limited to the formation of the electronic emission element of above-mentioned embodiment.For example, in the above-described embodiment, the 1st electrode 14 forms on the surperficial 12a of emtting electrode portion 12, and the 2nd electrode 16 forms on the 12b of the inside of emtting electrode portion 12, but two electrodes also can all form on above-mentioned surperficial 12a.In addition, also can form the 1st electrode 14, emtting electrode portion the 12, the 2nd electrode 16 are laminated into several layers multilayered structure.
In addition, as the substrate 11 of matrix, except pottery, can use glass or metal.This ceramic kind has no particular limits.But, consider from the aspect of thermotolerance, chemical stability and insulativity, preferably constitute by containing at least a pottery that is selected from the group of forming by the zirconium white after the stabilization, aluminum oxide, magnesium oxide, mullite, aluminium nitride, silicon nitride and glass, wherein, aspect big from physical strength, good-toughness considers, is more preferably by the zirconium white after the stabilization to constitute.
In addition, said among the present invention " zirconium white after the stabilization " is meant, by adding the zirconium white that stabilization agent suppresses the crystallization phase transformation, except stabilized zirconium white, comprises by the zirconium white of partially stabilizedization.As the zirconium white after the stabilization, can enumerate the material of the stabilization agents such as calcium oxide, magnesium oxide, yttrium oxide, Scium trioxide, ytterbium oxide, cerium oxide or rare-earth oxide that contain 1～30mol%.Wherein, high especially this point of the physical strength in the vibration section preferably contains yttrium oxide as stabilization agent, and at this moment, yttrium oxide preferably contains 1.5～6mol%, more preferably contains 2～4mol%.In addition, preferably further contain 0.1～5mol% aluminum oxide.In addition, more preferably further contain 0.1～10mol% titanium oxide.
Zirconic crystalline phase after the stabilization can be that a cube crystalline substance+monoclinic mixed phase, regular crystal+monoclinic mixed phase, cube crystalline substance+regular crystal+monoclinic mixing equate.But, from the viewpoint of intensity, toughness and weather resistance, preferred principal crystalline phase is the mixed phase of regular crystal or regular crystal+cube crystalline substance.
In addition, by the replacement of the Pb of Sr, La, Bi, shown in embodiment 2-10, can be simultaneously with two kinds of elements or carry out more than it (replacing Ti too) by Nb, Ta, Mo, W.Have again, replace Pb and replace Ti by Sr, La, Bi and also can carry out (being equivalent to above-mentioned the 6th dielectric composition) simultaneously by Nb, Ta, Mo, W.
In addition, the 1st electrode 14 or the 2nd electrode 16 also can use non-metallic conductive particles conductive material (metallics, metallic membrane, nonmetal conductive film etc.) in addition to constitute.As metal, can enumerate at least a metal that is selected from by in the group of platinum, palladium, rhodium, gold and silver and their alloy composition.Wherein, high this point of the thermotolerance during from thermal treatment piezoelectricity/electric variant part considers, preferred platinum or be the alloy of principal constituent with platinum.Perhaps consider preferred silver-palladium alloy from high this point of the low but thermotolerance of cost.
In addition, the shape of the peristome 20 of the 1st electrode 14 also can adopt the various shapes in addition of the shape shown in the above-mentioned embodiment.Promptly, section form in the cap portion 26 that the inner edge 26b of peristome 20 power line is concentrated, except thickness direction shown in Figure 2, the 1st electrode 14 has the shape of acute angle at middle body, for example have in the bottom of the thickness direction of the 1st electrode 14 acute angle shape etc., towards the thickness of inner edge 26b the 1st electrode 14 gradually the shape of attenuation also realize easily.In addition, above-mentioned peristome shape also can be adhered at the inner-wall surface of peristome from side section and be seen that the thrust of the shape with acute angle or conductive particle realize.In addition, above-mentioned peristome shape also can form hyperbolic planar (it is planar particularly to see that from side section upper end and bottom all become the hyperbolic of acute angle in the inner margin portion of peristome 20) by the inner-wall surface of peristome 20 and realize.
As the method that forms electrode, for example can enumerate methods such as ionic fluid method, sputtering method, vacuum vapour deposition, PVD method, ion plating method, CVD method, electrochemical plating, silk screen print method, spraying method or dip coating.Wherein, from matrix, and the connectivity aspect of dielectric film consider preferred silk screen print method or sputtering method.
Claims (18)
1. electronic emission element, it is characterized in that possessing: during by the electric field that applies 4kV/mm and the deformation rate electric field induction on this electric field vertical direction be deformed into 0.07% or the dielectric medium below it the emtting electrode portion, the electrode that forms on the surface of this emtting electrode portion that constitute and the matrix of supporting described emtting electrode portion and described electrode.
2. electronic emission element according to claim 1, it is characterized in that, described dielectric medium be by with the composition shown in the following general formula (1) as principal constituent, and the dielectric composition that contains Ni constitutes, the content of Ni in this dielectric composition, when being converted into the content of the NiO in this dielectric composition, be the amount that is equivalent to 0.05～2.0 weight %
General formula (1): Pb
xBi
p(Mg
Y/3Nb
2/3)
aTi
B-zM
zZr
cO
3
In the described general formula (1), 0.85≤x≤1.03,0.02≤p≤0.1,0.8≤y≤1.0, and a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), (0.375,0.425,0.200) and decimal in the scope of 5 encirclements, in addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.
3. electronic emission element according to claim 1, it is characterized in that, described dielectric medium be by with the composition shown in the following general formula (2) as principal constituent, and the dielectric composition that contains Ni constitutes, the content of Ni in this dielectric composition, when being converted into the content of the NiO in this dielectric composition, be the amount that is equivalent to 0.05～2.0 weight %
General formula (2): Pb
xBi
pSr
q(Mg
Y/3Nb
2/3)
aTi
B-zM
zZr
cO
3
In the described general formula (2), 0.65≤x≤1.01,0.02≤p≤0.1,0.02≤q≤0.20,0.8≤y≤1.0, and a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, to be in by (0.550,0.425,0.025), (0.550,0.150,0.300), (0.100,0.150,0.750), (0.100,0.525,0.375), (0.375,0.425,0.200) decimal in the scope of 5 encirclements, in addition, 0.02≤z≤0.10, M is select from Nb, Ta, Mo, W at least a.
4. according to claim 2 or 3 described electronic emission elements, it is characterized in that described dielectric composition contains and is being converted into MnO
2Containing ratio the time be equivalent to the Mn of the amount of 0.05～1.0 weight %.
5. electronic emission element according to claim 1 is characterized in that, described dielectric medium with the dielectric composition shown in the following general formula (3) as principal constituent,
General formula (3): Pb
x(Mg
Y/3Nb
2/3)
aTi
bZr
cO
3
In the described general formula (3), 0.95≤x≤1.05,0.90≤y≤1.10, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), the decimal in the scope of (0.250,0.360,0.390) 5 encirclements.
6. electronic emission element according to claim 1 is characterized in that, described dielectric medium with the composition shown in the following general formula (4) as principal constituent,
General formula (4): Pb
X-pMa
p(Mg
Y/3Nb
2/3)
aTi
bZr
cO
3
In the described general formula (4), 0.95≤x≤1.05,0.90≤y≤1.10, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), (0.250,0.360,0.390) and decimal in the scope of 5 encirclements, in addition, Ma is select from Sr, La, Bi at least a.
7. electronic emission element according to claim 6 is characterized in that, in the described general formula (4), the scope of the described p value p (Sr) when Ma is Sr is 0.03≤p (Sr)≤0.15.
8. according to claim 6 or 7 described electronic emission elements, it is characterized in that in the described general formula (4), the scope of the p when Ma is La and/or Bi (La+Bi) value is 0.002≤p (La+Bi)≤0.015.
9. electronic emission element according to claim 1 is characterized in that, described dielectric medium with the dielectric composition shown in the following general formula (5) as principal constituent,
General formula (5): Pb
x(Mg
Y/3Nb
2/3)
aTi
B-qMb
qZr
cO
3
In the described general formula (5), 0.95≤x≤1.05,0.90≤y≤1.10, and also a, b, c are with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), (0.250,0.360,0.390) and decimal in the scope of 5 encirclements, in addition, Mb is select from Nb, Ta, Mo, W at least a.
10. electronic emission element according to claim 9 is characterized in that, in the described general formula (5), the scope of described q is 0.10≤q≤0.15.
11. electronic emission element according to claim 1 is characterized in that, described dielectric medium with the dielectric composition shown in the following general formula (6) as principal constituent,
General formula (6): Pb
X-pMa
p(Mg
Y/3Nb
2/3)
aTi
B-qMb
qZr
cO
3
In the described general formula (6), 0.95≤x≤1.05,0.90≤y≤1.10, and a, b, c be with (a, b, c)=(1,0,0), (0,1,0), (0,0,1) 3 is in the trigonometric coordinates on summit, be in by (0.500,0.350,0.150), (0.500,0.100,0.400), (0.050,0.100,0.850), (0.050,0.425,0.525), (0.250,0.360,0.390) decimal in the scope of 5 encirclements, in addition, Ma is select from Sr, La, Bi at least a, and then Mb is select from Nb, Ta, Mo, W at least a.
12. electronic emission element according to claim 11 is characterized in that, in the described general formula (6), the scope of the described p value p (Sr) when Ma is Sr is 0.03≤p (Sr)≤0.15.
13., it is characterized in that in the described general formula (6), the scope of the p when Ma is La and/or Bi (La+Bi) value is 0.002≤p (La+Bi)≤0.015 according to claim 11 or 12 described electronic emission elements.
14. the described electronic emission element of arbitrary claim according in the claim 11～13 is characterized in that, in the described general formula (6), the scope of described q is 0.01≤q≤0.15.
15. the described electronic emission element of arbitrary claim according in the claim 5～14 is characterized in that, described dielectric medium is a principal phase with false cube crystalline substance or rhombohedron crystalline substance.
16. the described electronic emission element of arbitrary claim according in the claim 1～15 is characterized in that, described emtting electrode portion is arranged to be fixed on the surface of described matrix.
17. electronic emission element according to claim 16, it is characterized in that, described electrode is made of the 1st electrode of the face side that is arranged on described emtting electrode portion and the 2nd electrode that is arranged on the inside side of described emtting electrode portion, described the 2nd electrode is arranged to be fixed on the surface of described matrix, and described emtting electrode portion is arranged to be fixed on described the 2nd electrode.
18. the described electronic emission element of arbitrary claim according in the claim 1～17 is characterized in that, the thermal expansivity of described matrix is bigger than the thermal expansivity of described emtting electrode portion.
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| JP2005208337 | 2005-07-19 |
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| MY104019A (en) * | 1988-05-27 | 1993-10-30 | Mitsui Chemicals Inc | Ferroelectric ceramic material. |
| JP3161261B2 (en) * | 1994-11-28 | 2001-04-25 | 株式会社村田製作所 | Piezoelectric ceramic composition |
| US6091190A (en) * | 1997-07-28 | 2000-07-18 | Motorola, Inc. | Field emission device |
| JP2002151270A (en) * | 2000-11-07 | 2002-05-24 | Matsushita Electric Ind Co Ltd | El lamp |
| WO2002092533A1 (en) * | 2001-05-16 | 2002-11-21 | E.I. Du Pont De Nemours And Company | Dielectric composition with reduced resistance |
| WO2003056879A1 (en) * | 2001-12-21 | 2003-07-10 | Ifire Technology Inc. | Low firing temperature thick film dielectric layer for electroluminescent display |
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