JPH10287692A - Organometallic compound for forming electron release element, production of electron release element, and apparatus for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new water-soluble metallic compound, comprising a specified organometallic compound for forming an electron release element, having properties of decomposing at a high temperature and rapidly completing the decomposition and useful for the production, etc., of the electron release element used for an apparatus for forming images. SOLUTION: This new organometallic compound is represented by the formula [R1 is H or a 1-4C alkyl; R2 , R3 , R6 and R7 are each H or a 1-2C alkyl; R2 and R6 or R3 and R7 may be bound; R4 and R5 are each H or an alkylene; R4 and R5 may each be a cyclic group alone or bound to form the cyclic group; (R2 ) (R3 )N-R4 or R5 -N(R6 )(R7 ) or both may each be a cyclic group; (R2 )(R3 )N-R4 - R5 or R4 -R5 -N(R6 )(R7 ) may each be annularly bound; (m) and (n) are each 1-4; M is a metal] [e.g. palladium acetate-bis(propylenediamine)] and is used for forming an electron release element capable of forming an electron release part 5 of the electron release element equipped with the electron release part 5 between opposite electrodes 2 and 3 on a substrate 1. The compound is used for the electron release element, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organometallic compound for forming an electron-emitting device, a method for producing an electron-emitting device using the organometallic compound, and an image forming apparatus having an element produced using the organometallic compound. About.

[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. The 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-emitting device.

As an example of the FE type, W. P. Dyke &
W. W. Dolan, "Fielddemissio
n ", Advance in Electron Ph
ysics, 8, 89 (1956) or C.I. A. S
pindt, “PHYSICAL PROPERTYS
of thin-film field emiss
ion cathodes with mollybde
nium cones ", J. Appl. Phys.,
47, 5248 (1976) and the like are known. Examples of the MIM type include C.I. A. Mead, "
Operation of Tunnel-Emiss
ion Devices ”, J. Apply. Phys.
s. , 32, 646 (1961).

As an example of the surface conduction electron-emitting device,
M. I. Elinson, RadioEng. Elec
Tron Phys. , 10, 1290 (1965). Surface conduction electron-emitting devices are
This utilizes a phenomenon in which electron emission occurs when a current flows in 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 So
lid Films ", 9, 317 (1972)], I
n ₂ O ₃ / SnO ₂ thin film [M. Hartwe
ll and C.I. G. FIG. Fonstad: "IEEE
Trans. ED Conf. 519 (197
5)], using a carbon thin film [Hisashi Araki et al .: Vacuum,
26, No. 1, p. 22 (1983)].

As a typical example of these surface conduction electron-emitting devices, M. FIG. 14 schematically shows an element configuration of the Hartwell. In FIG. 1, reference numeral 1 denotes a substrate. Reference numeral 4 denotes a conductive film, which is formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and in which an electron emitting portion 5 is formed by an energization process called energization forming described later. The element electrode interval L in the figure is 0.5 to 1 mm,
W 'is set at 0.1 mm.

Heretofore, in these surface conduction electron-emitting devices, it has been general that the electron-emitting portion 5 is formed beforehand by performing an energization process called energization forming on the conductive film 4 before electron emission. That is, the energization forming means applying a DC voltage or a very slowly increasing voltage, for example, about 1 V / min, to both ends of the conductive film 4 and energizing it to locally destroy, deform or alter the conductive film, The purpose is to form the electron-emitting portion 5 in a state of high resistance. The electron emitting portion 5 is a portion where a crack is generated in a part of the conductive film 4 and electrons are emitted from the vicinity of the crack. The surface conduction type electron-emitting device which has been subjected to the energization forming process is configured to apply a voltage to the conductive film 4 and allow a current to flow through the device, thereby causing the electron-emitting portion 5 to emit electrons.

[0007]

Conventionally, the conductive film 4 has
After a solution obtained by dissolving an organometallic compound in an organic solvent was applied to a substrate and dried, the organic component was thermally decomposed and removed by heating and baking to obtain a metal or metal oxide. It is not desirable to use an organic solvent in the process of forming the conductive film 4 from the viewpoint of cost reduction and environmental protection, and it has been desired to complete an organometallic compound that easily dissolves in water. A compound such as a metal carboxylate monoalcoholamine complex (Japanese Patent Application Laid-Open No. Hei 7-11619) has been synthesized as an organic metal compound soluble in water, but when this compound is heated and calcined, a small amount of organic residue is generated. Sufficient time had to be spent in the firing step to remain. This is not preferable in terms of cost reduction and time reduction, and the completion of a compound capable of shortening the firing step has been desired.

Further, as a method of applying the organometallic compound between the electrodes in the form of droplets, a method of applying a physical impact to a solution of the organometallic compound by a piezo element to produce and apply droplets, A method in which a solution of an organometallic compound is rapidly foamed to form droplets and apply the droplets (hereinafter, referred to as a BJ method). When droplets are generated using the BJ method, kogation may be generated on the heater surface. In order not to generate kogation, it is necessary that the thermal decomposition temperature of the compound contained in the solution (the temperature at which the bond between the metal atom and the organic component is cut off) must be higher than the surface temperature of the heater. Development of stable organometallic compounds has been desired.

An object of the present invention is to solve the above-mentioned technical problems to be solved, and to produce an organic metal compound which is water-soluble, decomposable at high temperature and decomposes quickly, and manufacture of an electron-emitting device using the same. It is to provide a method. Also,
Another object of the present invention is to provide an image forming apparatus using an electron-emitting device obtained by the manufacturing method.

[0010]

SUMMARY OF THE INVENTION The present invention has been made intensively to solve the above-mentioned problems, and has the following structure.

That is, the organometallic compound for forming an electron-emitting device of the present invention is an organometallic compound for forming an electron-emitting device which forms the electron-emitting portion of an electron-emitting device having an electron-emitting portion between opposing electrodes on a substrate. And the organometallic compound is represented by the following formula (1):

[0012]

Embedded image (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon _{atoms, R 2, R 3, R} 6, R 7 is a hydrogen atom or an alkyl group having a carbon number of 1 to 2, R ₂ and R ₆ or R ₃ and R ₇ may be bonded, R ₄ and R _{5 each} represent a hydrogen atom or an alkylene group, and R ₄ and R ₅ may be each independently or bonded to form a cyclic group. , (R
_{2) (R 3) N-} R 4 and / or R ₅ -N (R ₆₎
(R ₇ ) may be a cyclic group, and (R ₂ ) (R ₃ ) N
—R ₄ —R ₅ or R ₄ —R ₅ —N (R ₆ ) (R ₇ ) may be each cyclically bonded, n is an integer of 1 to 4, m is an integer of 1 to 4, M Represents a metal, R ₂ ,
When R ₃ , R ₆ , and R ₇ are all hydrogen atoms, and
Except when R ₄ -R ₅ -is -CH ₂ -CH _2- )
It is characterized by being represented by

According to the method of manufacturing an electron-emitting device of the present invention, a step of applying a conductive film forming solution between opposing electrodes on a substrate, a step of heating and firing the applied solution to form a conductive film, and A method for manufacturing an electron-emitting device including a step of forming an electron-emitting portion in the conductive film, wherein a solution containing the organometallic compound according to any one of claims 1 to 6 is used as the conductive film-forming solution. It is characterized by being used.

Further, the image forming apparatus of the present invention comprises an electron source having an electron-emitting device and a means for applying a voltage to the device, a fluorescent film for receiving electrons emitted from the device and emitting light, And a drive circuit for controlling a voltage applied to the element by using the organic metal compound of the present invention, wherein the electron emission portion of the element is formed.

Formula (1) is a compound obtained by coordinating a metal with a diamine-based bidentate ligand that forms a chelate compound with a metal atom. This metal-diamine-based complex is used as a material for forming an electron-emitting device. By using it, it is water-soluble, the temperature range required for decomposition is smaller than that of the organometallic compounds conventionally used in the production of electron-emitting devices, and the residue can be removed in a shorter time than in the past in the firing step, and decomposed at high temperature Is obtained.

By using this compound as a material for forming an electron-emitting device, the compound can be easily dissolved in water, the occurrence of kogation on the heater surface is reduced, the cost required for firing and the time required for firing are reduced, and the cost is reduced. An easy electron-emitting device can be manufactured.

The metals used in the above equation (1) are Pt, P
d, Ru, Ag, Cu, Cr, Fe, Pb, Zn, Sn
Can be selected from the group consisting of -In the above formula (1)
R ₄ -R ₅ -is the following formula (2)

[0018]

Embedded image (However, R ₈ and R ₉ represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, p represents 0 or 1, and q represents an integer of 0 to 4).

-R ₄ -R _5- represented by the above formula (2)
Is 1,2-phenylene, 1,2-cyclohexylene,
It can be selected from the group consisting of 2,3-naphthylene, 1,8-naphthylene, 1-methylene-2-phenylene.
In the above formula (1), (R ₂ ) (R ₃ ) NR ₄ and / or R ₅ -N (R ₆ ) (R ₇ ) can be 2-pyridyl. In the above formula (1), (R ₂ ) (R
₃₎ N-R ₄ -R ₅ or _{R 4 -R 5 -N (R 6} ) (R
₇ ) is 1,2,3,4-tetrahydroquinoline-8-
Ill.

The means for applying the solution between the electrodes may be any method as long as it is possible to form and apply droplets. In particular, fine droplets can be efficiently generated and applied with appropriate accuracy. An ink jet system with good properties is convenient.
The ink jet method is a method of generating and applying liquid droplets by mechanical shock of a piezo element or the like, that is, a deformation force when a voltage is applied to a piezoelectric body (hereinafter, referred to as a piezo jet method), or a liquid heater by a minute heater or the like. There is a bubble jet method (hereinafter referred to as a BJ method) in which droplets are generated and generated by bubbles generated by heating the liquid, but in each case, the reproducibility of minute droplets from about 10 nanograms to about tens of micrograms is reproducible. It is generated well and can be provided between the electrodes. FIGS. 2 and 3 show examples of an ink jet head used in this method. 2 and 3, 21 is a head body, 22 is a heater or a piezo element, 23 is an ink flow path, 24 is a nozzle, 25 is an ink supply pipe, 26
Indicates an ink reservoir, respectively. Fig. 2 shows a single shot head, Fig. 3
Is intended to shorten the time required for discharging a solution for forming a conductive film and attaching the solution to a substrate or the like by arranging single-shot heads in parallel, and the number of nozzles is not particularly limited.

The solution applied between the electrodes by the above-described means becomes a conductive film through a drying and baking step,
A thin film for emitting electrons is formed between the electrodes. In the drying step, natural drying, blast drying, heat drying and the like may be used. The baking step may use a commonly used heating means. The drying step and the baking step do not necessarily have to be performed as separate and distinct steps, and may be performed continuously and simultaneously. Further, the droplets may be continuously applied, and the shape of the applied droplets may be linear or planar.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. A preferred electron-emitting device to which the present invention can be applied is a surface-conduction electron-emitting device. The basic structure of the surface-conduction electron-emitting device is roughly classified into two types: a planar type and a vertical type. The surface conduction electron-emitting device will be described.

FIG. 1 is a schematic view showing the structure of a surface conduction electron-emitting device according to the present invention. FIG. 1 (a) is a plan view and FIG.
(B) is a sectional view. In FIG. 1, 1 is a substrate, 2,
Reference numeral 3 denotes an element electrode, 4 denotes a conductive film, and 5 denotes an electron emitting portion. As the substrate 1, quartz glass, glass with a reduced content of impurities such as Na, blue plate glass, a glass substrate obtained by laminating SiO ₂ formed on a blue plate glass by a sputtering method, ceramics such as alumina, and a Si substrate are used. Can be.

The materials of the opposing device electrodes 2 and 3 are as follows.
General conductor materials can be used. This includes, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
metals such as u, Pd or alloys thereof, and Pd, A
g, Au, RuO ₂ , Pd—Ag and other metals, alloys or printed conductors composed of metal oxides and glass, In ₂ O
It can be appropriately selected from a transparent conductor such as _3- SnO ₂ and a semiconductor material such as polysilicon.

The element electrode interval L, the element electrode length W, the electrode thickness d, the shape of the conductive film 4 and the like are designed in consideration of the applied form and the like. The element electrode interval L can be preferably in the range of several thousand to several hundred μm, and more preferably in the range of several μm to several tens μm in consideration of the voltage applied between the element electrodes. be able to.

The element electrode length W can be set in a range from several μm to several hundred μm in consideration of the resistance value of the electrode and the electron emission characteristics. The film thickness d of the device electrodes 2 and 3 can be in the range of several hundreds of μm to several μm. In addition, not only the configuration shown in FIG. 1 but also a configuration in which a conductive film 4 and opposing element electrodes 2 and 3 are laminated on the substrate 1 in this order.

It is preferable to use a fine particle film composed of fine particles for the conductive film 4 in order to obtain good electron emission characteristics. The film thickness is determined by the step coverage of the device electrodes 2 and 3 and the device electrode. It is appropriately set in consideration of the resistance value between two or three and the energization forming conditions described below, but is usually preferably in the range of several to several thousand degrees, more preferably in the range of 10 to 500 degrees. Good to do. The resistance value is such that R _S is from 10 ² to 10 ⁷ Ω. Note that R _S
Is the amount of resistance R measured in the length direction of a thin film having a thickness of t, a width of w, and a length of 1 when R = R _s (l / w). Then, R _s = (ρ / t).

In this specification, the forming process will be described by taking an energizing process as an example. However, the forming process is not limited to this, and a process for forming a high resistance state by causing a crack in a film is described. Includes

The conductive film 4 is made of Pd in addition to the above metals.
Metal oxides such as O, SnO ₂ , In ₂ O ₃ , PbO, Sb ₂ O ₃ , HfB ₂ , ZrB ₂ , LaB ₆ , CeB ₆ ,
Metal borides such as YB ₄ and GdB ₄ , TiC, ZrC,
Metal carbide such as HfC, TaC, SiC, WC, Ti
Metal nitrides such as N, ZrN, and HfN, semiconductors such as Si and Ge, and carbon can be included.

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 overlap each other (when some fine particles are To form an island-like structure as a whole). The particle size of the fine particles is in the range of several to several thousand, preferably in the range of 10 to 200. In this 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. Also "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" (Kishio Kinoshita)
Ed., Kyoritsu Shuppan published on September 1, 1986).

In the present description, "fine particles have a diameter of about 2 to 3 μm to about 10 nm. In particular, 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. "Creative Science and Technology Promotion System" Ultra Fine Particle Project "(1981-198)
In 6), the particle size (diameter) is about 1 to 100 nm.
In the range of "ultra fine particles"
participant). Then, one ultrafine particle is an aggregate of about 100 to 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. ("Ultra Fine Particles-Creative Science and Technology-" Hayashi Chikyu, Ryoji Ueda, Akira Tazaki, ed .; Mita Publishing 1988 2
Lines 1 to 4) "Things smaller than ultrafine particles,
In other words, a single particle composed of several to several hundred atoms is usually called a cluster. "
-13th line) In view of the general term as described above, the term "fine particles" in the present specification is an aggregate of a large number of atoms and molecules. It refers to something of a few microns. The electron-emitting portion 5 is constituted by a high-resistance crack formed in a part of the conductive film 4 and depends on the thickness, the film quality, the material of the conductive film 4 and a method such as energization forming which will be described later. Become. In some cases, conductive fine particles having a particle size in the range of several Å to several hundreds Å depend on the inside of the electron-emitting portion 5. The conductive fine particles contain some or all of the elements of the material constituting the conductive film 4. Electron emitting portion 5 and conductive film 4 in the vicinity thereof
May also have carbon and carbon compounds.

Hereinafter, an example of the manufacturing method will be described with reference to FIGS. 4, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. 1) The substrate 1 is sufficiently washed with a detergent, pure water, an organic solvent, or the like, and a device electrode material is deposited by a vacuum evaporation method, a sputtering method, or the like. , 3 [FIG. 4 (a)].

2) A droplet of a conductive film forming solution is applied to the substrate 1 provided with the device electrodes 2 and 3 by an ink jet method (FIG. 4B), and the droplet is dried and fired. A conductive film 4 is formed (FIG. 4C). In the present invention, as described above, a conductive film forming solution containing a metal / non-metal element is used. Here, the method of applying a conductive film forming solution containing a metal / non-metal element has been described.
The method of forming is not limited to this.
A sputtering method, a chemical vapor deposition method, a dipping method, a spinner method, or the like can also be used.

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 current is applied between the device electrodes 2 and 3 using a power supply (not shown), an electron-emitting portion 5 having a changed structure is formed at the portion of the conductive film 4 (FIG. 4D). According to the energization forming, a portion where the structure of the conductive film 4 is locally broken, deformed or altered is formed. This portion constitutes the electron emission section 5. FIG. 5 shows an example of the voltage waveform of the energization forming.

The voltage waveform is preferably a pulse waveform. For this purpose, the method shown in FIG. 5A for continuously applying a pulse with a constant pulse peak value and the method shown in FIG. 5B for applying a voltage pulse while increasing the pulse peak value are used. is there. T1 and T2 in FIG. 5A are the pulse width and pulse interval of the voltage waveform. Normally T1 is 1 microsecond to 10m
Second and T2 are set in a range of 10 μsec to 100 msec. 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.
It can be similar to that shown in FIG. The peak value of the triangular wave (peak voltage during energization forming) can be increased, for example, by about 0.1 V steps.

The end of the energization forming process can be detected by applying a voltage that does not locally destroy or deform the conductive film 4 during the pulse interval T2, and measuring the current. 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 repeating the application of 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. 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 accordingly set as appropriate. Suitable organic substances include alkanes, alkenes, alkyne aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes,
Ketones, amines, phenols, carboxylic acids, organic acids such as sulfonic acid and the like, and specifically, methane, ethane, propane and the like, and saturated hydrocarbons represented by C _n H _{2n + 2} , ethylene, Unsaturated hydrocarbons represented by a composition formula such as C _n H _2n such as propylene, benzene, toluene, methanol, ethanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methylamine, ethylamine, phenol, formic acid, acetic acid, propionic acid, etc. 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 (including so-called highly oriented pyrolytic carbon HOPG, pyrolytic carbon PG, and amorphous carbon GC. HOPG is a crystal structure of almost perfect graphite, and PG is a crystal having a crystal grain of about 200 mm. The structure is slightly disturbed, GC indicates that the crystal grain is about 20 ° and the disorder of the crystal structure is further increased), amorphous carbon (amorphous carbon and a mixture of the amorphous carbon and the fine crystal of the graphite) The thickness is preferably in the range of 500 ° or less, more preferably in the range of 300 ° or less.

5) The electron-emitting device obtained through such a step 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, the partial pressure of this component must be kept 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 80 to 250 ° C, preferably 150 ° C.
As described above, it is desirable to perform the treatment for as long as possible. However, the present invention is not particularly limited to this condition.
This is performed under conditions appropriately selected according to various conditions such as 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, but 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.
As a result, the element current If and the emission current Ie are stabilized.
The basic characteristics of the electron-emitting device to which the present invention can be applied obtained through the above-described steps will be described with reference to FIGS.

FIG. 6 is a schematic view showing an example of a vacuum processing apparatus. This vacuum processing apparatus also has a function as a measurement and evaluation apparatus. In FIG. 6 as well, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as in FIG. In FIG. 6, reference numeral 65 denotes a vacuum vessel, and 66 denotes an exhaust pump. An electron-emitting device is provided in the vacuum vessel 65. That is, 1 is a substrate constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive film, and 5 is an electron-emitting portion. Reference numeral 61 denotes a power supply for applying a device voltage Vf to the electron-emitting device; 60, an ammeter for measuring a device current If flowing through the conductive film 4 between the device electrodes 2 and 3;
Reference numeral 4 denotes an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device. 63 is a high-voltage power supply for applying a voltage to the anode electrode 64, and 62 is an ammeter for measuring the emission current Ie emitted from the electron emission section 5 of the device. As an example, the voltage of the anode electrode is set to 1
The measurement can be performed with the range of kV to 10 kV and the distance H between the anode electrode and the electron-emitting device in the range of 2 mm to 8 mm.

In the vacuum vessel 65, 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 66 is composed of a normal high vacuum device system including a turbo pump and a rotary pump, and an ultrahigh 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. 7 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. 7, 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 is apparent from FIG. 7, 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) this element has a certain voltage (referred to as threshold voltage, Vth in FIG. 7)
When the above element voltage is applied, the emission current Ie sharply increases, while the emission current Ie is hardly detected below the threshold voltage Vth. That is, it is a nonlinear element having a clear threshold voltage Vth with respect to the emission current Ie.

(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 64 is:
It depends on the time for applying the element voltage Vf. That is, the amount of charge captured by the anode electrode 64 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.

In FIG. 7, an example in which the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as "MI characteristic") is shown by a solid line. 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.
An application example of the electron-emitting device of the present invention will be described below.
By arranging a plurality of the surface conduction electron-emitting devices of the present invention 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 electron-emitting device of the present invention has the characteristics (i) to (iii) as described above. That is, the electrons emitted from the surface conduction electron-emitting device are
Above the threshold voltage, it can be controlled by the peak value and width of the pulse voltage applied between the opposing element 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 of the devices, a surface-conduction electron-emitting device is selected according to an input signal to emit electrons. You can control the amount.

Hereinafter, based on this principle, an electron source substrate obtained by disposing a plurality of electron-emitting devices to which the present invention can be applied will be described with reference to FIG. 8, 81 is an electron source substrate, 82 is an X-direction wiring, and 83 is a Y-direction wiring.
84 is a surface conduction electron-emitting device, and 85 is a connection.
The surface conduction electron-emitting device 84 may be either a flat type or a vertical type.

The m X-direction wirings 82 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 83 is composed of n wirings DY1, DY2,... DYn, and is formed in the same manner as the X-directional wiring 82. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 82 and the n Y-directional wirings 83 to electrically separate them (m and n are both 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 81 on which the X-directional wiring 82 is formed. The material and the production method are appropriately set. The X-direction wiring 82 and the Y-direction wiring 83 are led out as external terminals. A pair of electrodes (not shown) constituting the surface conduction electron-emitting device 84 include m X-directional wires 82 and n Y wires.
It is electrically connected to the direction wiring 83 by a connection 85 made of a conductive metal or the like.

The material forming the wirings 82 and 83, the material forming the connection 85, the material forming the connection 85, 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.

A scanning signal applying means (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 84 arranged in the X direction is connected to the X-direction wiring 82. On the other hand, a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 84 arranged in the Y direction according to an input signal is connected to the Y-direction wiring 83. 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 constructed using such an electron source having a simple matrix arrangement will be described with reference to FIGS. 9, 10 and 11. FIG. FIG. 9 is a schematic diagram illustrating an example of a display panel of the image forming apparatus, and FIG. 10 is a schematic diagram of a fluorescent film used in the image forming apparatus of FIG. FIG.
FIG. 1 is a block diagram showing an example of a drive circuit for performing display in accordance with an NTSC television signal.

In FIG. 9, reference numeral 81 denotes an electron source substrate on which a plurality of electron-emitting devices are arranged, 91 denotes a rear plate on which the electron source substrate 81 is fixed, and 96 denotes a fluorescent film 94 on the inner surface of a glass substrate 93.
And a face plate on which a metal back 95 and the like are formed. Reference numeral 92 denotes a support frame, and a rear plate 91 and a face plate 96 are connected to the support frame 92 using frit glass or the like. Reference numeral 98 denotes an envelope, which is sealed by firing in air or nitrogen at a temperature range of 400 to 500 ° C. for 10 minutes or more.

Reference numeral 84 corresponds to the electron-emitting portion in FIG. Reference numerals 82 and 83 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 98 includes the face plate 96, the support frame 92, and the rear plate 91 as described above. Rear plate 9
Since 1 is provided mainly for the purpose of reinforcing the strength of the substrate 81, if the substrate 81 itself has sufficient strength, the separate rear plate 91 can be unnecessary. That is, the substrate 8
1, a supporting frame 92 is directly sealed, and a face plate 96,
The envelope 98 may be constituted by the support frame 92 and the substrate 81. On the other hand, by installing a support (not shown) called a spacer between the face plate 96 and the rear plate 91, an envelope 98 having sufficient strength against atmospheric pressure is provided.
Can also be configured.

FIG. 10 is a schematic diagram showing a fluorescent film. The fluorescent film 94 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 101 called a black stripe or a black matrix and a fluorescent material 102 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 102 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, other than a material mainly containing graphite which is usually used,
It is possible to use a material having conductivity and low transmission and reflection of light.

The method of applying the phosphor on the glass substrate 103 is not limited to monochrome or color, and may employ a precipitation method, a printing method, or the like. Usually, a metal back 95 is provided on the inner surface side of the fluorescent film 94. 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 96 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 can be manufactured by performing a smoothing process (usually called “filming”) on the inner surface of the fluorescent film after manufacturing the fluorescent film, and then depositing A1 by vacuum evaporation or the like.

The face plate 96 is further provided with a fluorescent film 9.
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 94 in order to increase the conductivity of No. 4. 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. 9 is manufactured, for example, as follows. The envelope 98 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 the envelope 98 in the same manner as in the above-described stabilization step, and is heated to about 10 ⁻⁷ Torr. After the atmosphere is made sufficiently low in the degree of vacuum of the organic substance, sealing is performed. In order to maintain a vacuum degree after the envelope 98 is sealed, a getter process may be performed. this is,
Immediately before or after the sealing of the envelope 98, the envelope 9 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 drive circuit for performing television display based on an NTSC television signal on a display panel configured using electron sources in a simple matrix arrangement will be described with reference to FIG. . In FIG.
111 is an image display panel, 112 is a scanning circuit, 113 is a control circuit, and 114 is a shift register. 115 is a line memory, 116 is a synchronization signal separation circuit, 117 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 111 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 element of the surface conduction electron-emitting device 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. It is an accelerating voltage for applying energy.

The scanning circuit 112 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),
It is electrically connected to terminals Dx1 to Dxm of the display panel 111. 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 the electron emission threshold. It is set to output a constant voltage that is equal to or lower than the value voltage. The control circuit 113 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. Control circuit 113
Is the synchronization signal Ts sent from the synchronization signal separation circuit 116.
Tscan and Ts for each part based on the sync
ft and Tmry control signals are generated.

The synchronizing signal separating circuit 116 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 116 includes a vertical synchronizing signal and a horizontal synchronizing signal, but is illustrated here as a Tsync signal for convenience of explanation. 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 114.

The shift register 114 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 113. (Ie, the control signal Tsft can be said to be a shift clock of the shift register 114). The data of one line of the image (corresponding to the drive data of the N electron-emitting devices) which has been subjected to the serial / parallel conversion is output from the shift register 114 as N parallel signals Id1 to Idn.

The line memory 115 is a storage device for storing data for one line of an image for a required time only, and stores the contents of Id1 to Idn as appropriate according to a control signal Tmry sent from the control circuit 113. The stored contents are output as I'd1 to I'dn,
The signal is input to the modulation signal generator 117. Modulation signal generator 1
Reference numeral 17 denotes a signal source for appropriately driving and modulating each of the surface-driven electron-emitting devices in accordance with each of the image data I'd1 to I'dn.
The voltage is applied to the surface conduction electron-emitting device in the display panel 111 through y1 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 employed. 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 117. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 117, 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. Shift register 114 and line memory 1
Reference numeral 15 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 separation circuit 116 into a digital signal. This can be achieved by providing an A / D converter at the output section of the 116. In connection with this, the line memory 115
The circuit used for the modulation signal generator 117 differs slightly 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 117, and an amplification circuit and the like are added as necessary. In the case of the pulse width modulation method, the modulation signal generator 117 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 a voltage modulation method using an analog signal, an amplification circuit using, for example, an operational amplifier can be used as the modulation signal generator 117, and a level shift circuit and 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 95 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 94 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 concept of the present invention. Although the NTSC system is used as the input signal, the input signal is not limited to the NTSC system, but may be a PAL, a SECAM system, or a TV signal including a larger number of scanning lines (for example, MUSE system, etc.). High-definition TV).

Next, the ladder-shaped 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. 12, reference numeral 120 denotes an electron source substrate, and 121 denotes an electron-emitting device. 122, Dx1 to Dx10 are common wirings for connecting the electron-emitting devices 121. A plurality of electron-emitting devices 121 are arranged on the substrate 120 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. 13 is a schematic diagram showing an example of a panel structure in an image forming apparatus having a ladder-type electron source. 130 is a grid electrode, 131 is a hole through which electrons pass, 132 is Dox1, Dox2. . . Dox
m outside the container. 133 is the grid electrode 1
30 connected to G1, G2. . . An external terminal 134 made of Gn is an electron source substrate in which the common wiring between the element rows is the same wiring. In FIG. 13, the same parts as those shown in FIGS. 9 and 12 are denoted by the same reference numerals as those shown in these figures. The image forming apparatus shown here and FIG.
The major difference from the image forming apparatus of the simple matrix arrangement shown in FIG. 7 is whether or not the grid electrode 130 is provided between the electron source substrate 120 and the face plate 96.

In FIG. 13, a grid electrode 130 is provided between the substrate 120 and the face plate 96. The grid electrode 130 is for modulating the electron beam emitted from the surface conduction electron-emitting device,
In order to allow an electron beam to pass through stripe-shaped electrodes provided orthogonally to the ladder-shaped element rows, one circular opening 131 is provided for each element. 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 external terminal 132 and the grid external terminal 133 are electrically connected to a control circuit (not shown). In the image forming apparatus of the present embodiment, a modulation signal for one line of an image is simultaneously applied to the grid electrode columns in synchronization with sequentially driving (scanning) the element rows one by one. This allows
By controlling the irradiation of each electron beam to the phosphor, an image can be displayed line by line. The image forming apparatus according to the invention includes
In addition to a display device for television broadcasting, a display device such as a video conference system and a computer, the present invention can also be used as an image forming device as an optical printer including a photosensitive drum or the like.

[0085]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples, and each element within a range in which the object of the present invention is achieved. This also includes those in which substitutions or design changes have been made.

Example 1 A complex for forming an electron-emitting device, palladium acetate-bis (propylenediamine), was synthesized as follows. 20 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.4 g of propylene diamine was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, which was crystallized and collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (propylenediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (propylenediamine) was 212 to 348 ° C.

Example 2 An electron-emitting device forming complex, palladium acetate-bis (2-
Methyl-1,2-propanediamine) was synthesized as follows. 35 g of isopropyl alcohol was added to 1.0 g of palladium acetate, and 2-methyl-1,2-
1.0 g of propanediamine was added and stirred at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered.

Acetone was added to the crystals, and the mixture was stirred well and filtered again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried in vacuo to obtain palladium acetate-bis (2-methyl-1,2-propanediamine). T in the air
As a result of the G measurement, the decomposition temperature of palladium acetate-bis (2-methyl-1,2-propanediamine) was 262 to 29.
7 ° C.

Example 3 An electron-emitting device forming complex, palladium acetate-bis (1,
2-cyclohexanediamine) was synthesized as follows. 45 g of isopropyl alcohol was added to 1.0 g of palladium acetate, and 1.5 g of 1,2-cyclohexanediamine was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration. Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (1,2-
Cyclohexanediamine) was obtained. As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (1,2-cyclohexanediamine) was 262 to 283 ° C.

Example 4 An electron-emitting device forming complex, palladium acetate-bis (o-
Phenylenediamine) was synthesized as follows. 0.5 g of palladium acetate and 25 m of isopropyl alcohol
and 0.51 g of o-phenylenediamine was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration.
Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation is repeated, and the crystals are sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (o-phenylenediamine).
I got As a result of TG measurement in air, palladium acetate
The decomposition temperature of bis (o-phenylenediamine) is 196 ~
286 ° C.

Example 5 A complex for forming an electron-emitting device, palladium acetate-bis (trimethylenediamine), was synthesized as follows. 25 g of isopropyl alcohol in 0.5 g of palladium acetate
Was added, and 0.4 g of trimethylenediamine was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (trimethylenediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (trimethylenediamine) was 207 to 274 ° C.

Example 6 A complex for forming an electron-emitting device, palladium acetate-bis (pentane-1,3-diamine), was synthesized as follows. 25 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.6 g of pentane-1,3-diamine was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (pentane-1,3-diamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (pentane-1,3-diamine) was 191 to 243 ° C.
Met.

Example 7 An electron-emitting device forming complex, palladium acetate-bis (2,
2-dimethyl-1,3-propanediamine) was synthesized as follows. 55 ml of ethyl alcohol was added to 2.0 g of palladium acetate, and 2,2-dimethyl-
2.4 g of 1,3-propanediamine was added, and the mixture was stirred at room temperature for 4.5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and after stirring,
It was collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (2,2-dimethyl-1,3-propanediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (2,2-dimethyl-1,3-propanediamine) was 23.
2-234 ° C.

Example 8 An electron-emitting device forming complex, palladium acetate-bis (2-
Hydroxy-1,3-propanediamine) was synthesized as follows. 30 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 2-hydroxy-
0.5 g of 1,3-propanediamine is added and 5
Stirred for hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration. Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (2-hydroxy-1,3-propanediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (2-hydroxy-1,3-propanediamine) was 212 to 377 ° C.

Example 9 An electron-emitting device forming complex, palladium acetate-bis (1,
4-butanediamine) was synthesized as follows. 0.5 g of palladium acetate and 25 m of isopropyl alcohol
1 and 0.5 g of 1,4-butanediamine was added with stirring, and the mixture was stirred at room temperature for 4.5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (1,4-butanediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (1,4-butanediamine) was 201 to 267 ° C.

Example 10 An electron-emitting device forming complex, palladium acetate-bis (N-
Methylethylenediamine) was synthesized as follows. 25 ml of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.43 g of N-methylethylenediamine was added with stirring, followed by stirring at room temperature for 5 hours. After the reaction,
The reaction mixture was filtered and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. Repeat this operation,
The crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (N-methylethylenediamine). As a result of TG measurement in air, palladium acetate-bis (N-
The decomposition temperature of methylethylenediamine) is 195 to 261.
° C.

Example 11 An electron-emitting device forming complex, palladium acetate-bis (N,
N′-dimethylethylenediamine) was synthesized as follows. 25 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.5 g of N, N'-dimethylethylenediamine was added with stirring, followed by stirring at room temperature for 5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered.

Acetone was added to the crystals, and the mixture was stirred well and filtered again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (N, N ′).
-Dimethylethylenediamine). TG in the air
As a result of the measurement, the decomposition temperature of palladium acetate-bis (N, N′-dimethylethylenediamine) was 192 to 272 ° C.

Example 12 An electron-emitting device forming complex, palladium acetate-bis (2-
Aminobenzylamine) was synthesized as follows.
Isopropyl alcohol 25 in 0.5 g of palladium acetate
and stirred under stirring with 0.6 g of 2-aminobenzylamine.
Was added and stirred at room temperature for 2.5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-
Bis (2-aminobenzylamine) was obtained. As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (2-aminobenzylamine) was 235 to 296 ° C.

Example 13 An electron-emitting device forming complex, palladium acetate-bis (2-
Aminomethylpyridine) was synthesized as follows.
Isopropyl alcohol 25 in 0.5 g of palladium acetate
Add 2-ml of 2-aminomethylpyridine under stirring.
Was added and stirred at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (2-aminomethylpyridine). TG in the air
As a result of the measurement, the decomposition temperature of palladium acetate-bis (2-aminomethylpyridine) was 177 to 268 ° C.

Example 14 An electron-emitting device forming complex, palladium acetate-bis (2,
3-naphthylenediamine) was synthesized as follows. 32 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.8 g of 2,3-naphthylenediamine was added with stirring, followed by stirring at room temperature for 6 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration. Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (2,3-naphthylenediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (2,3-naphthylenediamine) was 179 to 321 ° C.

Example 15 An electron-emitting device forming complex, palladium acetate-bis (1,
8-naphthylenediamine) was synthesized as follows. 38 ml of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.8 g of 1,8-naphthylenediamine was added with stirring, followed by stirring at room temperature for 6 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration. Further, acetone was added and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (1,8-naphthylenediamine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (1,8-naphthylenediamine) was 222 to 345 ° C.

Example 16 An electron-emitting device forming complex, palladium acetate- (2,2 ′)
-Bipyridyl) was synthesized as follows. 38 ml of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.8 g of 2,2′-bipyridyl was added with stirring, followed by stirring at room temperature for 6 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration. Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried in vacuo to obtain palladium acetate- (2,2′-bipyridyl). As a result of TG measurement in air, the decomposition temperature of palladium acetate- (2,2′-bipyridyl) was 245 to 357 ° C.

Example 17 An electron-emitting device forming complex, palladium acetate-bis (8-
Amino-1,2,3,4-tetrahydroquinoline) was synthesized as follows. 25 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and 0.8 g of 8-amino-1,2,3,4-tetrahydroquinoline was added with stirring, followed by stirring at room temperature for 4 hours. After the reaction, insolubles were collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration.
Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (8-amino-1,2,3,3).
4-tetrahydroquinoline). As a result of TG measurement in air, palladium acetate-bis (8-amino-11,
The decomposition temperature of 2,3,4-tetrahydroquinoline is 17
7-285 ° C.

Example 18 An electron-emitting device forming complex, palladium acetate-bis (homopiperazine), was synthesized as follows. To 0.5 g of palladium acetate, 25 ml of isopropyl alcohol was added, and with stirring, 0.5 g of homopiverazine was added, followed by stirring at room temperature for 3 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate-bis (homopiverazine). As a result of TG measurement in air, the decomposition temperature of palladium acetate-bis (homopiperazine) was 220-28.
5 ° C.

Example 19 An electron-emitting device forming complex, palladium acetate- (piperazine) was synthesized as follows. Palladium acetate 0.
Add 5 ml of isopropyl alcohol to 5 g, and under stirring,
0.43 g of piperazine was added and stirred at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred and filtered. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated, and the crystals were sufficiently washed with acetone and dried under vacuum to obtain palladium acetate- (piperazine). As a result of TG measurement in air, the decomposition temperature of palladium acetate- (piperazine) was 211 to 267 ° C.

Comparative Example 1 Palladium acetate-tetrakis (ethanolamine) [(C
H ₃ COO) decomposition temperature by TG measurement in the air of _{2 Pd (H 2 NC 2 H} 4 OH) 4] is about 133-315
° C, which is lower at the decomposition initiation temperature than the organometallic compound used in the present invention, and the temperature range required for decomposition is wide.

Example 20 A surface conduction electron-emitting device of the type shown in FIGS. 1A and 1B was prepared as the electron-emitting device of this example. FIG.
(A) is a plan view of the present element, and FIG. 1 (b) is a cross-sectional view. 1 (a) and 1 (b) are an insulating substrate, 2 and 3 are device electrodes for applying a voltage to the device, 4 is a conductive film including an electron emitting portion, and 5 is an electron emitting portion. Is shown. In the drawing, L represents the element electrode interval between the element electrodes 2 and 3, and W represents the width of the element electrodes.

With reference to FIG. 4, a method for manufacturing the electron-emitting device of this embodiment will be described. A quartz substrate is used as the insulating substrate 1. After sufficiently washing the substrate with an organic solvent, a pair of platinum element electrodes 2 and 3
A pair was formed (FIG. 4A). At this time, the device electrode interval L was 10 μm, the width W of the device electrode was 500 μm, and the thickness d was 1000 °. Palladium acetate-bis (2-
Methyl-1,2-propanediamine) [(CH ₃ CO
O) ₂ Pd (H ₂ NCH ₂ C (CH ₃ ) ₂ NH ₂ ) ₂ ]
Was taken, 0.6 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 0.05 g of isopropyl alcohol, and 1 g of ethylene glycol. Water was added to make a total amount of 100 g to obtain a palladium compound solution.

The palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm, and the filtrate was filtered using a bubble jet printer head BC-BC manufactured by Canon Inc.
01 and 20 V from the outside to the heater inside the specified head.
The palladium compound solution was discharged to the gap portions of the five pairs of device electrodes 2 and 3 on the quartz substrate [FIG. 4B].

The discharge was repeated five more times while maintaining the positions of the head and the substrate. The droplet was substantially circular and its straight line was about 110 μm. When this substrate was heated in an oven at 300 ° C. in the air atmosphere for 10 minutes to decompose and deposit the palladium compound on the substrate, a fine particle film (conductive film 4) composed of fine particles of palladium oxide was formed between the electrodes [ FIG. 4 (c)]. In addition, when these films were observed with an optical microscope, a uniform palladium oxide film was formed without precipitation of crystals. The variation in sheet resistance between the conductive films was 15%.

Next, as shown in FIG. 4D, a voltage is applied between the device electrodes 2 and 3, and the electron emitting portion 5 is formed by applying a current to the electron emitting portion forming thin film 4 (forming process). It was created. FIG. 5 shows a voltage waveform of the forming process. In FIG. 5, T1 and T2 are the pulse width and pulse interval of the voltage waveform, and in this embodiment, T1 is 1 millisecond, T1
2 is set to 10 milliseconds, 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 ×
This was performed for 60 seconds under a vacuum atmosphere of 10 ^-6 Torr. An activation step was also performed.

In the electron-emitting portion 5 thus prepared, fine particles mainly composed of palladium were dispersed and arranged, and the fine particles had an average particle diameter of 30 °. The electron emission characteristics of the device prepared as described above were measured. FIG. 6 shows a schematic configuration diagram of the measurement evaluation apparatus.

Also in FIG. 6, 1 is an insulating substrate, 2 and 3 are device electrodes, 4 is a conductive film, 5 is an electron emitting portion,
61 is a power supply for applying a voltage to the element, 60 is an ammeter for measuring the element current If, 64 is an anode electrode for measuring an emission current Ie generated from the element, and 63 is an anode electrode 64. High voltage power supply for applying voltage, 6
Reference numeral 2 denotes an ammeter for measuring an emission current. In measuring the device current If and the emission current Ie of the electron-emitting device, the power supply 61 and the ammeter 60 are connected to the device electrodes 2 and 3, and the power supply 63 and the ammeter 62 are connected above the electron-emitting device. Anode electrode 64 is arranged. Further, the electron-emitting device and the anode electrode 64 are installed in a vacuum device, and the vacuum device is equipped with a vacuum pump and other devices necessary for the vacuum device such as a vacuum gauge (not shown). 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 apparatus when measuring the electron emission characteristics was 1 × 10 ⁻⁶ Torr.

The device voltage was applied between the electrodes 2 and 3 of the electron-emitting device using the measurement and evaluation apparatus as described above, and the device current If and the emission current Ie flowing at that time were measured. The current-voltage characteristics as shown were obtained. On average, the element voltage of the five sets of the present elements is 7.3V.
The emission current Ie suddenly increases from about
In this case, the device current If is 2.4 mA and the emission current Ie is 1.1.
μA, and the electron emission efficiency η = Ie / If (%) is 0.1.
045%.

Instead of the anode electrode 64, a face plate having the above-described fluorescent film and metal back was arranged in a vacuum device. When electron emission from the electron source was attempted in this way, a part of the fluorescent film emitted light, and the intensity of light emission changed according to the device current Ie. Thus, it was found that this element functions as a light-emitting display element.

In the embodiments 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.

Comparative Example 2 Palladium acetate-tetrakis (ethanolamine)
[(CH ₃ COO) ₂ Pd (H ₂ NC ₂ H ₄ OH) ₄ ]
, 0.7 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 25 g of isopropyl alcohol and 1 g of ethylene glycol, and water was added to make a total amount of 100 g to obtain a palladium compound solution (Example 20). Pd concentration is the same as that of the palladium compound solution except that the organic palladium complex is different).

This palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm, and the filtrate was used as a bubble jet printer head BC-BC manufactured by Canon Inc.
01, and 20 V from outside to the heater inside the specified head
The palladium compound solution was discharged to each gap portion of the five pairs of device electrodes 2 and 3 on the quartz substrate in the same manner as in Example 20 by applying a DC voltage of 7 μsec. The ejection was repeated five more times while maintaining the position of the head and the substrate. The droplet was substantially circular and had a diameter of about 110 μm. When this substrate was heated in an oven at 350 ° C. in the air atmosphere for 12 minutes to decompose and deposit the metal compound on the substrate, a fine particle film composed of fine particles of palladium oxide was formed between the electrodes. The variation in the sheet resistance between the films was 20%.

Further, predetermined energization forming and activation processing were performed in the same manner as in Example 20, and evaluation as an electron-emitting device was performed. The average of the five elements is 1 element voltage.
At 6 V, the electron emission efficiency was 0.043%. As described above, when palladium acetate-tetrakis (ethanolamine) is used as the organic palladium compound, the temperature is 350 ° C.
It can be seen that the temperature is higher and takes longer to remove the organic residue than 12 minutes and palladium acetate-bis (2-methyl-1,2-propanediamine) used in the present invention.

Comparative Example 3 The same palladium compound solution as in Example 20 was applied to a quartz substrate having a device electrode pair formed on the surface in the same manner as in Example 20. This substrate was heated in an oven at 250 ° C. for 10 minutes in an air atmosphere. However, at this temperature and for this time, the calcination was insufficient and the palladium oxide was not completely formed.

As can be seen from this comparative example, Example 2
Like p. 0, the palladium compound solution is heated for 10 minutes, but is not sufficiently decomposed, and the organometallic compound used in the present invention is a compound which is decomposable at high temperatures and whose decomposition is rapidly terminated.

Examples 21 to 31 Organometallic compound solutions having the compositions shown in Tables 1 and 2 were prepared, and these were used in place of the palladium compound solution of Example 20. According to the method, the solution of each example was discharged to each gap portion of five sets of device electrodes. Substrate of each embodiment,
Heat treatment was performed at 400 ° C. for 15 minutes in a helium atmosphere containing 2% hydrogen, and the metal compound was thermally decomposed to form a conductive film between the electrodes. When these conductive films were observed with an optical microscope, they were confirmed to be uniform without crystal precipitation.

Further, an electron-emitting device was manufactured through the same forming and activating steps as in Example 20. After the device was formed, an electron emission phenomenon was confirmed at a device voltage of 14 to 18 V. In each case, the variation in the sheet resistance was 15% or less.

[0125]

[Table 1]

[0126]

[Table 2] Comparative Examples 4 to 10 Organometallic compound solutions having the compositions shown in Tables 3 and 4 were prepared and used in place of the organometallic compound solutions of Examples 21 to 31 by the bubble jet method in the same manner as in Example 20. Then, the solution of each comparative example was discharged to each gap portion of five sets of device electrodes. 2% of the substrate of each comparative example
Was performed at 400 ° C. for 30 minutes in a helium atmosphere containing hydrogen to thermally decompose the metal compound to form a conductive film between the electrodes. Further, an electron-emitting device was produced through the same forming and activation steps as in Example 20. After the device was formed, an electron emission phenomenon was confirmed at a device voltage of 14 to 18 V.

As described above, the heat treatment time is longer when the amino alcohol ligand is used than when the organometallic compound solution having a diami ligand is used as in Examples 21 to 31. I understand. In each case, the variation in the sheet resistance was 15% or less.

[0128]

[Table 3]

[0129]

[Table 4] Example 32 A quartz substrate was used as the insulating substrate 1, and after sufficiently washing with an organic solvent, five pairs of element electrodes 2 and 3 made of platinum were formed on the surface of the substrate 1. At this time, the distance L between the device electrodes was 10 μm, the width W of the device electrode was 500 μm, and the thickness thereof was 1000 °.

Next, a Cr film having a thickness of 1000 に was formed on the outer side of a rectangle having a width of 320 μm and a length of 160 μm centering on each of the opposing gap portions of the device electrodes 2 and 3. Take 2.9 g of palladium acetate-bis (2-methyl-1,2-propanediamine), 0.05 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 25 g of isopropyl alcohol, and add water to make the total amount 100 g. To obtain a palladium compound solution.

The palladium compound solution was subjected to 1000 rpm
Spin coating was performed between the electrodes on the substrate under the conditions of m and 60 seconds. The applied solution was heated in an oven at 300 ° C. in the air atmosphere for 10 minutes to decompose and deposit the metal compound on the substrate. As a result, a fine particle film composed of fine particles of palladium oxide was formed between the electrodes.

Next, each palladium oxide fine particle film formed on each of the above Cr films is removed together with the Cr film by an acid etchant, and the rectangular palladium oxide fine particle film is left as an electron emission portion forming film (conductive film) 4. And When these films were observed with an optical microscope, a uniform palladium oxide film was formed without the precipitation of crystals. The variation in the sheet resistance value between the conductive films was 14%. Further, predetermined energization forming and activation processing were performed in the same manner as in Example 20, and evaluation as an electron-emitting device was performed.
On average, the electron emission efficiency of the five devices was 0.044% at a device voltage of 16 V.

Examples 33 to 40 A palladium compound solution having the composition shown in Tables 5 and 6 was prepared, and the same treatment as in Example 32 was performed, except that the palladium compound solution of Example 32 was used. Five sets of electron-emitting devices were prepared. All the solutions could be easily applied to the substrate surface. After the fabrication of each device, an electron emission phenomenon was confirmed at a device voltage of 14 to 18 V. In addition, when the conductive film of each Example was observed with an optical microscope, it was uniform without precipitation of crystals. In addition, the variation in the sheet resistance value between the conductive films in each example was 15% or less.

[0134]

[Table 5]

[0135]

[Table 6] Comparative Examples 11 to 13 A palladium compound solution having the composition shown in Table 7 was prepared, and each solution was used between the five pairs of device electrodes under the same conditions as in Example 32, except that the palladium compound solution of Example 32 was used. Applied. The substrate was thermally decomposed in an oven at 350 ° C. in the air atmosphere for 15 minutes to form a conductive film. Further, an electron-emitting device was produced through the same forming and activation steps as in Example 32. After the device is prepared, the device voltage is 14 to 1
At 8 V, an electron emission phenomenon was confirmed.

As described above, the heat treatment time was longer when the amino alcohol ligand was used than when the organometallic compound solution having a diamine ligand was used as in Examples 32 to 40. I understand. In addition, the variation of the sheet resistance value between the conductive films of each comparative example was 15
% Or less.

[0137]

[Table 7] Example 41 In the same manner as in Example 20, the solution of the organometallic compound solution was applied between the respective counter electrodes of the substrate (see FIG. 8) on which 256 element electrodes of 16 rows and 16 columns and matrix wiring were formed. The droplets were applied by a bubble jet type ink jet apparatus, fired, and then subjected to a forming process to obtain an electron source substrate.

A rear plate 91, a support frame 92, and a face plate 96 were connected to this electron source substrate and vacuum-sealed to form an image forming apparatus according to the conceptual diagram of FIG. Terminal Dox
An arbitrary matrix image pattern could be displayed by applying a predetermined voltage to each element in a time-sharing manner through 1 to Dox 16 and terminals Doyl to Doy 16 and applying a high voltage to the metal back through the terminal Hv.

[0139]

As described above, the organometallic compound of the present invention is water-soluble, has a narrower thermal decomposition temperature range and a shorter decomposition time than conventional ones. Therefore, it is not necessary to use an organic solvent as a solvent for a droplet used when forming an electron-emitting portion of an electron-emitting device using this organometallic compound, so that the cost is low and the droplet can be fired in a short time.

Further, the generation of crystals in the conductive film formed using the organometallic compound of the present invention is suppressed, and the variation in the sheet resistance value of the conductive film can be suppressed within 15%. Variations between electron-emitting devices during electron emission can also be reduced. Further, since the electron emission characteristics are stable, an image forming apparatus in which a plurality of these elements are arranged becomes a high-quality image forming apparatus with less luminance unevenness.

[Brief description of the drawings]

FIG. 1 is a schematic plan view and a cross-sectional view illustrating a configuration of a surface conduction electron-emitting device applicable to the present invention.

FIG. 2 is a schematic view showing an example of a configuration of a conductive film forming solution discharge head applicable to the present invention.

FIG. 3 is a schematic view showing an example of a configuration of a parallel-type conductive film forming solution ejection head applicable to the present invention.

FIG. 4 is a schematic view illustrating an example of a method for manufacturing a surface conduction electron-emitting device according to the present invention.

FIG. 5 is a schematic diagram showing an example of a voltage waveform in a current forming process that can be employed in manufacturing the surface conduction electron-emitting device of the present invention.

FIG. 6 is a schematic diagram illustrating an example of a vacuum processing apparatus having a measurement evaluation function.

FIG. 7 is a graph showing an example of the relationship between the emission current Ie, the device current If, and the device voltage Vf for the surface conduction electron-emitting device of the present invention.

FIG. 8 is a schematic diagram showing an example of the electron source of the present invention arranged in a simple matrix.

FIG. 9 is a schematic diagram illustrating an example of a display panel of the image forming apparatus of the present invention in which a simple matrix is arranged.

FIG. 10 is a schematic diagram illustrating an example of a fluorescent film.

FIG. 11 is a block diagram illustrating an example of a drive circuit for performing display on an image forming apparatus according to an NTSC television signal.

FIG. 12 is a schematic diagram showing an example of the electron source of the present invention in which ladders are arranged.

FIG. 13 is a schematic diagram illustrating an example of a display panel of the image forming apparatus of the present invention in which ladders are arranged.

FIG. 14 is a schematic diagram illustrating an example of a surface conduction electron-emitting device of a Hartwell.

[Explanation of symbols]

1: substrate, 3: element electrode, 4: conductive film, 5: electron emitting portion, 21: nozzle body, 22: heater or piezo element, 23: ink flow path, 25: ink supply tube, 2
6: ink reservoir, 60: conductive film 4 between device electrodes 2 and 3
For measuring the device current If flowing through the device, 61:
A power supply for applying a device voltage Vf to the electron-emitting device, 6
2: Ammeter for measuring the emission current Ie emitted from the electron emission section 5, 63: High voltage power supply for applying a voltage to the anode electrode 64, 64: Emission current Ie emitted from the electron emission section of the element Electrode for trapping
5: vacuum device, 66: exhaust pump, 81: electron source substrate,
82: X direction wiring, 83: Y direction wiring, 84: Surface conduction electron-emitting device, 85: Connection, 91: Rear plate, 9
2: support frame, 93: glass substrate, 94: fluorescent film, 95:
Metal back, 96: face plate, 97: high voltage terminal, 98: envelope, 101: black conductive material, 102: phosphor, 103: glass substrate, 111: display panel, 11
2: scanning circuit, 113: control circuit, 114: shift register, 115: line memory, 116: synchronization signal separation circuit, 117: modulation signal generator, Vx and Va: DC voltage source, 120: electron source substrate, 121: Electron-emitting device, 1
22: Dx1 to Dx10 are common wirings for wiring the electron-emitting devices, 130: grid electrodes, 131: holes for passing electrons, 132: Dox1, Dox
2. . . Terminals outside the container made of Doxm, 133: G1, G2 connected to the grid electrode 130.

Claims (15)

[Claims] 1. An electron-emitting device forming organometallic compound for forming an electron-emitting portion of an electron-emitting device having an electron-emitting portion between opposed electrodes on a substrate, wherein the organometallic compound is as follows: Formula 1 (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon _{atoms, R 2, R 3, R} 6, R 7 is a hydrogen atom or an alkyl group having a carbon number of 1 to 2, R ₂ and R ₆ or R ₃ and R ₇ may be bonded, R ₄ and R _{5 each} represent a hydrogen atom or an alkylene group, and R ₄ and R ₅ may be each independently or bonded to form a cyclic group. , (R
_{2) (R 3) N-} R 4 and / or R ₅ -N (R ₆₎
(R ₇ ) may be a cyclic group, and (R ₂ ) (R ₃ ) N
—R ₄ —R ₅ or R ₄ —R ₅ —N (R ₆ ) (R ₇ ) may be each cyclically bonded, n is an integer of 1 to 4, m is an integer of 1 to 4, M Represents a metal, R ₂ ,
When R ₃ , R ₆ , and R ₇ are all hydrogen atoms, and
Except when R ₄ -R ₅ -is -CH ₂ -CH _2- )
An organometallic compound for forming an electron-emitting device, which is represented by the following formula: 2. The metal used in the formula (1) is Pt,
Pd, Ru, Ag, Cu, Cr, Fe, Pb, Zn, S
The organometallic compound for forming an electron-emitting device according to claim 1, wherein the organometallic compound is selected from the group consisting of n. 3. In the above formula (1), -R ₄ -R ₅ -is the following formula (2): (Wherein R ₈ and R ₉ represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, p represents 0 or 1, and q represents an integer of 0 to 4). The organometallic compound for forming an electron-emitting device according to claim 1. 4. -R ₄ -R ₅ represented by the formula (2)
Is selected from the group consisting of 1,2-phenylene, 1,2-cyclohexylene, 2,3-naphthylene, 1,8-naphthylene, 1-methylene-2-phenylene. The organometallic compound for forming an electron-emitting device according to the above. 5. The method according to claim 1, wherein (R ₂ ) (R ₃ )
N—R ₄ and / or R ₅ —N (R ₆ ) (R ₇ ) is 2
The organometallic compound for forming an electron-emitting device according to claim 1, wherein the compound is pyridyl. 6. In the above formula (1), (R ₂ ) (R ₃ )
N—R ₄ —R ₅ or R ₄ —R ₅ —N (R ₆ ) (R ₇ )
Is 1,2,3,4-tetrahydroquinolin-8-yl, the organometallic compound for forming an electron-emitting device according to claim 1, wherein 7. The electron-emitting device according to claim 1, wherein the electron-emitting device is a surface conduction electron-emitting device.
5. The organometallic compound for forming an electron-emitting device according to any one of the above. 8. A step of applying a conductive film forming solution between opposing electrodes on a substrate, a step of heating and firing the applied solution to form a conductive film, and an electron emitting portion in the conductive film. A method for manufacturing an electron-emitting device, comprising the step of forming an organic metal compound according to any one of claims 1 to 7 as the conductive film forming solution. A method for manufacturing an electron-emitting device. 9. The method according to claim 8, wherein the method for applying the solution droplets is an ink jet method. 10. The method according to claim 9, wherein the inkjet method is a piezo jet method. 11. The method according to claim 9, wherein the inkjet method is a bubble jet method. 12. The method according to claim 8, wherein the droplets are continuously applied to form the applied droplets in a linear or planar shape. A method for manufacturing an electron-emitting device. 13. The method according to claim 8, wherein the electron-emitting device is a surface conduction electron-emitting device. 14. An electron source including an electron-emitting device and a means for applying a voltage to the device, a fluorescent film that receives and emits electrons emitted from the device, and is applied to the device using an external signal. An image forming apparatus comprising: a driving circuit for controlling a voltage; wherein an electron emission portion of the element is formed using the organometallic compound according to claim 1. Image forming device. 15. The image forming apparatus according to claim 14, wherein the electron-emitting device is a surface conduction electron-emitting device.