JP3296549B2 - Ink jet ejecting apparatus and ink jet ink used therefor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet ejecting apparatus provided with an ejection nozzle for ejecting a liquid containing an organometallic complex metal component and a resin as a material for forming an electron emitting portion as droplets, and an ink jet ink used therefor.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices using a thermionic electron-emitting device and a cold-cathode electron-emitting device have been known. Cold cathode electron-emitting devices include a field emission type (hereinafter, referred to as “FE type”), a metal / insulating layer / metal type (hereinafter, referred to as “MIM type”), and a surface conduction type electron emission device (hereinafter, referred to as “MIM type”). SCE type ").
As an example of the FE type, W. P. Dyke & W. W. Do
lan, "Fieldmission", Advan
ce in Electron Physics, 8,
89 (1956) or C.I. A. Spindt, "P
HYSICALProperties of thin
-Film field emission cath
odes with molebdenium con
es ", J. Appl. Phys., 47, 5248.
(1976) are known.

As an example of the MIM type, C.I. A. Mea
d, “Operation of Tunnel-Em
issue Devices ", J. Apply. P
hys. , 32, 646 (1961).

As an example of the SCE type, M. I. Elin
son, Radio Eng. Electron Ph
ys. , 10, 1290 (1965) and the like are known.

[0005] The SCE type electron-emitting device utilizes the phenomenon that electron emission occurs when a current flows through a small-area thin film formed on a substrate in parallel with the film surface. Examples of the surface conduction electron-emitting device include a device using an SnO ₂ thin film by Elinson et al. And a device using an Au thin film [G. Dittmer: “Thin Solid Fi
lms ", 9,317 (1972)] , In 2 O 3 / S
nO ₂ thin film [M. Hartwell and
C. G. FIG. Fonstad: "IEEE Trans.
ED Conf. , 519 (1975)], using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1,
No. 22, p. 22 (1983)].

FIG. 1 schematically shows an example of an element configuration of these SCE type electron-emitting devices. In FIG. 1, reference numeral 1 denotes an insulating substrate, and reference numerals 2 and 3 denote device electrodes. Reference numeral 4 denotes a thin film for forming an electron-emitting portion, which is formed by applying a solution of an organometallic compound onto an H-shaped pattern, drying the resultant, and then thermally decomposing and removing an organic component by heating and baking to form a metal or metal oxide. The electron-emitting portion 5 is formed by an energization process called energization forming described below. Note that the element electrode interval L in the figure is 0.
5 mm to 1 mm, W 'is set to 0.1 mm.

Conventionally, in these SCE-type electron-emitting devices, the electron-emitting portion 5 is generally formed by applying a current to the electron-emitting portion-forming thin film 4 before the electron emission by an energization process called energization forming. Was. That is, the energization forming means that a DC voltage or a very slowly increasing voltage, for example, 1 V is applied to both ends of the thin film 4 for forming an electron emission portion.
/ Min. By applying an electric current at about / min to locally destroy, deform or alter the thin film for forming the electron emitting portion, thereby forming the electron emitting portion 5 in an electrically high resistance state. In the electron emitting portion 5, a crack is generated in a part of the thin film 4 for forming the electron emitting portion, and the electron is emitted from the vicinity of the crack. The SCE-type electron-emitting device that has been subjected to the energization forming process applies electrons to the thin film 4 for forming an electron-emitting portion and causes current to flow through the device, thereby causing the electron-emitting portion 5 to emit electrons.

[0008]

However, these conventional SCE devices have various problems as described below.

That is, since the above-mentioned SCE type element has a simple structure and is easy to manufacture, there is an advantage that a large number of elements can be arrayed over a large area. Therefore, taking advantage of this feature, application as a light emitting element or a display device is being studied. For example, by combining an electron source having a large number of SCE-type elements and a phosphor that emits visible light by electrons emitted from the electron source, the device can be used as an image forming apparatus that is a flat display device.

However, when the above-mentioned flat display device is made to have a large area, a large-sized manufacturing apparatus is required to manufacture a fine pattern such as an electrode on a large-sized substrate by using a conventional photolithography technique. Costly.

Further, the thin film 4 for forming an electron emission portion is formed by applying a solution obtained by dissolving an organometallic compound in an organic solvent to a substrate and drying it, and then thermally baking to remove the organic components by thermal decomposition to form a metal or metal oxide. It is not desirable to use an organic solvent in the process of forming the thin film 4 for forming the electron emission portion from the viewpoint of cost reduction and environmental protection, and it has been desired to complete an organometallic complex that easily dissolves in water. Further, it has been desired that the electron emission film formed using the organometallic complex has a uniform thickness and good electron emission characteristics.

Further, as a method of producing the thin film 4 for forming the electron-emitting portion, a production method by an ink jet or bubble jet method (hereinafter abbreviated as BJ method) has been proposed. It is desirable to use an aqueous solution of an organometallic complex from the viewpoint of stable drop generation.

An object of the present invention is to provide such a prior art SC.
In order to improve the disadvantages of the E-type element, a liquid containing a water-soluble organometallic complex metal component having a uniform film thickness and good electron emission characteristics is obtained as droplets, particularly as an electron-emitting element. An object of the present invention is to provide an ink jet ejecting apparatus having a discharge nozzle and an ink jet ink used therefor.

[0014]

Means for Solving the Problems As a result of diligent studies to achieve the above object, the present inventor has found that a liquid containing a water-soluble organometallic complex metal component having a specific chemical structure and a resin is converted into droplets. The present invention, which can solve the above-described problems, has been completed by using an inkjet ejecting apparatus having an ejection nozzle for ejecting the ink and an inkjet ink used therefor.

That is, the ink jet injection device of the present invention is characterized by comprising a discharge nozzle for discharging a liquid containing an organometallic complex metal component and a resin represented by the following formula as droplets.

[0016]

Embedded image (However, R ₁ , R ₂ ; an alkyl group having 1 to 4 carbon atoms, 1:
An integer of 2 to 4, an integer of m = 1 to 4, an integer of n = 0 to 2,
(M = metal) The inkjet ink of the present invention is characterized by comprising a liquid containing a metal component of an organometallic complex represented by the following formula and a resin.

[0017]

Embedded image (However, R ₁ and R ₂ : an alkyl group having 1 to 4 carbon atoms;
An integer of 2 to 4, an integer of m = 1 to 4, an integer of n = 0 to 2,
M = metal)

Hereinafter, the present invention will be described in more detail. As the material for forming an electron emission portion applied to the present invention, a material containing a water-soluble organometallic complex having a specific chemical structure and a specific resin is used. The organometallic complex having this specific chemical structure is represented by the following formula.

[0019]

Embedded image (However, R ₁ , R ₂ : an alkyl group having 1 to 4 carbon atoms, l:
An integer of 2 to 4, an integer of m = 1 to 4, an integer of n = 0 to 2,
M = metal)

The material for forming an electron-emitting portion applied to the present invention may contain one or more of the organometallic complexes represented by the above formula. Further, it is used as an aqueous solution to which a water-soluble resin is added for the purpose of adjusting the viscosity. As described above, in the material for forming an electron emission portion applied to the present invention, an aqueous solution of a specific organometallic complex is used, and a droplet of the aqueous solution is prevented from penetrating into a printing electrode having a low film density. In order to maintain the droplet shape, the aqueous solution contains a specific water-soluble resin, so that the aqueous solution is used as an aqueous solution adjusted to an appropriate viscosity.

Generally, a thin film formed by a printing method has a lower film density than a thin film formed by an evaporation method or the like. There is a risk of permeation into the electrode. When such a phenomenon occurs, the film thickness becomes non-uniform between the devices after subsequent drying or firing, and as a result, the conductive film of the electron-emitting portion becomes non-uniform, which causes variations in the characteristics of the electron-emitting devices. .

The water-soluble resin is added in order to prevent such a situation. By adjusting the viscosity of the aqueous solution by adding the resin, it is possible to prevent the permeation into the electrode and increase the retention of the droplet shape. And, as a result, a uniform conductive film can be formed.

The optimum range of the metal concentration of the aqueous solution is slightly different depending on the kind of the metal element and the kind of the metal salt to be used, but generally the range of 0.01% to 5% by weight is appropriate. As the central metal of the organometallic compound, one that easily emits electrons by applying a voltage, that is, one that has a relatively low work function and is stable, for example, Pt, Pd,
Platinum group such as Ru, Au, Ag, Cu, Cr, Ta, F
metals such as e, W, Pb, Zn, and Sn.

On the other hand, the water-soluble resin must be one that does not cause a chemical reaction with the organometallic compound as the main component. Examples of the resin used include polyvinyl alcohol, polyethylene oxide, starch, methyl cellulose, and hydroxyethyl cellulose. It is necessary that the water-soluble resin used in the present invention is completely decomposed at the heating and firing temperature and no residue remains after firing.

The means for applying the organic metal compound aqueous solution to the substrate may be any method as long as it is possible to form and apply droplets. An ink jet system which can be applied and has good controllability is convenient. Ink jet systems include those that generate and apply droplets by a mechanical impact such as a piezo element, and bubble jet (BJ) systems that generate and apply droplets by heating a liquid with a micro heater or the like and bump it. However, fine droplets of about 10 ng to about several tens μg can be generated with good reproducibility and applied to the substrate.

When droplets are applied by the BJ method, the viscosity of the aqueous solution at 25 ° C. is desirably 10 to 20 centipoise, and the resin is desirably added so as to have a viscosity in this range. If the concentration of the water-soluble resin is represented by the amount added, the preferred range is 0.01 to 0.5% by weight, and more preferably 0.03 to 0.1% by weight.
When the content is 0.01% by weight or less, the effect of the present invention cannot be obtained,
If the content is 0.5% by weight or more, it becomes difficult to continuously discharge by the ink jet method.

The material for forming an electron-emitting portion applied to the present invention is preferably used for an electron-emitting device in which the electron-emitting device is of a surface conduction type. A method for manufacturing an electron-emitting device to which the present invention is applied is a method for manufacturing an electron-emitting device having an electron-emitting portion between opposed electrodes, wherein the electron-emitting portion is formed through a process of heating and firing a metal compound. Wherein a step of applying a solution containing a metal complex and a water-soluble resin to the substrate having the opposed electrodes in the form of droplets, and a step of thermally decomposing the applied droplets are provided. is there.

The method of manufacturing an electron source to which the present invention is applied is as follows:
A method for manufacturing an electron source comprising an electron-emitting device and a means for applying a voltage to the device, wherein the electron-emitting device is manufactured by the method for manufacturing an electron-emitting device.

A method of manufacturing a display element to which the present invention is applied includes an electron source having an electron emitting element and a voltage applying means for the element, and a luminous element which emits light by receiving electrons emitted from the element. A method for manufacturing a display element provided, wherein the electron-emitting device is manufactured by the method for manufacturing an electron-emitting device.

A method of manufacturing an image forming apparatus to which the present invention is applied includes an electron source having an electron-emitting device and a means for applying a voltage to the device, a light-emitting body that receives and emits light from the device. And a drive circuit for controlling a voltage applied to the element based on an external signal, wherein the electron-emitting device is manufactured by the method for manufacturing an electron-emitting device. It is assumed that.

Next, the basic structure of a surface conduction electron-emitting device to which the present invention can be applied will be described with reference to the drawings. FIGS. 2A and 2B are a plan view and a sectional view, respectively, showing the configuration of a basic SCE-type electron-emitting device to which the present invention can be applied. In FIG. 2, 1 is an insulating substrate, 2 and 3 are device electrodes, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion.

As the insulating substrate 1, quartz glass, Na
Glass with reduced impurity content such as glass, blue plate glass, glass substrate laminated with SiO ₂ formed on blue plate glass by sputtering or the like, ceramics such as alumina, and Si
A substrate can be used. An offset printing method having a feature that the transfer film thickness of the ink can be reduced is suitable for forming the element electrode. Since the resolution can be increased as the thickness of the ink to be transferred is smaller, the offset printing method can perform high-definition printing. As a printing material for the electrodes, a resinate base made of an organic metal is used, the electrode interval between the pair of electrodes 2 and 3 is preferably several μm to several hundred μm, and the film thickness is preferably several hundred angstroms to several thousand angstroms.
Further, the wiring connected to the pair of electrodes can be formed by a screen printing method. That is, the present invention is characterized in that a printing method is used as a method for forming the element electrode, and an inkjet method and a BJ method are used as a method for manufacturing the thin film 4 for forming the electron-emitting portion.

It is preferable to use a fine particle film composed of fine particles for the electron emission portion forming thin film 4 in order to obtain good electron emission characteristics. It is appropriately set in consideration of the resistance value between the device electrodes 2 and 3 and the energizing forming conditions described later, but is usually preferably in the range of several angstroms to several thousand angstroms, and more preferably in the range of one thousand angstroms.
It is preferable that the angle be in the range of 0 to 500 degrees. The resistance value is such that R _s is 10 ² to 10 ⁷ ohm / □. Note that R _s is the resistance R of a thin film having a thickness t, a width w, and a length l.
Is set as R = R _s (l / w). In the specification of the present application, the forming process will be described by taking an energizing process as an example, but the forming process is not limited to this, and includes a process of forming a crack in a film to form a high resistance state. It is.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and has a fine structure in a state where the fine particles are dispersed and arranged here or in a state where the fine particles are adjacent to each other or overlapped (some fine particles are mixed). To form an island-like structure as a whole). The particle size of the microparticles ranges from a few Angstroms to several thousand Angstroms, preferably from 10 ° to 200 °.

In the present specification, the term “fine particles” is frequently used, and the meaning will be described. Small particles are called "fine particles" and smaller ones are called "ultra fine particles". It is widely practiced to call a “cluster” smaller than “ultrafine particles” and having a few hundred atoms or less.

However, each boundary is not strict, and changes depending on what kind of property is focused on. Further, “fine particles” and “ultrafine particles” may be collectively referred to as “fine particles”, and the description in this specification is in line with this. "Experimental Physics Course 14: Surfaces and Particles" (edited by Kinoshita Yoshio, published by Kyoritsu Shuppan, September 1, 1986) states as follows.

In the present description, "fine particles" have a diameter of about 2 to 3 μm to about 10 nm, and especially ultrafine particles have a particle diameter of about 10 nm to 2 to 3 nm.
It means up to about nm. It is not exactly strict because both are collectively written as fine particles, but it is a rough guide. When the number of atoms that make up a particle is two to several tens to several hundreds, it is called a cluster. "
(Pp. 195, lines 22-26) In addition, the definition of “ultrafine particles” in the “Hayashi / Ultrafine Particle Project” of the New Technology Development Corporation has a lower minimum particle size, as follows. Was.

In the “Ultra Fine Particle Project” of the Promotion System for Creative Science and Technology (1981-1986), a particle having a size (diameter) in the range of about 1 to 100 nm is called “ultra fine particle”. Then, one ultrafine particle is about 100-
It is an aggregate of about 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. ("Ultra Fine Particles-Creative Science and Technology-" Hayashi Tax, Ryoji Ueda, Akira Tazaki
Ed., Mita Publishing, 1988, page 2, lines 1 to 4) "A particle smaller than an ultrafine particle, that is, a single particle composed of several to several hundred atoms is usually called a cluster." Lines 12-13).

[0039] Based on the general notation as described above,
In this specification, the term "fine particles" refers to an aggregate of a large number of atoms and molecules, and the lower limit of the particle diameter is about several Angstroms to about 10 Angstroms, and the upper limit is about several microns.

The electron emitting portion 5 is composed of the electron emitting portion forming thin film 4.
Is formed by a high-resistance crack formed in a part of the thin film, and depends on the film thickness, film quality, and material of the electron-emitting-portion-forming thin film 4, a method such as energization forming described later, and the like. In some cases, conductive fine particles having a particle size in the range of several Angstroms to several hundred Angstroms depend inside the electron-emitting portion 5. The conductive fine particles contain some or all of the elements of the material constituting the thin film 4 for forming an electron emission portion. The electron-emitting portion 5 and the electron-emitting-portion-forming thin film 4 in the vicinity thereof may contain carbon and a carbon compound. Various methods are conceivable as a method for manufacturing the electron-emitting device having the electron-emitting portion 5, and an example is shown in FIG.

Hereinafter, a method of manufacturing an electron-emitting device will be described in order with reference to FIGS. 1) After sufficiently washing the insulating substrate 1 with a detergent, pure water, and an organic solvent, a resinate paste made of an organic metal is printed and baked by offset printing, and the device electrodes 2, 3 are formed.
To form

2) A droplet 8 containing an organometallic complex and a water-soluble resin is applied to the insulating substrate 1 on which the device electrodes 2 and 3 are formed by a droplet applying means 7 such as a BJ method, and is baked by heating. An electron emitting portion forming thin film 4 is formed using an inorganic compound. More specifically, the substrate coated with the organometallic complex is heated to a decomposition temperature or higher to decompose the organic component of the organometallic complex and the resin on the substrate, thereby forming the thin film 4 for forming the electron emission portion.
Get. When the above organometallic complex is heated and calcined, organic components and resins are decomposed at a temperature of 1000 ° C. or less, in most cases around 300 ° C., and inorganic compounds such as metals and metal oxides or simple organic substances having a small unit number are adsorbed on their surfaces. The substrate heating temperature is from 200 ° C. to 500 ° C. for most organometallic compounds. In the present invention, it is preferable to thermally decompose the organometallic complex in this heating step to obtain an inorganic compound such as a metal oxide or a metal nitride.

3) Subsequently, a forming step is performed.
As an example of a method of the forming step, a method by an energization process will be described. When an electric current is applied between the device electrodes 2 and 3 using a power supply (not shown), an electron emission portion 5 having a changed structure is formed at the portion of the electron emission portion forming thin film 4.
(C)). According to the energization forming, a portion having a structural change such as local destruction, deformation or alteration of the thin film 4 for forming an electron emission portion is formed. This portion constitutes the electron emission section 5. FIG. 4 shows an example of the voltage waveform of the energization forming.

The voltage waveform is preferably a pulse waveform. This includes the method shown in FIG. 4 in which a pulse having a pulse peak value of a constant voltage is continuously applied, and the method shown in FIG. 4b in which a voltage pulse is applied while increasing the pulse peak value.

T1 and T2 in FIG. 4A are the pulse width and pulse interval of the voltage waveform. Usually, T1 is set in the range of 1 microsecond to 10 milliseconds, and T2 is set in the range of 10 microseconds to 100 milliseconds. The peak value of the triangular wave (peak voltage during energization forming) is appropriately selected according to the form of the surface conduction electron-emitting device. Under such conditions, for example, a voltage is applied for several seconds to several tens minutes. The pulse waveform is not limited to a triangular wave, and a desired waveform such as a rectangular wave can be adopted.

T1 and T2 in FIG. 4b can be similar to those shown in FIG. 4a. The peak value of the triangular wave (peak voltage during energization forming) is, for example, 0.1
It can be increased by about V steps.

When the energization forming process is completed, the thin film 4 for forming an electron emission portion is locally destroyed during the pulse interval T2.
By applying a voltage that does not cause deformation, the current can be measured and detected. For example, an element current flowing by applying a voltage of about 0.1 V is measured, and a resistance value is obtained. When the resistance value indicates 1 M ohm or more, the energization forming is terminated.

4) It is preferable to perform a process called an activation step on the device after the forming. The activation step means that the element current If and the emission current Ie are
This is a process that changes significantly.

The activation step can be performed, for example, by repeatedly applying a pulse in an atmosphere containing an organic substance gas, similarly to the energization forming. This atmosphere can be formed by using an organic gas remaining in the atmosphere when the inside of the vacuum vessel is evacuated using, for example, an oil diffusion pump or a rotary pump, or a vacuum once sufficiently evacuated by an ion pump or the like. It can also be obtained by introducing a gas of an appropriate organic substance therein. The preferable gas pressure of the organic substance at this time varies depending on the above-described application form, the shape of the vacuum vessel, the type of the organic substance, and the like, and is appropriately set according to the case. Suitable organic substances include aliphatic hydrocarbons of alkanes, alkenes, and alkynes, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, and organic acids such as phenols, carboxylic acids, and sulfonic acids. Specifically, methane,
Saturated hydrocarbons represented by C _n H _{2n + 2} such as ethane and propane, unsaturated hydrocarbons represented by a composition formula such as C _n H _2n such as ethylene and propylene, benzene, toluene, methanol, ethanol, formaldehyde and acetaldehyde , Acetone, methyl ethyl ketone, methylamine, ethylamine, phenol, formic acid, acetic acid, propionic acid and the like can be used. By this treatment, carbon or a carbon compound is deposited on the device from the organic substance existing in the atmosphere, and the device current If and the emission current Ie are significantly changed.

The end of the activation step is determined as appropriate while measuring the device current If and the emission current Ie. The pulse width, pulse interval, pulse crest value, and the like are set as appropriate.

Carbon and carbon compounds include graphite (so-called highly oriented pyrolytic carbon HOPG, pyrolytic carbon P).
G, including amorphous carbon (GC), HOPG has a crystal structure of almost perfect graphite, PG has a crystal grain of about 200 ° and has a slightly disordered crystal structure, and GC has a crystal grain of 20 °.
It means that the degree of crystal structure disorder has further increased. ) Amorphous carbon (amorphous carbon and
The thickness is preferably in the range of 500 ° or less, and more preferably in the range of 300 ° or less.

5) The electron-emitting device obtained through the above steps is preferably subjected to a stabilization step. This step is a step of exhausting the organic substance in the vacuum container. It is preferable to use a vacuum exhaust device that does not use oil so that the oil generated from the device does not affect the characteristics of the element. Specifically, a vacuum exhaust device such as a sorption pump or an ion pump can be used.

In the activation step, when an oil diffusion pump or a rotary pump is used as an exhaust device and an organic gas derived from an oil component generated from the oil diffusion pump or the rotary pump is used, it is necessary to keep the partial pressure of this component as low as possible. . The partial pressure of the organic component in the vacuum vessel is preferably 1 × 10 ⁻⁸ Torr or less, more preferably 1 × 10 ⁻¹⁰ Torr or less, at a partial pressure at which the carbon and carbon compounds are not newly deposited. Further, when evacuating the inside of the vacuum vessel, it is preferable to heat the entire vacuum vessel to facilitate evacuating the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device. The heating condition at this time is preferably 80 to 200 ° C. for 5 hours or more, but is not particularly limited to this condition, and the heating is performed under conditions appropriately selected according to various conditions such as the size and shape of the vacuum vessel and the configuration of the electron-emitting device. . The pressure in the vacuum vessel needs to be as low as possible, preferably 1 to 3 × 10 ⁻⁷ Torr or less, and more preferably 1 × 10 ⁻⁸ Torr or less.

It is preferable that the atmosphere at the time of driving after the stabilization process is performed is the same as that at the end of the stabilization process. However, the present invention is not limited to this. Even if the degree of vacuum itself is slightly reduced, sufficiently stable characteristics can be maintained. By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed, and as a result, the device current If and the emission current I
e becomes stable.

The basic characteristics of the electron-emitting device to which the present invention obtained through the above-described steps can be applied will be described with reference to FIGS. FIG. 5 is a schematic diagram showing an example of a vacuum processing apparatus, and this vacuum processing apparatus also has a function as a measurement evaluation apparatus. Also in FIG. 5, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. In FIG. 5, 55 is a vacuum vessel, and 56 is an exhaust pump. An electron-emitting device is provided in the vacuum vessel 55. That is, 1 is a base constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a thin film for forming an electron-emitting portion, and 5 is an electron-emitting portion. Reference numeral 51 denotes a power supply for applying a device voltage Vf to the electron-emitting device; 50, an ammeter for measuring a device current If flowing through the thin film 4 for forming an electron-emitting portion between the device electrodes 2 and 3; An anode electrode for capturing an emission current Ie emitted from the electron emission portion. Reference numeral 53 denotes a high-voltage power supply for applying a voltage to the anode electrode 54, and reference numeral 52 denotes an ammeter for measuring an emission current Ie emitted from the electron emission section 5 of the device.
As an example, the voltage of the anode electrode is in the range of 1 kV to 10 kV, and the distance H between the anode electrode and the electron-emitting device is 2
Measurements can be made in the range of mm to 8 mm.

In the vacuum vessel 55, equipment necessary for measurement in a vacuum atmosphere such as a vacuum gauge (not shown) is provided.
Measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump 56 is composed of a normal high vacuum device system including a turbo pump and a rotary pump, and an ultra high vacuum device system including an ion pump and the like. The entire vacuum processing apparatus equipped with the electron source substrate shown here is
It can be heated up to 200 degrees by a heater (not shown). Therefore, by using this vacuum processing apparatus, the steps after the energization forming described above can also be performed.

FIG. 6 shows emission current Ie, device current If and device voltage Vf measured using the vacuum processing apparatus shown in FIG.
FIG. 5 is a diagram schematically showing the relationship of FIG. In FIG. 6, since the emission current Ie is significantly smaller than the device current If,
Shown in arbitrary units. Note that both the vertical and horizontal axes are linear scales.

As apparent from FIG. 6, the surface conduction electron-emitting device to which the present invention can be applied has three characteristic characteristics with respect to the emission current Ie.

That is, (i) when an element voltage higher than a certain voltage (referred to as a threshold voltage, Vth in FIG. 6) is applied to the present element, the emission current Ie rapidly increases, while the threshold voltage V
Below th, the emission current Ie is hardly detected. That is, a clear threshold voltage Vth for the emission current Ie
Is a non-linear element having

(Ii) Since the emission current Ie depends monotonically on the device voltage Vf, the emission current Ie can be controlled by the device voltage Vf.

(Iii) The emission charge captured by the anode electrode 54 depends on the time during which the device voltage Vf is applied.
That is, the amount of charge captured by the anode electrode 54 can be controlled by the time during which the device voltage Vf is applied.

As understood from the above description, the surface conduction electron-emitting device to which the present invention can be applied can easily control the electron emission characteristics according to the input signal.
By utilizing this property, it is possible to apply to various fields such as an electron source and an image forming apparatus having a plurality of electron-emitting devices.

FIG. 6 shows an example in which the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as “MI characteristic”). The element current If is equal to the element voltage Vf.
May exhibit a voltage control type negative resistance characteristic (hereinafter, referred to as “VCNR characteristic”) in some cases (not shown). Further, these characteristics can be controlled by controlling the above-described steps.

Hereinafter, application examples of the electron-emitting device to which the present invention can be applied will be described. By arranging a plurality of surface conduction electron-emitting devices to which the present invention can be applied on a substrate, for example, an electron source or an image forming apparatus can be configured.

Various arrangements of the electron-emitting devices can be adopted. As an example, each of a large number of electron-emitting devices arranged in parallel is connected at both ends, a large number of rows of electron-emitting devices are arranged (referred to as a row direction), and a direction perpendicular to the wiring (referred to as a column direction). There is a ladder-like arrangement in which electrons from the electron-emitting devices are controlled and driven by control electrodes (also referred to as grids) disposed above the electron-emitting devices. Separately, a plurality of electron-emitting devices are arranged in rows and columns in the X and Y directions, and one of the electrodes of the plurality of electron-emitting devices arranged in the same row is commonly connected to a wiring in the X direction, and the same. One example is one in which the other of the electrodes of the plurality of electron-emitting devices arranged in a row is commonly connected to a wiring in the Y direction. This is a so-called simple matrix arrangement. First, the simple matrix arrangement will be described in detail below.

The surface conduction type electron-emitting device to which the present invention can be applied is as described above in (i) to (iii).
There is a characteristic. That is, when the electron emission from the surface conduction electron-emitting device is equal to or higher than the threshold voltage, it can be controlled by the peak value and the width of the pulse voltage applied between the opposing device electrodes. On the other hand, when the voltage is equal to or lower than the threshold voltage, it is hardly emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, if a pulse-like voltage is appropriately applied to each device,
The electron emission amount can be controlled by selecting the surface conduction electron-emitting device according to the input signal.

Hereinafter, based on this principle, an electron source substrate obtained by arranging a plurality of electron-emitting devices to which the present invention can be applied will be described with reference to FIG. In FIG. 7, reference numeral 71 denotes an electron source substrate, 72 denotes an X-direction wiring, and 73 denotes a Y-direction wiring. 74 is a surface conduction electron-emitting device, and 75 is a connection. Incidentally, the surface conduction electron-emitting device 74 may be either the above-mentioned flat type or vertical type.

The m X-direction wires 72 are DX1, DX2,
... made of DXm, and can be made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The material, thickness, and width of the wiring are appropriately set. Y
The directional wiring 73 includes n wirings DY1, DY2,... DYn, and is formed in the same manner as the X-directional wiring 72. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 72 and the n Y-directional wirings 73 to electrically separate them (m and n are both Is a positive integer).

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by using a vacuum deposition method, a printing method, a sputtering method, or the like. For example, it is formed in a desired shape on the entire surface or a part of the substrate 71 on which the X-directional wiring 72 is formed. The material and the production method are appropriately set. The X-direction wiring 72 and the Y-direction wiring 73 are respectively drawn out as external terminals.

A pair of electrodes (not shown) constituting the surface conduction electron-emitting device 74 are electrically connected by m X-directional wires 72 and n Y-directional wires 73 and a connection 75 made of a conductive metal or the like. It is connected.

The material forming the wiring 72 and the wiring 73, the material forming the connection 75, the material forming the connection 75, and the material forming the pair of element electrodes have some or all of the same constituent elements. May also be different. These materials are appropriately selected, for example, from the above-described materials for the device electrodes. When the material forming the element electrode is the same as the wiring material, the wiring connected to the element electrode can also be called an element electrode.

The X-direction wiring 72 is connected to a scanning signal applying means (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 74 arranged in the X direction. On the other hand, a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 74 arranged in the Y direction according to an input signal is connected to the Y-direction wiring 73. The driving voltage applied to each electron-emitting device is supplied as a difference voltage between a scanning signal and a modulation signal applied to the device. In the above configuration, individual elements can be selected and driven independently using a simple matrix wiring.

An image forming apparatus configured using such an electron source having a simple matrix arrangement will be described with reference to FIGS. 8, 9 and 10. FIG. FIG. 8 is a schematic view showing an example of a display panel of the image forming apparatus, and FIG. 9 is a schematic view of a fluorescent film used in the image forming apparatus of FIG. FIG. 10 is a block diagram showing an example of a driving circuit for performing display according to an NTSC television signal.

8, reference numeral 71 denotes an electron source substrate on which a plurality of electron-emitting devices are arranged; 81, a rear plate on which the electron source substrate 71 is fixed; 86, a fluorescent film 84 on the inner surface of a glass substrate 83;
And a face plate on which a metal back 85 and the like are formed. Reference numeral 82 denotes a support frame, to which a rear plate 81 and a face plate 86 are connected using frit glass or the like. Reference numeral 88 denotes an envelope, which is sealed by baking in a temperature range of 400 to 500 ° C. for 10 minutes or more in the atmosphere or nitrogen, for example. 7
Reference numeral 4 corresponds to the electron-emitting portion in FIG. Reference numerals 72 and 73 denote an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

The envelope 88 includes the face plate 86, the support frame 82, and the rear plate 81 as described above.
Since the rear plate 81 is provided mainly for the purpose of reinforcing the strength of the substrate 71, if the substrate 71 itself has sufficient strength, the separate rear plate 81 can be unnecessary. That is, the support frame 82 is directly sealed to the substrate 71, and the envelope 88 is formed by the face plate 86, the support frame 82 and the substrate 71.
May be configured. On the other hand, by installing a support (not shown) called a spacer between the face plate 86 and the rear plate 81, an envelope 88 having sufficient strength against atmospheric pressure can be formed.

FIG. 9 is a schematic view showing a fluorescent film. The fluorescent film 84 can be composed of only a phosphor in the case of monochrome. In the case of a color fluorescent film, it can be composed of a black conductive material 91 called a black stripe or a black matrix and a fluorescent material 92 depending on the arrangement of the fluorescent materials. The purpose of providing the black stripes and the black matrix is to make the mixed portions inconspicuous by making the painted portions between the phosphors 92 of the necessary three primary color phosphors black in the case of color display, An object of the present invention is to suppress a decrease in contrast due to light reflection. As a material for the black stripe, a material which is conductive and has little light transmission and reflection can be used in addition to a commonly used material mainly containing graphite.

The method of applying the fluorescent substance to the glass substrate 93 can employ a precipitation method, a printing method, or the like irrespective of monochrome or color. Usually, a metal back 8 is provided on the inner side of the fluorescent film 84.
5 are provided. The purpose of providing the metal back is to improve the brightness by mirror-reflecting the light toward the inner surface side of the phosphor emission toward the face plate 86 side, to act as an electrode for applying an electron beam acceleration voltage, The purpose is to protect the phosphor from damage due to collision of negative ions generated in the envelope. The metal back is
After the formation of the fluorescent film, the inner surface of the fluorescent film may be smoothed (usually called "filming"), and then aluminum may be deposited by vacuum evaporation or the like.

The face plate 86 further has the fluorescent film 8
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 84 in order to increase the conductivity of the phosphor film 84. When performing the above-described sealing, in the case of color, it is necessary to make each color phosphor correspond to the electron-emitting device, and sufficient alignment is indispensable.

The image forming apparatus shown in FIG. 8 is manufactured, for example, as follows. The envelope 88 is evacuated through an exhaust pipe (not shown) by an exhaust device that does not use oil, such as an ion pump and a sorption pump, while appropriately heating, as in the above-described stabilizing step, and is discharged at about 10 ⁻⁷ Torr. After the atmosphere is made sufficiently low in the degree of vacuum of the organic substance, sealing is performed. To maintain the degree of vacuum after the envelope 88 is sealed, a getter process may be performed. this is,
Immediately before or after sealing of the envelope 88, the envelope 8 is heated by resistance heating or high-frequency heating.
This is a process of heating a getter disposed at a predetermined position (not shown) in the step 8 to form a vapor deposition film. Getter is usually B
a is a main component, and maintains a vacuum degree of, for example, 1 × 10 ^{−5 to} 1 × 10 ⁻⁷ Torr by the adsorption action of the deposited film. Here, steps after the forming process of the surface conduction electron-emitting device can be appropriately set.

Next, an example of the configuration of a driving circuit for performing television display based on NTSC television signals on a display panel configured using electron sources in a simple matrix arrangement will be described with reference to FIG. . In FIG.
101 is an image display panel, 102 is a scanning circuit, 103 is a control circuit, and 104 is a shift register. 105 is a line memory, 106 is a synchronization signal separation circuit, 107 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 101 is connected to an external electric circuit via terminals Dox1 to Doxm, terminals Doy1 to Doyn, and a high voltage terminal Hv. Terminal Do
x1 to Doxm are provided for sequentially driving electron sources provided in the display panel, that is, a group of surface conduction electron-emitting devices arranged in a matrix of M rows and N columns, one row (N element) at a time. A scanning signal is applied.

To the terminals Dy1 to Dyn, a modulation signal for controlling the output electron beam of each of the surface conduction electron-emitting devices in one row selected by the scanning signal is applied. The high voltage terminal Hv is supplied with a DC voltage of, for example, 10 K [V] from a DC voltage source Va, which is sufficient to excite the phosphor into an electron beam emitted from the surface conduction electron-emitting device. An accelerating voltage for applying energy.

The scanning circuit 102 will be described. This circuit includes M switching elements inside (in the drawing, S1 to Sm are schematically shown). Each switching element selects either the output voltage of the DC voltage source Vx or 0 [V] (ground level),
The display panel 101 is electrically connected to terminals Dx1 to Dxm. Each of the switching elements S1 to Sm is
It operates based on a control signal Tscan output from the control circuit 103, and can be configured by combining switching elements such as FETs, for example.

In the case of the present embodiment, the DC voltage source Vx is based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device, and the driving voltage applied to the unscanned device is an electron emission threshold. It is set to output a constant voltage that is equal to or lower than the value voltage.

The control circuit 103 has a function of matching the operation of each unit so that appropriate display is performed based on an image signal input from the outside. The control circuit 103 generates control signals Tscan, Tsft, and Tmry for each unit based on the synchronization signal Tsync sent from the synchronization signal separation circuit 106.

The synchronizing signal separating circuit 106 is a circuit for separating a synchronizing signal component and a luminance signal component from an NTSC television signal input from the outside, and uses a general frequency separating (filter) circuit or the like. Can be configured. The synchronizing signal separated by the synchronizing signal separating circuit 106 includes a vertical synchronizing signal and a horizontal synchronizing signal. Here, for the sake of explanation, it is illustrated as a Tsync signal. The luminance signal component of the image separated from the television signal is referred to as a DATA signal for convenience. The DATA signal is input to the shift register 104.

The shift register 104 is for serially / parallel converting the DATA signal input serially in time series for each line of an image, and is based on a control signal Tsft sent from the control circuit 103. (Ie, the control signal Tsft can be said to be a shift clock of the shift register 104). The data for one line of the image subjected to the serial / parallel conversion (corresponding to drive data for N electron-emitting devices) is output from the shift register 104 as N parallel signals Id1 to Idn.

The line memory 105 is a storage device for storing data for one line of an image for a required time, and stores the contents of Id1 to Idn as appropriate according to a control signal Tmry sent from the control circuit 103. The stored contents are output as Id′1 to Id′n and input to the modulation signal generator 107.

The modulation signal generator 107 is a signal source for appropriately driving and modulating each of the surface motor type electron-emitting devices in accordance with each of the image data Id'1 to Id'n. Is applied to the surface conduction electron-emitting device in the display panel 101 through the terminals Doy1 to Doyn.

As described above, the electron-emitting device to which the present invention can be applied has the following basic characteristics with respect to the emission current Ie. That is, a clear threshold voltage Vth is required for electron emission.
And electron emission occurs only when a voltage higher than Vth is applied. For a voltage equal to or higher than the electron emission threshold, the emission current also changes according to the change in the voltage applied to the device. From this, when applying a pulsed voltage to this element,
For example, when a voltage lower than the electron emission threshold is applied, electron emission does not occur. However, when a voltage at the electron emission threshold is applied, an electron beam is output. At that time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm. Further, by changing the pulse width Pw, it is possible to control the total amount of charges of the output electron beam.

Therefore, as a method of modulating the electron-emitting device in accordance with the input signal, a voltage modulation method, a pulse width modulation method, or the like can be adopted. When implementing the voltage modulation method, a circuit of a voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 107. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 107, a pulse width modulation type circuit that generates a voltage pulse having a constant peak value and appropriately modulates the width of the voltage pulse according to input data can be used.

The shift register 104 and the line memory 10
5 can be a digital signal type or an analog signal type. This is because the serial / parallel conversion and storage of the image signal may be performed at a predetermined speed.

When the digital signal type is used, it is necessary to convert the output signal DATA of the synchronizing signal separating circuit 106 into a digital signal. This can be achieved by providing an A / D converter at the output section of the circuit 106. In connection with this, the line memory 105
The circuit used for the modulation signal generator 107 is slightly different depending on whether the output signal is a digital signal or an analog signal. That is, in the case of the voltage modulation method using a digital signal, for example, a D / A conversion circuit is used as the modulation signal generator 107, and an amplification circuit and the like are added as necessary. In the case of the pulse width modulation method, the modulation signal generator 107 includes, for example, a high-speed oscillator, a counter for counting the number of waves output from the oscillator, and a comparison for comparing the output value of the counter with the output value of the memory. The circuit which combined the device (comparator) is used. If necessary, an amplifier for voltage-amplifying the pulse-width-modulated signal output from the comparator to the drive voltage of the surface-motor-driven electron-emitting device can be added.

In the case of the voltage modulation method using an analog signal, an amplification circuit using, for example, an operational amplifier or the like can be used as the modulation signal generator 107, and a level shift circuit or the like can be added as necessary. In the case of the pulse width modulation method, for example, a voltage-controlled oscillation circuit (VCO) can be employed, and an amplifier for amplifying the voltage up to the drive voltage of the surface conduction electron-emitting device can be added as necessary.

In the image display apparatus to which the present invention can be applied in such a configuration, external terminals Dox1 to Doxm, Doy1 to Doy are provided to each electron-emitting device.
By applying a voltage through n, electron emission occurs. A high voltage is applied to the metal back 85 or a transparent electrode (not shown) via the high voltage terminal Hv to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 84 and emit light to form an image.

The configuration of the image forming apparatus described here is an example of an image forming apparatus to which the present invention can be applied, and various modifications can be made based on the technical idea of the present invention. Although the NTSC system has been used as the input signal, the input signal is not limited to the NTSC system. In addition to the PAL and SECAM systems, a TV signal including a larger number of scanning lines (for example, the MUSE system, etc.) High-definition TV).

Next, the ladder-type arrangement of the electron source and the image forming apparatus will be described with reference to FIGS. FIG.
FIG. 2 is a schematic view showing an example of an electron source having a ladder arrangement.
In FIG. 11, reference numeral 110 denotes an electron source substrate, and 111 denotes an electron-emitting device. 112, Dx1 to Dx10 are common wirings for connecting the electron-emitting devices 111. A plurality of electron-emitting devices 111 are arranged on the substrate 110 in parallel in the X direction (this is called an element row). A plurality of the element rows are arranged to constitute an electron source. By applying a drive voltage between the common wires of each element row, each element row can be driven independently. That is, a voltage equal to or higher than the electron emission threshold is applied to an element row that wants to emit an electron beam, and a voltage equal to or lower than the electron emission threshold is applied to an element row that does not emit an electron beam. Common wiring Dx2 to Dx between each element row
For example, Dx2 and Dx3 can be the same wiring.

FIG. 12 is a schematic diagram showing an example of a panel structure in an image forming apparatus having a ladder-type electron source. 120 is a grid electrode, 121 is a hole for passing electrons, 122 is Dox1, Dox2,.
xm. Reference numeral 123 denotes an external terminal composed of G1, G2,... Gn connected to the grid electrode 120, and reference numeral 124 denotes an electron source substrate in which the common wiring between the element rows is the same. In FIG. 12, FIGS.
Are given the same reference numerals as those shown in these figures. The major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG.
Is provided with the grid electrode 120 between them.

In FIG. 12, a grid electrode 120 is provided between a substrate 110 and a face plate 86. The grid electrode 120 is for modulating the electron beam emitted from the surface conduction electron-emitting device,
One circular opening 121 is provided for each element in order to allow an electron beam to pass through a striped electrode provided orthogonal to the ladder-shaped element rows. The shape and installation position of the grid are not limited to those shown in FIG. For example, a large number of passage openings may be provided in a mesh shape as openings, and a grid may be provided around or near the surface conduction electron-emitting device. The outer container terminal 122 and the outer grid container terminal 123 are electrically connected to a control circuit (not shown).

In the image forming apparatus of this embodiment, a modulation signal for one line of an image is simultaneously applied to the grid electrode rows in synchronization with sequentially driving (scanning) the element rows one by one. This makes it possible to control the irradiation of each electron beam to the phosphor and display an image one line at a time.

The image forming apparatus of the present invention is used not only as a display device for a television broadcast, a display device such as a video conference system and a computer, but also as an image forming device as an optical printer using a photosensitive drum or the like. You can also.

[0103]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to the following examples. Example 1 An electron-emitting device of the type shown in FIGS. 2A and 2B was manufactured as the electron-emitting device of this example. FIG. 2A is a plan view of the element, and FIG. 2B is a cross-sectional view. 2 (a) and 2 (b), 1 is an insulating substrate, 2 and 3 are device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion. . Note that L1 in FIG.
Represents the element electrode interval between the element electrodes 2 and 3, W1 represents the width of the element electrode, d represents the thickness of the element electrode, and W2 represents the width of the element.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. Using a quartz substrate as the insulating substrate 1,
This is thoroughly washed with an organic solvent and pure water,
It dried with the hot air of ° C. The device electrodes 2 and 3 were formed on the surface of the substrate 1 by offset printing. In this embodiment, an Au resinate paste composed of an organic metal was used as the ink. The ink is dried on a glass substrate at about 70 ° C and
It can be used as an element electrode made of Au by baking at ℃. The thickness of the Au electrode after firing was as thin as about 1000 °. Here, as the pattern shape of the device electrodes, the dimension between the device electrodes on which the electron-emitting material is arranged was set to about 30 microns.

Next, 0.84 g of palladium acetate-monoethanolamine (hereinafter abbreviated as PA-ME) was dissolved in 12 g of water, and polyvinyl alcohol (hereinafter abbreviated as PVA) was added to adjust the solution viscosity to 20 centipoise. This was used as an aqueous solution for BJ application. PA-ME was synthesized as follows.

10 g of Pd acetate was added to 200 cm ³ of IPA.
, And 16.6 g of monoethanolamine was further added, followed by stirring at room temperature for 4 hours. After completion of the reaction, IPA was removed by evaporation, and ethanol was added to the solid to dissolve and filter, and PA-ME was recrystallized from the filtrate. As a result of scanning differential thermal analysis in air, the decomposition temperature of PA-ME was 272 ° C. PVA has a degree of saponification of 98%
The above Kuraray poval was used.

Next, a BJ type ink jet apparatus (Ca
Non-BJ-10V) was used to apply a PA-ME aqueous solution between the device electrodes 2 and 3 (FIG. 3B) and dried. As a result of applying liquid droplets to a plurality of elements, the applied liquid droplets could be applied with good reproducibility without penetrating the electrodes.

This was placed in an air oven at 300 ° C.
Then, the PA-ME and PVA were decomposed and deposited on the substrate to form a fine particle film composed of fine particles of palladium oxide (average particle size: 65 °), thereby forming a thin film 4 for forming an electron-emitting portion (FIG. 3). It was confirmed by X-ray analysis that it was palladium oxide. The electron-emitting-portion-forming thin film 4 has a width (element width) W2 of 300 μm, and is disposed substantially at the center between the element electrodes 2 and 3. Further, the thin film 4 for forming the electron emitting portion is formed.
Had a thickness of 100 ° and a sheet resistance of 5 × 10 ⁴ Ω / port.

The fine particle film described here is a film in which a plurality of fine particles are gathered, and has a fine structure not only in a state where the fine particles are individually dispersed and arranged, but also in a state where the fine particles are adjacent to each other or overlap each other ( (Including an island shape), and the particle size refers to the diameter of the fine particles whose particle shape can be recognized in the above state.

Next, as shown in FIG. 3D, the electron-emitting portion 5 is formed by applying a voltage between the device electrodes 2 and 3 and applying a current to the thin film 4 for forming the electron-emitting portion (forming process). did. FIG. 4 shows a voltage waveform of the forming process.

In FIG. 4, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms, T1 is
2 is set to 10 ms, the peak value of the triangular wave (peak voltage at the time of forming) is set to 5 V, and the forming process is about 1 × 1.
This was performed for 60 seconds in a vacuum atmosphere of 0 ^-6 torr. Further, palladium oxide was reduced to metallic palladium by a reduction treatment. The electron-emitting portion 5 thus manufactured was in a state in which fine particles containing palladium as a main component were dispersed and arranged, and the fine particles had an average particle size of 28 °.

The electron emission characteristics of the electron-emitting device manufactured as described above were measured. FIG. 5 shows a schematic configuration diagram of a vacuum processing apparatus having a measurement evaluation function.

In FIG. 5, 1 is an insulating substrate, 2 and 3
Denotes a device electrode, 4 denotes a thin film including an electron-emitting portion, 5 denotes an electron-emitting portion, 51 denotes a power source for applying a voltage to the device, 5
0 is an ammeter for measuring the device current If, 54 is an anode electrode for measuring the emission current Ie generated from the device, 53 is a high-voltage power supply for applying a voltage to the anode electrode 54, and 55 is the emission current. It is an ammeter for measuring. In measuring the device current If and the emission current Ie of the electron-emitting device, a power supply 51 and an ammeter 50 are connected between the device electrodes 2 and 3, and a power supply 53 is provided above the electron-emitting device.
And an anode electrode 54 to which an ammeter 55 is connected. Further, the electron-emitting device and the anode electrode 54 are installed in a vacuum device, and the vacuum device is provided with equipment necessary for a vacuum device such as an exhaust pump (not shown) and a vacuum gauge. The device can be measured and evaluated below. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 KV, and the degree of vacuum in the vacuum device when measuring the electron emission characteristics was 1
× 10 ^-6 torr.

Using the measurement and evaluation apparatus as described above, a device voltage was applied between the electrodes 2 and 3 of the electron-emitting device, and the device current If and the emission current Ie flowing at that time were measured. Such a current-voltage characteristic was obtained. In the present device, the emission current Ie rapidly increases from a device voltage of about 8 V, and the device current If becomes 1.6 m at a device voltage of 16 V.
A, the emission current Ie becomes 0.8 μA, and the electron emission efficiency η
= Ie / If (%) was 0.05%.

In the embodiment described above, when forming the electron-emitting portion, the forming process is performed by applying a triangular wave pulse between the electrodes of the device, but the waveform applied between the electrodes of the device is limited to the triangular wave. However, a desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. Can be selected.

Example 2 Offset printing of a resinate paste ink was carried out on a well-washed substrate made of blue plate glass, and an Au element electrode having a thickness of 1000 mm was patterned by firing.

As an organometallic complex, 1.07 g of palladium acetate diethanolamine (hereinafter abbreviated as PA-DE) was added to 1
After dissolving in 2 g, methyl cellulose was further added to adjust the solution viscosity to 20 cm. The droplet applied on the substrate did not permeate the electrode, and a droplet having good reproducibility in both shape and amount could be applied to the electrode portion. Thereafter, an electron-emitting device was manufactured by the same method as that of Example 1.

In this device, the emission current Ie sharply increases from the device voltage of about 7.9 V. At the device voltage of 16 V, the device current If becomes 1.6 mA, the emission current Ie becomes 0.8 μA, and the electron emission efficiency η = Ie / If (%) is 0.052%
Met.

Embodiment 3 FIG. 13 is a plan view of a part of the electron source, and FIG.
FIG. 14 is a cross-sectional view, and FIG. 15 shows a method for manufacturing an electron source. 13, 14, 15, and 16, the same symbols indicate the same components. Where 1
Denotes an insulating substrate, 72 denotes an X-direction wiring (also referred to as a lower wiring) corresponding to Dxm in FIG. 8, 73 denotes a Y-direction wiring (also referred to as an upper wiring) corresponding to Dyn in FIG. 8, and 4 includes an electron emitting portion. Thin films, 2 and 3, device electrodes, 111, an interlayer insulating layer, 112
Is a contact hole for electrical connection between the element electrode 2 and the lower wiring 72.

Step-a A thin film of Au element electrodes 2 and 3 having a thickness of 1000 mm was formed on a cleaned blue plate glass by offset printing and firing of a resinate-based ink. Next, an Ag paste ink was screen-printed and baked to form a lower printed wiring 72 having a width of 300 μm and a thickness of 7 μm.

Step-b Next, a glass paste ink was screen-printed and baked to form an insulating layer 111 having a width of 500 μm and a thickness of about 20 μm, and a contact hole 112 having an opening size of 100 μm square.

Step-c Further, an Ag paste ink was screen-printed on the insulating layer 111 and baked to form an upper printed wiring 73 having a width of 300 μm and a thickness of 10 μm.

Step-d The aqueous solution for BJ application used in Example 1 was applied between the device electrodes 2 and 3 using a BJ type ink jet apparatus (BJ-10V manufactured by Canon), and heated and baked at 300 ° C. for 10 minutes. Processed. The electron emitting portion forming thin film 4 formed of fine particles of Pd as the main element thus formed had a thickness of 100 ° and a sheet resistance of 5 × 10 ⁴ Ω / port. The fine particle film described here is, as described above, a film in which a plurality of fine particles are aggregated, and as its fine structure, not only a state in which the fine particles are individually dispersed and arranged, but also the fine particles are adjacent to each other or overlap each other. A film in a state (including an island shape) is referred to, and the particle size is a diameter of a fine particle that can be recognized in a particle form in the state. Through the above steps, the lower wiring 72, the interlayer insulating layer 111,
Upper wiring 73, element electrodes 2, 3, thin film 4 for forming electron-emitting portion
Etc. were formed.

Next, an example in which a display device is configured by using the electron source created as described above will be described with reference to FIGS. 8 and 9. FIG.

After fixing the substrate 1 on which many planar surface conduction electron-emitting devices have been manufactured as described above on the rear plate 81, the face plate 8 is placed 5 mm above the substrate 1.
6 (formed by forming a fluorescent film 84 and a metal pack 85 on the inner surface of a glass substrate 93) via a support frame 82, and a frit is provided at the joint of the face plate 86, the support frame 82 and the rear plate 81. Glass was applied and sealed by baking at 400 ° C. to 500 ° C. for 10 minutes or more in air or nitrogen atmosphere (FIG. 9). The fixing of the substrate 1 to the rear plate 81 was also performed with frit glass.

In FIG. 8, reference numeral 74 denotes an electron-emitting device;
Reference numerals 2 and 73 denote wirings in the X and Y directions, respectively.

The phosphor film 84 is made of only a phosphor in the case of a monochrome, but in this embodiment, the phosphor is formed in a stripe shape, a black stripe is formed first, and each color phosphor is placed in the gap. It was applied to form a fluorescent film 84. A slurry method was used to apply a phosphor to a glass substrate 93 using a material mainly composed of graphite, which is commonly used as a material of a black stripe.

On the inner surface side of the fluorescent film 84, a metal back 85 is usually provided. The metal back was manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film 84 after the fluorescent film was manufactured, and then performing vacuum deposition of Al.

The face plate 86 is further provided with a fluorescent film 8.
In some cases, a transparent electrode (not shown) is provided on the outer surface side of the fluorescent film 84 in order to increase the conductivity of the phosphor film 4. However, in the present embodiment, a sufficient conductivity is obtained only with the metal back, so that the description is omitted. did.

When the above-mentioned sealing is performed, in the case of color, the phosphors of each color must correspond to the electron-emitting devices, so that sufficient alignment is performed.

The atmosphere in the glass container completed as described above is evacuated by a vacuum pump through an exhaust pipe (not shown), and after a sufficient degree of vacuum is reached, the external terminals (Dxo1 to Dxo1).
Electron emitting device 74 through Doxm and Doy1 to Doxm
A voltage was applied between the electrodes 2 and 3 to form an electron emitting portion 5 by applying a current to the thin film 4 for forming the electron emitting portion 4 (forming process). FIG. 4 shows a voltage waveform of the forming process.

In FIG. 4, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms, T1 is
2 is set to 10 ms, the peak value of the triangular wave (peak voltage at the time of forming) is set to 5 V, and the forming process is about 1 × 1.
This was performed for 60 seconds in a vacuum atmosphere of 0 ^-6 torr.

In the electron-emitting portion 5 thus formed, fine particles containing palladium as a main component were dispersed and arranged, and the average particle size of the fine particles was 30 °. Forming was performed to form the electron-emitting portion 5, thereby manufacturing the electron-emitting device 74. Next, at a degree of vacuum of about 10 ⁻⁶ torr, an exhaust pipe (not shown) was welded by heating with a gas burner to seal the envelope.

Finally, in order to maintain the degree of vacuum after sealing,
Getter processing was performed. In this method, a getter disposed at a predetermined position (not shown) in the image forming apparatus was heated by a heating method such as high-frequency heating or the like just before sealing to form a deposited film. The getter was mainly composed of Ba or the like.

In the image display device of the present invention completed as described above, each electron-emitting device has external terminals Dx1 to Dx1.
A scanning signal and a modulation signal are applied from Dxm and Dy1 to Dyn from a signal generation unit (not shown) to emit electrons, and a high voltage of several KV or more is applied to the metal pack 9 through a high voltage terminal, Bv. An image was displayed by accelerating the electron beam, colliding with the fluorescent film 8, and exciting and emitting light.

Further, in order to grasp the characteristics of the flat surface conduction electron-emitting device manufactured in the above-described steps, at the same time, FIG.
A standard comparative sample in which L1, W1, W2, etc. of the planar surface conduction electron-emitting device shown in FIG. 4 were made the same was prepared, and its electron emission characteristics were measured using the above-described measurement and evaluation apparatus of FIG. .

The measurement conditions of the comparative sample were as follows: the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 KV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics was 1 × 10 ^-6 torr. did. When a device voltage was applied between the electrodes 2 and 3 and the device current If and the emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained. In this device, the emission current Ie rapidly increases from an element voltage of about 8 V. At an element voltage of 16 V, the element current If becomes 1.6 mA, the emission current Ie becomes 0.8 μA, and the electron emission efficiency = η = Ie / If (% ) Is 0.05%
Met.

Comparative Example 1 Element electrodes 2 and 3 were formed on an insulating substrate by offset printing in the same manner as in Example 1. Next, palladium acetate-
A solution of monoethanolamine dissolved in 12 g of water
An aqueous solution for J application was obtained. This aqueous solution is applied between the device electrodes 2, 3
Was given. When droplets were applied to a plurality of devices, a phenomenon occurred in which the droplets permeated the electrodes in a small number of devices, and the film thickness of these devices after firing was smaller than that of the other devices.

[0139]

As described above, by forming the element electrodes by using the offset printing method, the area of the image forming apparatus can be increased and the manufacturing cost can be reduced.

Further, the electron emission element formed using the material for forming an electron emission portion and the droplet applying means of the present invention not only improves the cost and environment but also allows the applied droplet to penetrate the electrode. And the variation in the thickness of the electron-emitting portion film can be suppressed, and the variation between the electron-emitting devices at the time of forming and at the time of electron emission can be made smaller than before. Furthermore, in the case of an image forming apparatus, it is possible to reduce defective products due to uneven brightness and defects in the electron emission portion.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

FIG. 2 is a schematic plan view and a cross-sectional view illustrating a configuration of a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 3 is a schematic view showing one example of a method for manufacturing an electron-emitting device of the present invention.

FIG. 4 is a schematic diagram showing an example of a voltage waveform in a current forming process that can be employed in manufacturing a surface conduction electron-emitting device applicable to the present invention.

FIG. 5 is a schematic diagram illustrating an example of a vacuum process having a measurement evaluation function.

FIG. 6 shows emission current Ie, device current If, and device voltage Vf for a surface conduction electron-emitting device applicable to the present invention.
6 is a graph showing an example of the relationship.

FIG. 7 is a schematic diagram showing an example of an electron source arranged in a simple matrix to which the present invention can be applied.

FIG. 8 is a schematic diagram illustrating an example of a display panel of an image forming apparatus to which the present invention can be applied.

FIG. 9 is a schematic diagram illustrating an example of a fluorescent film.

FIG. 10 is a block diagram illustrating an example of a driving circuit for performing display according to an NTSC television signal on the image forming apparatus.

FIG. 11 is a schematic diagram showing an example of an electron source having a ladder arrangement to which the present invention can be applied.

FIG. 12 is a schematic diagram illustrating an example of a display panel of an image forming apparatus to which the present invention can be applied.

FIG. 13 is a schematic view showing a plan view (partly) of an electron source of the image forming apparatus shown in Embodiment 3 of the present invention.

FIG. 14 is a cross-sectional view of the electron source of the image forming apparatus according to the third embodiment taken along line AA ′ in FIG.

FIG. 15 is a schematic view showing a method for manufacturing the electron source shown in Embodiment 3 of the present invention.

FIG. 16 is a schematic view showing a method for manufacturing the electron source shown in Embodiment 3 of the present invention.

[Explanation of symbols]

1: substrate, 2: 3: device electrode, 4: conductive thin film, 5: electron emitting portion, 21: droplet applying means, 50: device electrode 2, 3
Ammeter for measuring the device current If flowing through the conductive thin film 4 between the devices; 51: a power supply for applying the device voltage Vf to the electron-emitting device; 52: an emission current Ie emitted from the electron-emitting portion 5 of the device. , A high-voltage power supply for applying a voltage to the anode electrode, an anode electrode for capturing an emission current Ie emitted from an electron emission portion of the element, a vacuum device, 56: exhaust pump, 71: electron source substrate, 72: X direction wiring, 73: Y direction wiring, 74: surface conduction electron-emitting device, 75: connection,
81: rear plate, 82: support frame, 83: glass substrate, 84: fluorescent film, 85: metal back, 86: face plate, 87: high voltage terminal, 88: envelope, 91: black conductive material, 92: fluorescent Body, 93: glass substrate, 101:
Display panel, 102: scanning circuit, 103: control circuit, 1
04: shift register, 105: line memory, 10
6: synchronization signal separation circuit, 107: modulation signal generator, Vx
And Va: DC voltage source, 110: electron source substrate, 11
1: electron-emitting device; 112: common wiring for wiring the electron-emitting devices; 120: grid electrode; 121: hole for passing electrons;
2: Dox1, Dox2,... Doxm external terminal made of Doxm, 123: G connected to grid electrode 120
1, G2.

Continuation of the front page (56) References JP-A-8-277294 (JP, A) JP-A-9-106754 (JP, A) JP-A-7-182972 (JP, A) JP-A-7-192613 (JP, A) JP-A-7-192615 (JP, A) JP-A-8-337747 (JP, A) JP-A-8-104810 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C09D 11/00-11/20 C07F 15/00 H01J 1/30 H01J 9/02

Claims (2)

(57) [Claims] 1. An ink jet apparatus comprising a discharge nozzle for discharging a liquid containing an organometallic complex metal component and a resin represented by the following formula as droplets. Embedded image (However, R _1, R _2; alkyl group having a carbon number of 1 to 4, 1:
An integer of 2 to 4, an integer of m = 1 to 4, an integer of n = 0 to 2,
M = metal) 2. An ink-jet ink comprising a liquid containing an organometallic complex metal component represented by the following formula and a resin. Embedded image (However, R _1, R _2: an alkyl group having a carbon number of 1 to 4, 1:
An integer of 2 to 4, an integer of m = 1 to 4, an integer of n = 0 to 2,
M = metal)