JPH10283911A - Organic metallic compound for forming electron emission element, manufacture of electron emission element, and picture image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize theremally stable water solubility and decomposition in high temperature, reduce costs and shorten a baking time, by forming the electron emission part for an electron emission element, having an electron emission part between opposite electrodes, on a base plate, by a specific organic metallic compound. SOLUTION: An organic metallic compound for forming an electron emitting element is to be a compound expressed in a formula (1) where, R1 : alkyl group of H or C1-4 ; R4 , R6 , R8 : -(CH2 )s-(CRa)(Rb)-(CH2 )t- respectively, R2 , R3 , R5 , R7 , R9 , and R10 : an alkyl group of H or C1-3 , Ra and Rb: an alkyl group of H or C1-2 , n=1-4, m=1 and 2, p=0.1, s=0, 1 and 2, t=1 and 2, and M: metal. A conductive film 4 is formed to perform forming by electrocution treatment, thereby obtaining the electron emitting element, by forming element electrodes 2 and 3 on a base plate 1, and imparting a solution droplet for forming a conductive film including the organic metallic compound to dry and bake the droplet.

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 of manufacturing an electron-emitting device by heating and baking a solution containing the compound, and an electron-emitting device obtained by the method. The present invention relates to an image forming apparatus used.

[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). Examples of surface conduction electron-emitting devices include:
M. I. Elinson, RadioEng. Elec
Tron Phys. , 10, 1290 (1965).

[0004] The surface conduction electron-emitting device utilizes the phenomenon that 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 Solid Fi
lms ", 9,317 (1972)] , In 2 O 3 / S
nO ₂ thin film [M. Hartwell and
C. G. FIG. Fonstad: "IEEE Trans.
ED Conf. , 519 (1975)], using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1,
No. 22, p. 22 (1983)].

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-alcoholamine complex (Japanese Patent Application Laid-Open No. H7-101619) has been synthesized as an organic metal compound soluble in water. However, 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 the solution of the organometallic compound by a piezo element to produce and apply droplets, or using a heater (Hereinafter referred to as BJ method) by rapidly bubbling a solution of the organometallic compound to form and apply droplets. 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 of the electron-emitting device having an electron-emitting portion between opposed electrodes on a substrate, The organometallic compound has the following formula (1)

[0011]

Embedded image (However, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ , R ₆ and R ₈ are each independently — (CH
_{2) s-C (Ra)} (Rb) - (CH 2) t- and _{represents, R 2, R 3, R} 5, R 7, R 9, R 10 is a hydrogen atom or an alkyl having 1 to 3 carbon atoms R ₃ and R
₉ , or R ₂ and R ₁₀ may be bonded to each other;
a and Rb are a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, n is an integer of 1 to 4, m is an integer of 1 or 2, p is 0 or 1, s is 0, 1 or 2 , T represents 1 or 2, and M represents a metal).

The metals used in equation (1) are Pd, Ag,
It can be selected from the group consisting of Ru, Cu, Cr, Fe, Pb, Zn and Sn. In the formula (1), R ₂ ,
R ₃ , R ₉ and R ₁₀ can be hydrogen atoms. In the formula (1), R ₃ and R ₉ or R ₂ and R ₁₀
There are _{bound, [(R 2) (R} 3) N-R 4 - {N
(R ₅ ) -R _6- ｝ pN (R ₇ ) -R ₈ -N (R ₉ )
(R ₁₀ )] can be a cyclic compound.

According to the method of manufacturing an electron-emitting device of the present invention, a step of applying a droplet of a conductive film forming solution between opposing electrodes on a substrate, and heating and firing the droplet to form a conductive film And a step of forming an electron emission portion in the conductive film, wherein a solution containing the organometallic compound of the present invention is used as the conductive film forming solution. It is characterized by the following.

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-mentioned 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. Further, the image forming apparatus of the present invention has an electron source including an electron-emitting device and voltage applying means for the device, a phosphor film that receives and emits electrons emitted from the device,
A driving circuit for controlling a voltage applied to the element using an external signal, wherein the element includes an electron-emitting portion formed using the organometallic compound of the present invention. Features.

The formula (1) is a compound obtained by coordinating a metal with a tri- or tetraamine-based tridentate or tetradentate ligand which forms a chelate compound with a metal atom. An organic material that is water-soluble by using it as a device forming material, has a narrower temperature range for decomposition than organometallic compounds conventionally used in the production of electron-emitting devices, leaves no residue in the firing step, and decomposes at high temperatures It is a metal compound. By using this complex as a material for forming an electron-emitting device, it can be easily dissolved in water to reduce the occurrence of kogation on the heater surface, reduce the cost and time required for firing, and achieve low-cost and easy electron formation. An emission element can be made.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. A preferred embodiment of the 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 can be 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.

Materials for the opposing element electrodes 2 and 3 include:
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 length W of the device electrode can be in the range of 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 the present 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 crack in a film to form a high resistance state is performed. Includes The conductive film 4 is made of PdO, SnO in addition to the above metals.
₂ , metal oxides such as In ₂ O ₃ , PbO, Sb ₂ O ₃ ,
HfB ₂ , ZrB ₂ , LaB ₆ , CeB ₆ , YB ₄ , G
dB ₄ of a metal such as boron hydride, TiC, ZrC, HfC, T
aC, SiC, metal carbide such as WC, TiN, ZrN,
Metal nitrides such as 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 formed). 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 Surface / Particle"
(Edited by Kinoshita Yoshio, Kyoritsu Shuppan published September 1, 1986)
Then, it is described as follows. "When we say fine particles in this paper, the diameter is about 2-3 μm to 10n.
m, and especially when it is referred to as ultrafine particles, the particle size is 10
It means from about nm to about 2 to 3 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. ”(P. 195, lines 22 to 26) In addition, the New Technology Development Corporation's“ Hayashi and Ultrafine Particle Project ” The definition of “ultrafine particles” in the above was that the lower limit of the particle size was even smaller, and was as follows.

In the “Ultra Fine Particle Project” of the Creative Science and Technology Promotion System (1981 to 1986), a particle having a particle size (diameter) in the range of about 1 to 100 nm is called “ultra fine particle”. Then, one ultrafine particle is about 100-
It is an aggregate of about 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. ("Ultra Fine Particles-Creative Science and Technology-" Hayashi Tax, Ryoji Ueda, Akira Tazaki
Ed., Mita Publishing, 1988, page 2, lines 1 to 4) "A particle smaller than an ultrafine particle, that is, a single particle composed of several to several hundred atoms is usually called a cluster." Lines 12 to 13) Based on 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. Refers to those of several 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, film quality, material, and the method such as energization forming described later of the conductive film 4. It will be. 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. The electron emitting portion 5 and the conductive film 4 near the electron emitting portion 5
It can also have carbon and carbon compounds.

An example of the manufacturing method will be described below 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 element after the forming. The activation step is a step in which the element current If and the emission current Ie are significantly changed by this step.

The activation step can be performed, for example, by repeatedly applying a pulse in an atmosphere containing an organic substance gas, similarly to the energization forming. This atmosphere can be formed by using an organic gas remaining in the atmosphere when the inside of the vacuum vessel is evacuated using, for example, an oil diffusion pump or a rotary pump, or a vacuum once sufficiently evacuated by an ion pump or the like. It can also be obtained by introducing a gas of an appropriate organic substance. 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 element current If and the emission current Ie. The pulse width, pulse interval, pulse crest value, and the like are set as appropriate.

Carbon and carbon compounds include graphite (so-called highly oriented pyrolytic carbon HOPG, pyrolytic carbon P).
G, including amorphous carbon GC, HOPG has a crystal structure of almost perfect graphite, PG has a crystal grain of about 200 ° and has a slightly disordered crystal structure, and GC has a crystal grain of about 20 ° and has a disordered crystal structure. And amorphous carbon (refer to amorphous carbon and a mixture of amorphous carbon and the above-mentioned graphite microcrystals), and the film thickness is preferably in the range of 500 ° or less, more preferably 300 ° or less. Is more preferably in the range of

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, it is necessary to keep the partial pressure of this component as low as possible. . The partial pressure of the organic component in the vacuum vessel is preferably 1 × 10 ⁻⁸ Torr or less, more preferably 1 × 10 ⁻¹⁰ Torr or less, at a partial pressure at which the carbon and carbon compounds are not newly deposited. Further, when evacuating the inside of the vacuum vessel, it is preferable to heat the entire vacuum vessel to facilitate evacuating the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device. The heating condition at this time is 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 step is performed is the same as that at the end of the stabilization treatment, 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 employing 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 clear 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) the emission current Ie sharply increases when an element voltage higher than a certain voltage (referred to as a threshold voltage, Vth in FIG. 7) or more is applied to the element, and the emission current Ie decreases below the threshold voltage Vth. Ie is hardly detected. 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 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 are electrically connected by m X-directional wirings 82, n Y-directional wirings 83, and a connection 85 made of a conductive metal or the like. It is connected. The material forming the wiring 82 and the wiring 83, the material forming the connection 85, the material forming the connection 85, and the material forming the pair of element electrodes, even if some or all of the constituent elements are the same, Each may be different. These materials are appropriately selected, for example, from the above-described materials for the device electrodes. When the material forming the element electrode is the same as the wiring material, the wiring connected to the element electrode can also be called an element electrode.

The X-direction wiring 82 is connected to a scanning signal applying means (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 84 arranged in the X direction. On the other hand, a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 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 fluorescent substance to the glass substrate 103 can employ a precipitation method, a printing method, or the like irrespective of monochrome or color. 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.

[0060] The envelope 98, similar to the aforementioned stabilization step, while being heated appropriately, ion pump, by an exhaust device not using oil, such as a sorption pump evacuated through an exhaust pipe (not shown), 10 ^-7 After the atmosphere is made sufficiently low in an organic substance having a degree of vacuum of about Torr, sealing is performed. In order to maintain a vacuum degree after the envelope 98 is sealed, a getter process may be performed. This is the envelope 9
Immediately before or after the sealing of 8, the getter disposed at a predetermined position (not shown) in the envelope 98 is heated by heating using resistance heating, high-frequency heating, or the like to form a vapor deposition film. This is the processing to be performed. The getter is usually composed mainly of Ba or the like.
The vacuum degree of 10 ^-5 or 1 × 10 ^-7 Torr is maintained. 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 NTSC television signals on a display panel configured using electron sources arranged 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 an output electron beam of each element of one row of surface conduction electron-emitting devices 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 non-scanned 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, 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 adopted. When implementing the voltage modulation method, a circuit of a voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 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 of the synchronization signal separation circuit 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 the voltage modulation method using an analog signal, for example, an amplification circuit using an operational amplifier or the like can be used as the modulation signal generator 117, and a level shift circuit or the like can be added as necessary. In the case of the pulse width modulation method, for example, a voltage-controlled oscillation circuit (VCO) can be employed, and an amplifier for amplifying the voltage up to the drive voltage of the surface conduction electron-emitting device can be added as necessary.

In an image display apparatus to which the present invention can be applied, which has 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, a ladder-type arrangement of the electron source and the image forming apparatus will be described with reference to FIGS. FIG.
FIG. 2 is a schematic view showing an example of an electron source having a ladder arrangement.
In FIG. 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 of the present invention is used not only as a display device for television broadcasting, a display device such as a video conference system or a computer, but also as an image forming device as an optical printer using a photosensitive drum or the like. You can also.

[0081]

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- (triethylenetetramine), was synthesized as follows. 30 ml of isopropyl alcohol was added to 0.5 g of palladium acetate, 0.4 g of triethylenetetramine was added with stirring, and the mixture was stirred 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, 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 in vacuo to obtain palladium acetate- (triethylenetetramine). As a result of TG measurement in air, the decomposition temperature of palladium acetate- (triethylenetetramine) was 195 to 283 ° C.

Example 2 Palladium acetate- (N, N ′) complex for forming an electron-emitting device
-(2-aminoethyl) propanediamine)) was synthesized as follows. 25 g of isopropyl alcohol was added to 0.5 g of palladium acetate, and N, N'-
0.43 g of (2-aminoethyl) propanediamine was added, and the mixture was stirred 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 to remove the supernatant. After repeating this operation, drying was performed to obtain palladium acetate- (N, N '-(2-aminoethyl) propanediamine). As a result of TG measurement in the air, the decomposition temperature of palladium acetate- (N, N '-(2-aminoethyl) propanediamine) was 208 to 322 ° C.

Example 3 An electron-emitting device forming complex, palladium acetate- (1,4,
8,11-tetraazacyclotetradecane) was synthesized as follows. To 0.5 g of palladium acetate, 20 ml of ethyl alcohol was added, and with stirring, 0.44 g of 1,4,8,11-tetraazacyclotetradecane was added, followed by stirring at room temperature for 5.5 hours.

After the reaction, the reaction mixture was filtered and the filtrate was kept at 30 ° C.
The solvent was distilled off under reduced pressure. Acetone was added to the residue, and the mixture was stirred to remove the supernatant. After repeating this operation, dry,
Palladium acetate- (1,4,8,11-tetraazacyclotetradecane) was obtained. As a result of TG measurement in air,
The decomposition temperature of palladium acetate- (1,4,8,11-tetraazacyclotetradecane) was 216 to 371 ° 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 4 A surface conduction electron-emitting device of the type shown in FIGS. 1A and 1B was prepared as an electron-emitting device of this embodiment. FIG.
(A) is a plan view of the present element, and FIG. 1 (b) is a cross-sectional view. 1 (a) and 1 (b), reference numeral 1 denotes an insulating substrate, 2 and 3 denote device electrodes for applying a voltage to the device, 4 denotes a conductive film, and 5 denotes an electron emitting portion. In the drawings, L represents the element electrode interval between the element electrodes 2 and 3, and W represents the width of the element electrodes.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. A quartz substrate was used as the insulating substrate 1, and after sufficiently washing it with an organic solvent, five pairs of element electrodes 2 and 3 made of platinum were formed on the surface of the substrate 1 [FIG.
(A)]. 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 d thereof was 1000 °.

Palladium acetate- (triethylenetetramine) [(CH ₃ COO) ₂ Pd (H ₂ NCH ₂ CH ₂ N)
HCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ) ₂ ]
g, 86% saponified polyvinyl alcohol (average degree of polymerization 50
0) 0.05 g, isopropyl alcohol 25 g,
Take 1 g of ethylene glycol and add water to make the total amount 10
0 g, to give a palladium compound solution.

This palladium compound solution was filtered with 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 device electrodes 2 and 3 of the quartz substrate by applying the DC voltage of 7 μsec (FIG. 4B). The ejection was repeated five more times while maintaining the positions of the head and the substrate. The droplet was substantially circular and had a diameter of about 110 μm. This substrate is placed in air atmosphere 3
When the metal compound was decomposed and deposited on the substrate by heating in an oven at 00 ° C. for 10 minutes, a fine particle film (conductive film 4) composed of fine particles of palladium oxide was formed between the electrodes [FIG. 4 (c)]. ]. Observation of these films with an optical microscope confirmed that the films were uniform without crystal precipitation. The variation in sheet resistance between the conductive films was 13%.

Next, as shown in FIG. 4D, the electron-emitting portion 5 was formed by applying a voltage between the device electrodes 2 and 3 and conducting (forming) the conductive film 4. . FIG. 4 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. In this embodiment, T1 is 1 millisecond,
T2 is 10 milliseconds, the peak value of the triangular wave (peak voltage during forming) is 5 V, and the forming process is about
This was performed for 60 seconds in a vacuum atmosphere of × 10 ^-6 Torr.

In the electron-emitting portion 5 thus prepared, fine particles mainly composed of palladium were dispersed and arranged, and the average particle size of the fine particles was 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 thin film including an electron emitting portion, 5 is an electron emitting portion, 61 is a power supply for applying a voltage to the device,
Reference numeral 60 denotes an ammeter for measuring an element current If, 64 denotes an anode electrode for measuring an emission current Ie generated from the element, 63 denotes a high-voltage power supply for applying a voltage to the anode electrode 64, and 62 denotes an emission current. It is an ammeter for measuring. 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. 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). This enables measurement and evaluation of the present element. In this embodiment, the distance between the anode and the electron-emitting device is 4 mm, and the potential of the anode is 1 k.
V, the degree of vacuum in the vacuum device at the time of measuring the electron emission characteristics is 1 × 1
It was set to 0 ^-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 emission current Ie of the five sets of elements rapidly increases from an element voltage of about 7.3 V. At an element voltage of 16 V, the element current If becomes 2.4 mA, the emission current Ie becomes 1.1 μA, and the electron emission efficiency η = Ie / If was 0.045%.

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 phosphor film emitted light, and the intensity of light emission changed according to the device current If. Thus, it was found that this element functions as a light-emitting display element.

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

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 4). Pd concentration is the same as that of the palladium compound solution except that the organic palladium complex is different). The palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm, and the filtrate was filled in a bubble jet printer head BC-01 of Canon Inc., and a 20 V DC voltage was externally applied to a heater in a predetermined head by 7 μm. Seconds,
In the same manner as in Example 4, a filtered palladium compound solution was discharged to each gap portion of five pairs of device electrodes 2 and 3 on a quartz substrate. The ejection was repeated five more times while maintaining the positions of the head and the substrate. The droplet is approximately circular and has a diameter of about 110
μm. The metal compound was decomposed and deposited on the substrate by heating the substrate in an oven at 350 ° C. in the air atmosphere for 12 minutes. As a result, a fine particle film (conductive film) composed of fine particles of palladium oxide was formed. The variation in the sheet resistance value between the conductive films was 22%. Further, predetermined energization forming and activation processing were performed in the same manner as in Example 4, and evaluation as an electron-emitting device was performed. The average electron emission efficiency of the five sets of devices was 0.043% at a device voltage of 16 V.

When palladium acetate-tetrakis (ethanolamine) is used as the organic palladium compound, it must be calcined at 350 ° C. for 12 minutes, and the organic residue is higher than that of palladium acetate- (triethylenetetramine) used in the present invention. The temperature is high and the time is long to remove the objects.

Comparative Example 3 The same palladium compound solution as in Example 4 was applied to a quartz substrate having a device electrode pair formed on the same surface as in Example 4. 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, even at the same heating time as in Example 4, the palladium compound solution was not sufficiently decomposed at 250 ° C., and the organometallic compound used in the present invention was decomposable at high temperatures and decomposition was terminated quickly. Compound.

Example 5-21 An organometallic compound solution having the composition shown in Tables 1 to 3 was prepared and used in place of the palladium compound solution of Example 4 by the bubble jet method in the same manner as in Example 4. ,
The solution of each example was discharged into each gap portion of five sets of device electrodes. This substrate was subjected to a heat treatment at 400 ° C. for 15 minutes in a helium atmosphere containing 2% hydrogen, and each metal compound was thermally decomposed to form a conductive film. When each conductive film was observed with an optical microscope, it was confirmed that the film was uniform without precipitation of crystals.

Further, an electron-emitting device was manufactured through the same forming and activating steps as in Example 4. After the device was formed, an electron emission phenomenon was confirmed at a device voltage of 14 to 18 V. The variation of the sheet resistance value between the conductive films in each example was 15% or less.

[0104]

[Table 1]

[0105]

[Table 2]

[0106]

[Table 3]

Comparative Examples 4 to 10 Organometallic compound solutions having the compositions shown in Tables 4 and 5 were prepared, and were used in place of the organometallic compound solutions of Examples 4 to 21. The solution of each comparative example was discharged to each gap portion of five sets of device electrodes by a jet method. This substrate was subjected to a heat treatment at 400 ° C. for 30 minutes in a helium atmosphere containing 2% hydrogen to thermally decompose the metal compound to form a conductive film. Further, an electron-emitting device was produced through the same forming and activation steps as in Example 4. After the device is created, the device voltage 1
An electron emission phenomenon was confirmed at 4 to 18 V. The variation of the sheet resistance value between the conductive films of each comparative example was 20% or more. Compared to the case where the organometallic compound solution having a polyamine ligand is used as in Examples 5 to 21, the heat treatment time is longer when the organometallic compound solution having an amino alcohol ligand is used. Recognize.

[0108]

[Table 4]

[0109]

[Table 5]

Example 22 A quartz substrate was used as the insulating substrate 1. After sufficiently washing the substrate 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 d thereof was 1000 °.

Next, a Cr film having a thickness of 1000 Å was formed on the outside 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. 2.6 g of palladium acetate- (N, N '-(2-aminoethyl) propanediamine), 0.05 g of 186% saponified polyvinyl alcohol (average degree of polymerization 500), 25 g of isopropyl alcohol, and water were added to the total amount. Was set to 100 g to obtain a palladium compound solution.

The palladium compound solution is supplied at 1000 rpm
A film was formed on the insulating substrate 1 on which the device electrodes 2 and 3 were formed by spin coating between the electrodes under the conditions of m and 60 seconds. This was heated in an air atmosphere oven at 300 ° C. for 10 minutes to decompose and deposit the metal compound on the substrate. As a result, a fine particle film composed of fine palladium oxide particles 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 a thin film for forming an electron emitting portion (conductive film 4). And When each conductive film was observed with an optical microscope, it was confirmed that the film was uniform without precipitation of crystals. The variation in sheet resistance between the conductive films was 14%.

Further, predetermined energization forming and activation processing were performed in the same manner as in Example 4, and evaluation as an electron-emitting device was performed. The five sets of devices have an average device voltage of 16
At V, the electron emission efficiency was 0.045%.

Examples 23 to 27 A palladium compound solution having the composition shown in Table 6 was prepared and treated in the same manner as in Example 22 except that the palladium compound solution of Example 22 was used. Was produced. All the solutions could be easily applied to the substrate surface. 300 applied solution
The resultant was heated and baked at 10 ° C. for 10 minutes to form a conductive film. When each conductive film was observed with an optical microscope, it was confirmed that each film was a uniform film without precipitation of crystals. After the device was formed, an electron emission phenomenon was observed at a device voltage of 14 to 18 V. The variation of the sheet resistance value between the conductive films in each example was 15% or less.

[0116]

[Table 6]

Comparative Examples 11 to 13 A palladium compound solution having the composition shown in Table 7 was prepared, and instead of the palladium compound solution of Example 22, the solution of each comparative example was used under the same conditions as in Example 22. It was applied between the electrodes. This was thermally decomposed in an oven at 350 ° C. in the air atmosphere for 15 minutes to form a conductive film.

Further, through the same forming and activating steps as in Example 22, an electron-emitting device was produced. After the device was formed, an electron emission phenomenon was confirmed at a device voltage of 14 to 18 V. It can be seen that the heat treatment time is longer when an amino alcohol ligand is used than when an organometallic compound solution having a diamine or tetraamine ligand is used as in Examples 22 to 27. The variation in the sheet resistance was 20% or more.

[0119]

[Table 7]

Example 28 In the same manner as in Example 4, an organic metal compound solution was applied to each of the opposite electrodes on the substrate (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 device, baked, 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 produce an image forming apparatus according to the conceptual diagram of FIG. Terminal Dox
By applying a predetermined voltage to each element in a time-sharing manner through l to Dox16 and terminals Doy1 to Doy16 and applying a high voltage to the metal back through the terminal Hv, an arbitrary matrix image pattern with less luminance unevenness can be displayed. .

[0122]

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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 11/06 C09K 11/06 Z H01J 9/02 H01J 9/02 E 31/12 31/12 C

Claims (13)

[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 (However, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ , R ₆ and R ₈ are each independently — (CH
_{2) s-C (Ra)} (Rb) - (CH 2) t- and _{represents, R 2, R 3, R} 5, R 7, R 9, R 10 is a hydrogen atom or an alkyl having 1 to 3 carbon atoms R ₃ and R
₉ , or R ₂ and R ₁₀ may be bonded to each other;
a and Rb are a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, n is an integer of 1 to 4, m is an integer of 1 or 2, p is 0 or 1, s is 0, 1 or 2 , T represents 1 or 2, and M represents a metal). 2. The metal used in the formula (1) is Pd, A
The organometallic compound for forming an electron-emitting device according to claim 1, wherein the compound is selected from the group consisting of g, Ru, Cu, Cr, Fe, Pb, Zn, and Sn. 3. In the formula (1), R ₂ , R ₃ , R ₉ ,
Electron-emitting devices formed organometallic compound of claim 1 in which R ₁₀ is characterized in that it is a hydrogen atom. 4. In the formula (1), R ₃ and R ₉ or R ₂ and R ₁₀ are bonded, and [(R ₂ ) (R ₃ ) N—R
_{4 - {N (R 5)} -R 6 -} pN (R 7) -R 8 -N
The organic metal compound for forming an electron-emitting device according to claim 1, wherein (R ₉ ) (R ₁₀ )] is a cyclic compound. 5. The electron-emitting device according to claim 1, wherein said 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. 6. A step of applying a droplet of a conductive film forming solution between opposing electrodes on a substrate, a step of heating and firing the droplet to form a conductive film, and a step of forming a conductive film in the conductive film. Forming an electron emitting portion on the substrate, wherein the solution containing the organometallic compound according to any one of claims 1 to 5 is used as the conductive film forming solution. A method for manufacturing an electron-emitting device. 7. The method according to claim 6, wherein the method of applying the droplet is an ink-jet method. 8. The method according to claim 7, wherein the inkjet method is a piezo jet method. 9. The method according to claim 7, wherein the inkjet method is a bubble jet method. 10. The electron according to claim 6, wherein the droplets are continuously applied to form the applied droplets in a linear or planar shape. A method for manufacturing an emission element. 11. The method according to claim 6, wherein the electron-emitting device is a surface conduction electron-emitting device. 12. An electron source comprising an electron-emitting device and a means for applying a voltage to the device, a fluorescent film for receiving and emitting electrons emitted from the device, and applying the signal to the device using an external signal. An image forming apparatus comprising: a driving circuit for controlling a voltage; wherein the element includes an electron emitting portion formed using the organometallic compound according to any one of claims 1 to 5. Characteristic image forming apparatus. 13. The image forming apparatus according to claim 12, wherein the electron-emitting device is a surface conduction electron-emitting device.