Patent Application
20060044730
The present invention relates to a dielectric composition, and to a dielectric film element employing the dielectric composition. More particularly, the present invention relates to a dielectric composition which is suitable for use in an electron emitter as an electron beam sources in various devices and apparatus that utilize electron beams, such as displays (e.g., field emission displays (FEDs)), electron beam irradiation apparatus, light sources, electronic-component-manufacturing apparatus, and electronic circuit components; and to a dielectric film element employing the dielectric composition.
As is generally known, the aforementioned electron emitter is configured such that a predetermined electric field is applied to an emitter section (electron emission section) in a vacuum having a predetermined vacuum level, whereby electrons are emitted from the emitter section. In application to FEDs, a plurality of electron emitters are two-dimensionally arrayed, and a plurality of phosphors corresponding to the electron emitters are arrayed with a predetermined spacing held therebetween. Among the two-dimensionally arrayed electron emitters, certain electron emitters are selectively driven so as to emit electrons therefrom. The emitted electrons collide with phosphors corresponding to the driven electron emitters. The phosphors hit by the electrons fluoresce, thereby displaying a desired image.
Specific examples of the electron emitter are disclosed in, for example, in the following Patent References 1 to 5. Such a disclosed electron emitter includes an emitter section formed of a fine conductive electrode having a pointed tip end portion, and a counter electrode provided so as to face the emitter section, and the electron emitter is configured such that when a predetermined drive voltage is applied to the emitter section and the counter electrode, electrons are emitted from the tip end portion of the emitter section.
Accordingly, forming such a fine conductive electrode requires micromachining that employs etching, forming, or the like, and thus production of the electron emitter involves a complicated process. Meanwhile, a certain high level of drive voltage must be applied to the electron emitter for emitting a predetermined number of electrons from the tip end portion of the conductive electrode to a vacuum having a predetermined vacuum level. Therefore, driving the electron emitter requires an expensive drive element (e.g., IC) which is applicable to high-voltage drive.
Thus, the above-disclosed electron emitter, which includes an emitter section formed of a conductive electrode, involves a problem in that high cost is required for producing the electron emitter per se, or a device employing the electron emitter.
Therefore, an electron emitter in which an emitter section is formed of a dielectric material is devised, which emitter is disclosed in, for example, in Patent References 6 and 7. General findings regarding electron emission in the case where a dielectric material is used to form an emitter section are disclosed in, for example, in the following Non-Patent References 1 to 3.
The electron emitter disclosed in Patent References 6 and 7 (hereinafter may be referred to simply as a “conventional electron emitter”) is configured such that a cathode electrode covers a portion of the top surface of an emitter section formed of a dielectric material, and an anode electrode is provided on the bottom surface of the emitter section, or on the top surface of the emitter section with a predetermined spacing maintained between the same and the cathode electrode. Specifically, the electron emitter is configured such that an exposed portion of the top surface of the emitter section at which neither the cathode electrode nor the anode electrode is formed is present in the vicinity of a peripheral edge portion of the cathode electrode.
Then, in a first stage, voltage is applied between the cathode electrode and the anode electrode such that the cathode electrode is higher in electric potential. An electric field generated by the applied voltage brings the emitter section (in particular, the aforementioned exposed portion) into a predetermined polarization state. In a second stage, voltage is applied between the cathode electrode and the anode electrode such that the cathode electrode is lower in electric potential. At this time, primary electrons are emitted from the peripheral edge portion of the cathode electrode, and the polarization of the emitter section is inverted. The primary electrons collide with the exposed portion of the polarization-inverted emitter section, whereby secondary electrons are emitted from the emitter section (particularly from the exposed portion). The secondary electrons fly in a predetermined direction by means of an externally applied, predetermined electric field; i.e., the electron emitter emits electrons.
However, the conventional electron emitter, which includes an emitter section formed of a dielectric material, involves a problem in that the electron emission quantity is considerably reduced due to deterioration of the emitter section as a result of repeated use of the electron emitter.
The present invention has been accomplished in view of the above-described problems, and an object of the present invention is to provide a dielectric composition which, when applied to an electron emitter, enables suppression of reduction of electron emission quantity due to repeated use of the electron emitter. Another object of the invention is to provide a dielectric film element employing the dielectric composition.
Accordingly, the present invention provides a dielectric composition containing, as a primary component, a composition represented by the following formula (1):
PbxBip(Mgy/3Nb2/3)aTib-zMzZrcO3 (1)
[wherein x, p, and y satisfy the following relations: 0.85≦x≦1.03, 0.02≦p≦0.1, and 0.8≦y≦1.0; a, b, and c are decimal numbers falling within a region formed by connecting the following five points (0.550, 0.425, 0.025), (0.550, 0.150, 0.300), (0.100, 0.150, 0.750), (0.100, 0.525, 0.375), and (0.375, 0.425, 0.200) in a triangular coordinate system of (a, b, c) having the following three vertexes (1, 0, 0), (0, 1, 0), and (0, 0, 1); z satisfies the following relation: 0.02≦z≦0.10; and M is at least one element selected from among Nb, Ta, Mo, and W], which dielectric composition contains Ni in an amount of 0.05 to 2.0 wt. % as reduced to NiO (hereinafter, this dielectric composition will be referred to as “a first dielectric composition of the present invention”).
More preferably, the dielectric composition of the present invention containing, as a primary component, a composition represented by the following formula (2):
PbxBipSrq(Mgy/3Nb2/3)aTib-zMzZrcO3 (2)
[wherein x, p, q, and y satisfy the following relations: 0.65≦x≦1.01, 0.02≦p≦0.1, 0.02≦q≦0.20, and 0.8≦y≦1.0; a, b, and c are decimal numbers falling within a region formed by connecting the following five points (0.550, 0.425, 0.025), (0.550, 0.150, 0.300), (0.100, 0.150, 0.750), (0.100, 0.525, 0.375), and (0.375, 0.425, 0.200) in a triangular coordinate system of (a, b, c) having the following three vertexes (1, 0, 0), (0, 1, 0), and (0, 0, 1); z satisfies the following relation: 0.02≦z≦0.10; and M is at least one element selected from among Nb, Ta, Mo, and W], which dielectric composition contains Ni in an amount of 0.05 to 2.0 wt. % as reduced to NiO (hereinafter, this dielectric composition will be referred to as “a second dielectric composition of the present invention,” and the first and second dielectric compositions and subordinate compositions thereof will be collectively called “the dielectric composition of the present invention”).
Preferably, the first dielectric composition of the present invention contains, as a primary component, a composition represented by the following formula (3):
Pbx(Mgy/3Nb2/3)aTibZrcO3 (3)
[wherein x and y satisfy the following relations: 0.95≦x≦1.05 and 0.8≦y≦1.0; a, b, and c are decimal numbers falling within a region formed by connecting the following five points (0.550, 0.425, 0.025), (0.550, 0.150, 0.300), (0.100, 0.150, 0.750), (0.100, 0.525, 0.375), and (0.375, 0.425, 0.200) in a triangular coordinate system of (a, b, c) having the following three vertexes (1, 0, 0), (0, 1, 0), and (0, 0, 1)], wherein 2 to 10 mol % of Pb is substituted by Bi, 2 to 10 mol % of Ti is substituted by at least one element selected from among Nb, Ta, Mo, and W, and the NiO content is 0.05 to 2.0 wt. % on the basis of the entirety of the dielectric composition. In particular, for example, oxides, carbonates, etc. of elements (e.g., Pb, Mg, Nb, Ti, Zr, Ni, Bi, and Ta) are mixed such that the mole fractions of the elements fall within the above-described ranges. After that, the mixture is placed in a hermetic container and calcined at a predetermined temperature. Next, the thus-calcined product is milled so as to form particles having a predetermined particle size, and then the dielectric composition of the present invention may be obtained. A dielectric film element of the present invention can be produced by forming the emitter section 12 through a generally employed production process such as screen printing, dipping, application, electrophoresis, aerosol deposition, the ion beam process, sputtering, vacuum deposition, ion plating, chemical vapor deposition (CVD), plating, and the green sheet process.
Preferably, the second dielectric composition of the present invention contains, as a primary component, a composition represented by formula (3), wherein 2 to 10 mol % of Pb is substituted by Bi, 2 to 20 mol % of Pb is substituted by Sr, 2 to 10 mol % of Ti is substituted by at least one element selected from among Nb, Ta, Mo, and W, and the NiO content is 0.05 to 2.0 wt. % on the basis of the entirety of the dielectric composition. The second dielectric composition of the present invention can be prepared in a manner similar to that of the first dielectric composition.
More preferably, the first or second dielectric composition of the present invention contains Mn in an amount of 0.05 to 1.0 wt. % as reduced to MnO2.
In the above-mentioned range in the present invention, the amount of Pb substituted by Bi is more preferably 2 to 5 mol % (i.e., x and p in formula (1) satisfy the following relations: 0.90≦x≦1.03 and 0.02≦p≦0.05). The amount of Pb substituted by Sr is more preferably 1 to 15 mol % (i.e., x and p in formula (2) satisfy the following relations: 0.70≦x≦1.02 and 0.02≦p≦0.10 (more preferably 0.75≦x≦1.02 and 0.02≦p≦0.05), and q in formula (2) satisfies the following relation: 0.01≦q≦0.15). Yet more preferably, the amount of Pb substituted by Sr is 1 to 12 mol % (i.e., x and p in formula (2) satisfy the following relations: 0.73≦x≦1.02 and 0.02≦p≦0.10 (more preferably 0.78≦x≦1.02 and 0.02≦p≦0.05), and q in formula (2) satisfies the following relation: 0.01≦q≦0.12). The amount of Ti substituted by Nb, etc. is more preferably 3 to 8 mol % (i.e., z in formula (1) or (2) satisfies the following relation: 0.03≦z≦0.08). The Ni content is more preferably 0.50 to 1.0 wt. % as reduced to NiO. The Mn content is more preferably 0.01 to 0.2 wt. % as reduced to MnO2.
When a dielectric emitter section is formed of the dielectric composition of the present invention containing the aforementioned components, deterioration of the emitter section due to repeated use thereof can be suppressed, as compared with the case of a dielectric emitter section of the conventional electron emitter. That is, an electron emitter including the emitter section formed of the dielectric composition exhibits enhanced durability. Therefore, when the dielectric composition according to the present invention is applied to an electron emitter, reduction of the electron emission quantity, which is attributed to repeated use of the electron emitter, can be suppressed.
The present invention also provides a dielectric film element comprising a dielectric layer formed of the aforementioned dielectric composition; a first electrode provided on the top surface of the dielectric layer; a second electrode provided on the top surface or the bottom surface of the dielectric layer; and a substrate which is provided on the bottom surface of the dielectric layer and which supports the dielectric layer, wherein, when a drive voltage is applied to the first and second electrodes, electrons are emitted from the top surface of the dielectric layer.
In the dielectric film element having the aforementioned configuration, preferably, the second electrode is bonded onto the surface of the substrate, and the dielectric layer is bonded onto the second electrode. Specifically, in this preferred configuration, the second electrode is bonded onto the surface of the substrate, the dielectric layer is bonded onto the second electrode, and the first electrode is bonded onto the top surface of the dielectric layer. With this configuration, the area of the substrate required for forming a single electron emitter can be reduced, and the mounting density of electron emitters can be increased, as compared with the case where both the first and second electrodes are provided on the top surface of the dielectric layer. Therefore, particularly when this configuration is applied to an FED, high resolution is readily attained. In this configuration, the first electrode and the second electrode are respectively provided on different surfaces (more preferably, the top surface and the bottom surface) of the dielectric layer; i.e., the dielectric layer is provided between the first and second electrodes. Therefore, when a relatively high voltage is applied to these electrodes, discharge tends not to occur, as compared with the case where both the electrodes are provided on the top surface of the dielectric layer. Thus, the aforementioned configuration enables provision of an electron emitter which exhibits enhanced durability and increased electron emission quantity.
In the dielectric film element having the aforementioned configuration, the dielectric layer is preferably formed so as to have a thickness of 1 to 300 μm. When the thickness of the dielectric layer is less than 1 μm, the number of defects in the dielectric layer increases, and the layer is insufficiently densified. Therefore, the electric field intensity at defects of the resultant electron emitter becomes higher than that at electron emission sites of the emitter, and thus favorable electron emission characteristics are difficult to attain. In the case where the first electrode and the second electrode are respectively provided on different surfaces (particularly on the top surface and the bottom surface) of the dielectric layer, when the thickness of the dielectric layer is less than 1 μm; i.e., the distance between these electrodes is excessively small, dielectric breakdown may occur under application of a drive voltage. In contrast, when the thickness of the dielectric layer exceeds 300 μm, a large amount of stress is generated in the dielectric layer through application of a drive voltage. When such a large amount of stress is generated, in order to properly support the dielectric layer by the substrate, the thickness of the substrate must be increased. However, increasing the dielectric layer thickness leads to difficulty in miniaturizing and thinning an electron emitter, which is disadvantageous from the viewpoint of application of the electron emitter to a display (in particular, an FED). In the case where the first electrode and the second electrode are provided on different surfaces of the dielectric layer, when the thickness of the dielectric layer exceeds 300 μm, excessively high drive voltage must be applied for attaining an electric field intensity necessary for electron emission, and therefore, for example, a high-voltage-resistance drive IC is required, leading to an increase in production cost of an electron emitter.
The thickness of the dielectric layer is more preferably 5 to 100 μm, from the viewpoints of densification of the structure of the dielectric layer, prevention of dielectric breakdown, miniaturization and thinning of an electron emitter, reduction of drive voltage, enhancement of production yield, and attainment of reliable electron emission performance.
Preferably, the electron emitter employing the dielectric film element of the present invention is configured such that it can be operated as follows: in the first stage, a drive voltage is applied such that the first electrode becomes lower in electric potential than the second electrode, whereby electrons are emitted (supplied) from the first electrode toward the surface of the dielectric layer; i.e., electrons are accumulated on the surface of the dielectric layer; and in the second stage, a drive voltage is applied such that the first electrode becomes higher in electric potential than the second electrode, whereby the electrons accumulated on the surface of the dielectric layer are emitted. Such a configuration allows relatively easy control of the quantity of the charge on the surface of dielectric layer in the first stage, so that high electron emission quantity can be reliably attained with high controllability.
Particularly preferably, the dielectric film element is configured such that an opening is formed in the first electrode, and a portion of the top surface of the dielectric layer corresponding to the opening is exposed to the outside. With this configuration, the electron emission quantity of a single electron emitter is increased, and the opening can serve as a gate electrode or a focusing electron lens with respect to electrons emitted from the surface of the dielectric layer. Thus, this configuration can enhance rectilinearity of the emitted electrons. Therefore, when a plurality of electron emitters are arranged on a flat plane, crosstalk between adjacent electron emitters is reduced. Particularly when the electron emitter is applied to an FED, the resolution of the FED is enhanced.
Preferred embodiments of the present invention will next be described with reference to the Tables and, if needed, the drawings.
(Schematic Description of FED Including Electron Emitter)
The display 100 includes the electron emitter 10; a transparent plate 30 provided above the electron emitter 10; a collector electrode 132 formed on the lower surface of the transparent plate 130 (i.e., the surface facing the electron emitter 10); a phosphor layer 34 formed on the lower surface of the collector electrode 132 (i.e., the surface facing the electron emitter 10); a bias voltage source 136 which is connected via a resistor to the collector electrode 132; and a pulse generator 18 which is connected to the electron emitter 10.
The transparent plate 130 is formed of a glass plate or an acrylic plate. The collector electrode 132 is formed of a transparent electrode such as an ITO (indium tin oxide) thin film. The space between the electron emitter 10 and the phosphor layer 134 is a vacuum atmosphere having a predetermined vacuum level of, for example, 102 to 10−6 Pa (more preferably 10−3 to 10−5 Pa). A collector voltage Vc is applied to the collector electrode 132 from the bias voltage source 136 via a predetermined resistor. The display 100 is configured such that electrons are emitted from the electron emitter 10 through an electric field generated through application of the collector voltage Vc, and the electrons fly toward the collector electrode 132 and collide with the phosphor layer 134, whereby light is emitted from predetermined pixel positions.
Numerous electron emitters 10 are two-dimensionally arrayed on a ceramic substrate 11. Notably,
The emitter section 12 is a dielectric layer formed of a polycrystalline material containing the dielectric composition employed in the present invention, and the thickness h of the emitter section is preferably 1 to 300 μm, more preferably 5 to 100 μm.
The first electrode 14 is formed so as to attain a thickness of 0.1 to 20 μm and has a plurality of opening portions 20 which are formed such that the top surface 12a of the emitter section 12 is exposed to the exterior of the electron emitter 10 (i.e., the aforementioned vacuum atmosphere; the same shall apply hereinafter). The top surface 12a of the emitter section 12 is exposed to the exterior of the electron emitter 10 also at peripheral edge portions 21 of the first electrode 14. Preferably, the opening portions 20 are formed in the first electrode 14 such that the total of the areas of the opening portions 20 accounts for 10 to 80% of the entire surface area of the emitter section 12 capable of contributing to electron emission. The first electrode 14 is formed of a metallic film, metallic particles, an electrically conductive non-metallic film (e.g., a carbon film or an electrically conductive non-metallic oxide film), or electrically conductive non-metallic particles (e.g., carbon particles or electrically conductive oxide particles). The first electrode 14 is formed on the top surface 12a through application, deposition, or a similar technique, so as to attain the aforementioned and predetermined thickness. The aforementioned metallic film or metallic particles are preferably formed of platinum, gold, silver, iridium, palladium, rhodium, molybdenum, tungsten, or an alloy thereof. The aforementioned electrically conductive non-metallic film or electrically conductive non-metallic particles are preferably formed of graphite, ITO (indium tin oxide), or LSCO (lanthanum strontium copper oxide). When the first electrode 14 is formed of metallic particles or electrically conductive non-metallic particles, preferably, the particles assume a scale-like, plate-like, foil-like, acicular, rod-like, or coil-like form. The second electrode 16 is formed of a metallic film so as to attain a thickness of preferably 20 μm or, less (more preferably 5 μm or less). Similar to the case of the aforementioned first electrode, the second electrode 16 is formed on the substrate 11 through application, deposition, or a similar technique.
Specifically, in the electron emitter 10, the second electrode 16 is bonded to the upper surface of the substrate 11; the emitter section 12 is bonded to the upper surface of the second electrode 16; and the first electrode 14 is provided on the top surface 12a of the emitter section 12. As used herein, the term “bonded” refers to the case where a component is joined directly and closely to another component without employment of an organic or inorganic adhesive.
As described below in detail, the electron emitter 10 is configured such that electrons supplied from the first electrode 14 are accumulated on the top surface 12a of the emitter section 12 corresponding to the opening portions 20 and the peripheral edge portions 21, and the thus-accumulated electrons are emitted toward the exterior of the electron emitter 10 (i.e., toward the phosphor layer 134).
(Detailed Description of Electron Emitter)
As shown in
Also, in the electron emitter 10, the top surface 12a of the emitter section 12 (i.e., the surface in the vicinity of the vertexes of convexities), and the lower surface 26a of the overhanging portion 26 of the first electrode 14 form a maximum angle θ that satisfies the following relation: 1°≦θ≦60°.
Also, in the electron emitter 10, the emitter section 12 and the first electrode 14 are formed such that the maximum gap d measured vertically between the top surface 12a of the emitter section 12 and the lower surface 26a of the overhanging portion 26 of the first electrode 14 is regulated so as to satisfy the following relation: 0 μm≦d≦10 μm, and that the surface roughness Ra (centerline average roughness, unit: μm) of the top surface 12a is regulated to 0.005 or more and 0.5 or less.
Then, triple junctions (formed by contact among the first electrode 14, the emitter section 12, and a vacuum) 26c are formed at contact sites among the top surface 12a of the emitter section 12, the first electrode 14, and a medium (e.g., a vacuum) surrounding the electron emitter 10. The triple junctions 26c are sites (electric field concentration points) at which lines of electric force concentrate (where electric field concentration occurs) when a drive voltage Va is applied to the first electrode 14 and the second electrode 16. As used herein, the expression “site at which lines of electric force concentrate” refers to a site at which lines of electric force that are generated from the second electrode 16 at even intervals concentrate, when the electric force lines are drawn under the assumption that the first electrode 14, the emitter section 12, and the second electrode 16 are flat plates each having a cross section extending infinitely. The state of the concentration of lines of electric force (i.e., the state of electric field concentration) can be readily observed through simulation by means of numerical analysis employing the finite-element method.
Further, in the electron emitter 10, the opening portions 20 are shaped such that the inner edges 26b thereof serve as the aforementioned electric field concentration points. Specifically, the overhanging portion 26 of the opening portion 20 has such a cross-sectional shape as to be acutely pointed toward the inner edge 26b (the tip end of the overhanging portion 26); i.e., the thickness gradually decreases. The electric field concentration points, which are formed at the inner edge 26b of the opening portion 20 as described above, and the triple junctions 26c are also formed at sites corresponding to the peripheral edge portions 21 of the first electrode 14.
In this instance, the opening portions 20 may be formed to assume a variety of shapes as viewed in plane, including, a circular shape, an elliptical shape, a polygonal shape, and an irregular shape. The opening portions 20 are formed such that, when the openings 20a as viewed in plane are approximated to circles having areas identical to those of the openings 20a as viewed in plane, the average diameter of the circles becomes 0.1 μm or more and 20 μm or less. The reason for this is described below. As shown in
Next will be described the principle of electron emission of the electron emitter 10 with reference to FIGS. 3 to 5. In the electron emitter 10, as shown in
In the initial state, the emitter section 12 is polarized unidirectionally. In the subsequent description, it is assumed that the emitter section 12 is initialized such that the negative poles of dipoles face toward the top surface 12a of the emitter section 12 (see
Firstly, in the initial state in which the reference voltage is applied, as shown in
Subsequently, when the negative voltage V2 is applied, polarization is inverted (see
Subsequently, when the drive voltage Va is changed from the negative voltage V2 to the reference voltage as shown in
In a manner similar to that described above, electrons are emitted from the peripheral edge portions 21 of the first electrode 14 at which the opening portions 20 are not present.
As shown in
However, the equivalent circuit, in which the capacitor C2 associated with the aforementioned aggregate is connected in series to the entirety of the capacitor C1 associated with the emitter section 12, is not practical. This is because, the percentage of the capacitor C1 to be connected in series to the capacitor C2 varies depending on, for example, the number of the opening portions 20 formed in the first electrode 14 and the overall area of the opening portions 20.
Capacitance will now be calculated under the assumption that, as shown in
Since the aforementioned portion of series connection and the remaining portion are connected in parallel, the overall capacitance is 27.5 pF, which is 78% of the capacitance of the capacitor C1 associated with the emitter section 12 (i.e., 35.4 pF). That is, the overall capacitance is lower than the capacitance of the capacitor C1 associated with the emitter section 12.
As described above, concerning the capacitors Ca associated with the gaps 28, the capacitance of the capacitor Ca associated with the aggregate of the gaps 28 is relatively low. So, most of the voltage Va is applied to the gaps 28 because of the divided voltage of the capacitor C1. Therefore, high emission of electrons is attained.
Since the capacitor C2 associated with the aggregate is connected, in series, to the capacitor C1 associated with the emitter section 12, the overall capacitance becomes lower than the capacitance of the capacitor C1 associated with the emitter section 12. This provides favorable characteristics of reduction in overall power consumption.
Specifically, the emitter section 12 employed in the first embodiment is formed from a dielectric composition containing, as a primary component, a composition represented by the following formula (1), and containing NiO in a predetermined amount.
PbxBip(Mgy/3Nb2/3)aTib-zMzZrcO3 (1)
[wherein x, p, and z satisfy the following relations: 0.85≦x≦1.03, 0.02≦p≦0.1, and 0.8≦y≦1.0; a, b, and c are decimal numbers falling within a region formed by connecting the following five points (0.550, 0.425, 0.025), (0.550, 0.150, 0.300), (0.100, 0.150, 0.750), (0.100, 0.525, 0.375), and (0.375, 0.425, 0.200) in a triangular coordinate system of (a, b, c) having the following three vertexes (1, 0, 0), (0, 1, 0), and (0, 0, 1); z satisfies the following relation: 0.02≦z≦0.10; and M is at least one element selected from among Nb, Ta, Mo, and W].
When this dielectric composition is employed, the dielectric layer forming the emitter section 12 can be densified, and electron emission characteristics can be improved. Specifically, when the dielectric layer forming the emitter section 12 is densified, the number of defects in the dielectric layer is reduced, and therefore, during application of the drive voltage Va, the electric field intensity at the aforementioned gaps 28 is enhanced, resulting in an increase in the electron emission quantity. In addition, even when the electron emitter 10 is repeatedly used for a long period of time, deterioration of the electron emission performance of the emitter section 12 is suppressed; i.e., the electron emitter 10 exhibits enhanced durability.
In contrast, as described below in the Examples and the Comparative Examples, when a, b, and c in formula (1), the Pb or Ti substitution amount, or the NiO content falls outside the aforementioned specific range, the electron emission performance of the emitter section 12 is considerably deteriorated when the electron emitter is repeatedly used.
When the NiO content is very low (i.e., less than 0.05%), the dielectric layer is insufficiently densified, and the electron emission performance is deteriorated. Specifically, the number of defects (e.g., pores) increases in the dielectric layer forming the emitter section 12, and electric field concentration occurs at such defects, which have lower dielectric constant, whereby the electric field intensity decreases at the electron emission sites corresponding to the gaps 28, resulting in reduction of the electron emission quantity.
From the viewpoint of suppression of deterioration of the emitter section 12 due to repeated use, in the aforementioned ranges specified by the present invention, the amount of Pb substituted by Bi is more preferably 2 to 5 mol %, the amount of Ti substituted by Nb, etc. is more preferably 3 to 8 mol %, and the NiO content is more preferably 0.50 to 1.0 wt. %.
(Production Method for Electron Emitter)
Firstly, on a substrate 11 formed of Y2O3-stabilized ZrO2, a second electrode 16 containing Pt and having predetermined dimensions and shape and a thickness of 3 μm is formed through screen printing. Subsequently, the second electrode 16 and the substrate 11 are bonded and combined by applying a thermal treatment at about 1,000 to about 400° C.
Subsequently, a dielectric composition containing, as a primary component, a composition represented by formula (1) and containing NiO in a predetermined amount (mass %) is applied onto the second electrode 16 through screen printing, so as to form a thick layer having a thickness of 40 μm.
In this instance, examples of the raw materials for the dielectric composition which may be employed include oxides of Pb, Mg, Nb, Zr, Ti, Ni, etc. (e.g., PbO, Pb3O4, MgO, Nb2O5, TiO2, ZrO2, and NiO); carbonates of these elements; compounds containing two or more species of these elements (e.g., MgNb2O); these metallic elements per se; and alloys of these elements. These raw materials may be employed singly or in combination of two or more species.
No particular limitation is imposed on the preparation method for the dielectric composition, and the composition may be prepared through, for example, the following procedure. Firstly, the aforementioned raw materials are mixed together such that the corresponding elements are contained in predetermined amounts. Subsequently, the resultant raw material mixture is calcined at 750 to 300° C., to thereby yield a dielectric composition. When the dielectric composition obtained through calcination is subjected to X-ray diffractometry, the ratio of the intensity of the strongest diffraction line of a phase other than a perovskite phase (e.g., a pyrochlore phase) to that of the strongest diffraction line of a perovskite phase is preferably 5% or less, more preferably 2% or less. Finally, the dielectric composition obtained through calcination is milled by use of, for example, a ball mill, to thereby prepare dielectric composition powder particles having a predetermined particle size (e.g., an average particle size of 0.1 to 1 μm as measured by means of laser diffractometry). The thus-prepared dielectric composition powder particles are dispersed in a predetermined binder, to thereby prepare a paste. The paste is applied onto the second electrode 16 through screen printing as described above, to thereby form a thick layer.
The thus-formed dielectric composition layer is thermally treated, to thereby evaporate the binder and densify the dielectric layer. Through this procedure, the emitter section 12 is formed.
Subsequently, a Pt-resinate-containing precursor is applied onto the above-formed emitter section 12 through screen printing, followed by thermal treatment, to thereby form a first electrode (Pt electrode) 14. Thus, the electron emitter 10 of dielectric film type is produced.
As described below, in Examples 1 through 8 and Comparative Examples 1 through 9, dielectric-film-type electron emitters were produced through the aforementioned production method. In each of these Examples and Comparative Examples, a display as shown in
In Example 1, there was employed a dielectric composition containing, as a primary component, Pb0.96Bi0.04(Mg1/3Nb2/3)0.20Ti0.38Nb0.05Zr0.37O3 and containing NiO in an amount of 1.0 mass %. Meanwhile, in each of Comparative Examples 1 through 3, there was employed a dielectric composition in which a, b, and c in formula (1) are changed so as to fall outside the scope of the present invention; i.e., a dielectric composition in which the Bi content, the Nb content, and the NiO content are the same as those of the dielectric composition employed in Example 1, and the (Mg1/3Nb2/3) content, the Ti content, and the Zr content are changed so as to fall outside the scope of the present invention. The results are shown in Table 1.
As is clear from the results shown in Table 1, in the case of Example 1, in which the (Mg1/3Nb2/3) content, the Ti content, and the Zr content fall within the scope of the present invention, the post-durability-test brightness is 77%. In contrast, in the cases of Comparative Examples 1 through 3, the post-durability-test brightness is a half or less that in the case of Example 1.
In each of Examples 2 and 3 and Comparative Examples 4 and 5, there was employed a dielectric composition in which the (Mg1/3Nb2/3) content, the Ti content, the Zr content, the Nb content, and the NiO content are the same as those of the dielectric composition employed in Example 1, and the Bi content is changed. The results are shown in Table 2.
As is clear from the results shown in Table 2, in the cases of Examples 1 through 3, in which the Bi content falls within the scope of the present invention, the post-durability-test brightness is about 60% or more. In contrast, in the cases of Comparative Examples 4 and 5, in which the Bi content falls outside the scope of the present invention, the post-durability-test brightness is less than 40%. Particularly when the amount of Pb substituted by Bi falls within a range of 2 to 5 mol %, the post-durability-test brightness is envisaged to become 70% or more. In the cases of Examples 1 and 2, in which the Pb substitution amount is 2 to 4 mol %, very high post-durability-test brightness is attained.
In each of Examples 4 and 5 and Comparative Examples 6 and 7, there was employed a dielectric composition in which the (Mg1/3Nb2/3) content, the Ti content, the Zr content, the Bi content, and the NiO content are the same as those of the dielectric composition employed in Example 1, and the Nb content is changed. The results are shown in Table 3.
As is clear from the results shown in Table 3, in the cases of Examples 1, 4, and 5, in which the Nb content falls within the scope of the present invention, the post-durability-test brightness exceeds 60%. In contrast, in the cases of Comparative Examples 6 and 7, in which the Nb content falls outside the scope of the present invention, the post-durability-test brightness is less than 50%. Particularly when the amount of Ti substituted by Nb falls within a range of 3 to 8 mol %, the post-durability-test brightness is envisaged to become 70% or more. In the cases of Examples 1 and 5, in which the Ti substitution amount is 5 to 8 mol %, very high post-durability-test brightness is attained.
In each of Examples 6 through 8 and Comparative Examples 8 and 9, there was employed a dielectric compositions in which the (Mg1/3Nb2/3) content, the Ti content, the Zr content, the Bi content, and the Nb content are the same as those of the dielectric composition employed in Example 1, and the NiO content is changed. The results are shown in Table 4.
As is clear from the results shown in Table 4, in the cases of Examples 1, 6, 7, and 8, in which the NiO content falls within the scope of the present invention, the post-durability-test brightness is 55% or more. In contrast, in the cases of Comparative Examples 8 and 9, in which the NiO content falls outside the scope of the present invention, the post-durability-test brightness is less than 40%. Particularly, in the cases of Examples 1 and 7, in which the NiO content falls within a range of 0.50 to 1.0 wt. %, the post-durability-test brightness is very high (about 70% or more).
In Example 9, 10, or 11, the element corresponding to M in formula (1) was changed from Nb to Ta, Mo, or W, respectively. In each of these Examples, high post-durability-test brightness was attained. The results are shown in Table 5.
As described above, a clear difference is observed in post-durability-test brightness between the case of Example 1, which falls within the scope of the present invention, and the case of Comparative Example 1, which falls outside the scope of the present invention; and the electron emitters of the Examples, which are invention products, exhibit good durability. Particularly, in the case of Example 1, which employs the dielectric composition containing, as a primary component, Pb0.96Bi0.04(Mg1/3Nb2/3)0.20Ti0.38Nb0.05Zr0.37O3, and containing NiO in an amount of 1.0 mass %, or in the case where the amount of Pb substituted by Bi is 2 to 5 mol %, the amount of Ti substituted by Nb, etc. is 3 to 8 mol %, and the NiO content is 0.50 to 1.0 wt. %, the post-durability-test brightness becomes very high (70% or more), which is remarkably preferable.
The emitted section 12 employed in the second embodiment is formed from a dielectric composition containing, as a primary component, a composition represented by formula (1), and containing NiO and MnO2 in predetermined amounts. That is, the dielectric composition forming the emitter section 12 according to the second embodiment contains the dielectric composition employed in the first embodiment, and contains Mn (MnO2) in a predetermined amount. The emitter section 12 and the electron emitter 10 including the emitter section 12 can be produced in a manner similar to that described above in the first embodiment.
In a manner similar to that described above in the first embodiment, a display as shown in
As is clear from the result shown in Table 6, the post-durability-test brightness is high in the cases of Example 12 (MnO2 content: 0.05 wt. %), Example 13 (MnO2 content: 0.2 wt. %), and Example 14 (MnO2 content: 1.0 wt. %). Particularly, in the cases of Examples 12 and 13, in which the MnO2 content falls within a range of 0.01 to 0.2 wt. %, the post-durability-test brightness is very high (75% or more).
The emitter section 12 employed in the third embodiment is formed from a dielectric composition containing, as a primary component, a composition represented by the following formula (2), and containing NiO in a predetermined amount (as in the cases of the aforementioned embodiments) (note: the dielectric composition is the aforementioned second dielectric composition).
PbxBipSrq(Mgy/3Nb2/3)aTib-zMzZrcO3 (2)
[wherein x, p, q, and y satisfy the following relations: 0.70≦x≦1.01, 0.02≦p≦0.1, 0.02≦q≦0.150; and 0.8≦y≦1.0; a, b, and c are decimal numbers falling within a region formed by connecting the following five points (0.550, 0.425, 0.025), (0.550, 0.150, 0.300), (0.100, 0.150, 0.750), (0.100, 0.525, 0.375), and (0.375, 0.425, 0.200) in a triangular coordinate system of (a, b, c) having the following three vertexes (1, 0, 0), (0, 1, 0), and (0, 0, 1); z satisfies the following relation: 0.02≦z≦0.10; and M is at least one element selected from among Nb, Ta, Mo, and W].
The dielectric composition forming the emitter section 12 according to the third embodiment is obtained by partially substituting Pb of the dielectric composition employed in the first embodiment by Sr in a predetermined amount. The emitter section 12 and the electron emitter 10 including the emitter section 12 can be produced in a manner similar to that of the above-described embodiments. In the third embodiment, the electron emitter was evaluated in a manner similar to that described above. The results are shown in Table 7.
As is clear from the results shown in Table 7, the post-durability-test brightness is high in the cases of Example 15 (amount of Pb substituted by Sr: 2 mol %), Example 16 (amount of Pb substituted by Sr: 10 mol %), and Example 17 (amount of Pb substituted by Sr: 20 mol %). Particularly, when the Pb substitution amount falls within a range of 1 to 15 mol %, the post-durability-test brightness is envisaged to become 75% or more. In the cases of Examples 15 and 16, in which the Pb substitution amount falls within a range of 1 to 12 mol %, the post-durability-test brightness is very high (about 80%).
(Suggestion of Some Modifications)
The present invention is not limited to the above-described embodiments and Examples, and appropriate modifications of the invention may be made so long as the essentials of the present invention are not changed. Modifications of the present invention will next be described, but the invention is not limited to the following modifications.
Addition of Ni may be performed through any technique, so long as the Ni content (as reduced to NiO) falls within the aforementioned range. For example, there may be employed a technique in which NiO is added to a dielectric composition which has been prepared in advance. Preferably, the thus-added Ni (NiO) is uniformly dispersed in the emitter section 12. However, the Ni (NiO) may be dispersed in the emitter section 12 such that the Ni (NiO) concentration increases in a thickness direction of the emitter section 12 from the bottom surface 12b (which is bonded to the substrate 11) toward the top surface 12a.
The dielectric composition forming the emitter section 12 may be prepared through a variety of techniques other than the technique described above in the Examples. For example, the dielectric composition may be prepared through the alkoxide method or the coprecipitation method. Although thermal treatment is preferably performed after formation of the first electrode 14 or the second electrode 16, the thermal treatment is not necessarily carried out. However, in order to bond and combine the second electrode 16 with the substrate 11, preferably, thermal treatment is performed after the second electrode 16 is formed on the substrate 11 as described above the Examples.
The configuration of the dielectric film element of the present invention is not limited to that of the electron emitter described above in the embodiments. For example, both the first electrode 14 and the second electrode 16 may be formed on the top surface 12a of the electron emitter 12, although, in the aforementioned embodiments, the first electrode 14 and the second electrode 16 are respectively formed on the top surface 12a and the bottom surface 12b of the emitter section 12. The dielectric film element may have the multi-layer configuration; the first electrodes 14, the emitter sections 12, and the second electrodes 16 may be layered to form the multi-layer configuration.
The substrate 11 may be formed of a glass or metallic material in place of a ceramic material. No particular limitation is imposed on the type of the ceramic material to be employed. However, from the viewpoints of heat resistance, chemical stability, and insulating property, the substrate 11 is preferably formed of a ceramic material containing at least one species selected from the group consisting of stabilized zirconium oxide, aluminum oxide, magnesium oxide, mullite, aluminum nitride, silicon nitride, and glass. More preferably, the substrate 11 is formed of stabilized zirconium oxide, from the viewpoints of high mechanical strength and excellent toughness.
As used herein, the term “stabilized zirconium oxide” refers to zirconium oxide in which crystal phase transition is suppressed through addition of a stabilizer. The stabilized zirconium oxide encompasses partially stabilized zirconium oxide. Examples of the stabilized zirconium oxide include zirconium oxide containing a stabilizer (e.g., calcium oxide, magnesium oxide, yttrium oxide, scandium oxide, ytterbium oxide, cerium oxide, or an oxide of a rare earth metal) in an amount of 1 to 30 mol %. From the viewpoint of further enhancement of the mechanical strength of a vibration section, zirconium oxide containing yttrium oxide as a stabilizer is preferably employed. In this case, the yttrium oxide content is preferably 5 to 6 mol %, more preferably 2 to 4 mol %. Zirconium oxide containing, in addition to yttrium oxide, aluminum oxide in an amount of 0.1 to 5 mol % is more preferred.
The stabilized zirconium oxide may have, for example, a cubic-monoclinic mixed crystal phase, a tetragonal-monoclinic mixed crystal phase, or a cubic-tetragonal-monoclinic mixed crystal phase. From the viewpoints of strength, toughness, and durability, the stabilized zirconium oxide preferably has, as a primary crystal phase, a tetragonal crystal phase or a tetragonal-cubic mixed crystal phase.
The first electrode 14 or the second electrode 16 may be formed of an electrically conductive material (e.g., metallic particles, metallic film, or electrically conductive non-metallic film) other than electrically conductive non-metallic particles. Examples of the metal which may be employed include at least one metal selected from the group consisting of platinum, palladium, rhodium, gold, silver, and an alloy thereof. Particularly, from the viewpoint that high heat resistance is required during thermal treatment of a piezoelectric/electrostrictive section, platinum or an alloy predominantly containing platinum is preferably employed. Alternatively, from the viewpoint of low cost and high heat resistance, a silver-palladium alloy is preferably employed.
The opening portions 20 of the first electrode 14 may assume a variety of shapes other than the shapes described above in the embodiments. Specifically, the overhanging portion 26 corresponding to each of the opening portions 20, at which lines of electric force concentrate, may have a cross-sectional shape such that the thickness of the first electrode 14 gradually decreases toward the inner edge 26b; for example, a cross-sectional shape as shown in
10 . . . electron emitter, 11 . . . substrate, 12 . . . remitter section, 12a . . . top surface, 12b . . . bottom surface, 14 . . . first electrode, 16 . . . second electrode, 20 . . . opening portion, 26 . . . overhanging portion, 28 . . . gap
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-245833 | Aug 2004 | JP | national |
| 2005-208366 | Jul 2005 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| 60611926 | Sep 2004 | US |
