JPH06231678A - Manufacture of electron emitting film and electron emitting element - Google Patents

Abstract

PURPOSE:To make the thickness and the shape of an electron emitting film uniform, and thereby enhance both electron emitting efficiency and characteristics by holding an organic metallic film at temperature equal to or more than the melting teperature + or -10 deg.C of the organic metallic film, but less than decompression temperature for a specified period of time, desirably equal to or more than one minute. CONSTITUTION:At the time when temperature is raised up to Tb equal to or more than the decompression temperature of an organic metal at the time of heattreatment, the temperature is kept at one equal to or more than the melting temperature + or -10 deg.C of the organic metal, and at the temperature of Ta which is less than the decompression temperature of the organic metal for a definite period of time. This constitution thereby allows the organic metal formed over a substrate to be uniformly developed over the substrate so as to be made uniform, and subsequently when the developed metal is heattreated at the temperature of Tb which is equal to or more than the decpmpression temperature of the organic metal, the organic metal is transformed into particulates so as to be two dimensionally formed into the condition of one layer over the substrate. This constitution thereby enables the film thickness and the shape of an electron emitting film (particulate film) to be uniform, and also enables the grain size of each particulate and a space between the particulates to be controlled in an area suitable for electrons to be emitted. Therefore, the electron emitting film and electron emitting elements which are excellent in electron emitting efficiency and electron emitting characteristics, can thereby be provided stably with excellent reproducibility kept.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electron emitting film and an electron emitting element used as an electron source for an electron beam generator, an image forming apparatus and the like.

[0002]

2. Description of the Related Art Conventionally, as a device which can emit electrons with a simple structure, for example, MI Elinson (M.
I. A cold cathode device announced by Elinson et al. Is known [Radio Engineering Electron Physics (Radio Eng.
ron Phys. ) Volume 10, 1290-1296
P. 1965]. This utilizes a phenomenon in which an electron is emitted by flowing a current in parallel to a thin film having a small area formed on a substrate, and is generally called a surface conduction electron-emitting device. As the surface conduction electron-emitting device, the SnO ₂ (S
b) Using thin film, using Au thin film [Gee Ditmer: "Sin Solid Films" (G. Di
ttmer: "Thin Solid Films")
Volume 9, p. 317, 1972], by ITO thin film [M Hartwell and CG Fon, M. Hartwellland CG Fon]
stad: "IEEE Trans.ED Con
f. ") Page 519, 1975], etc. are reported.

FIG. 24 shows a typical device configuration of these surface conduction electron-emitting devices. In the figure, 2 and 3 are electrodes for obtaining electrical connection, 5 is a thin film formed of an electron emitting material, 1 is a substrate, and 4 is an electron emitting portion. Conventionally, in these surface conduction electron-emitting devices, an electron-emitting portion is formed in advance by an energization heating process called forming before the electron emission. That is, by applying a voltage between the electrodes 2 and 3, the thin film 5 is energized, and the thin film 5 is locally destroyed, deformed or altered by the Joule heat generated thereby, and the electrical resistance is high. An electron emission function is obtained by forming the electron emission portion 4 in the state.
Incidentally, the electrically high resistance state means that a part of the thin film 5 has a resistance of 0.
It refers to a discontinuous state film having a crack with a length of 5 μm to 5 μm and having a so-called island structure inside the crack. The island structure generally refers to a film in which fine particles having a diameter of several tens of angstroms to several microns are present on the substrate 1, and each fine particle is spatially discontinuous and electrically continuous. Conventionally, a surface conduction electron-emitting device is one in which electrons are emitted from the above-mentioned fine particles by applying a voltage to the above-mentioned high resistance discontinuous film by means of electrodes 2 and 3 and causing a current to flow on the device surface.

The inventors of the present invention have also disclosed in Japanese Patent Laid-Open No. 2005-2005.
No. 32 and JP-A-2-56822,
A technology of a surface conduction type emission device in which fine particles for emitting electrons are dispersedly arranged between electrodes has been disclosed. This electron-emitting device is
(1) High electron emission efficiency can be obtained. (2) Since the structure is simple, manufacturing is easy. (3) A large number of elements can be arrayed and formed on the same substrate. It is an element having advantages such as. FIG. 25 shows a typical device configuration of these surface conduction electron-emitting devices. In FIG. 25, 2 and 3 are electrodes for obtaining electrical connection, 6 is an electron emitting portion in which fine particles for emitting electrons are dispersed, and 1 is a substrate.

The electrical characteristics (current-voltage characteristics) of the conventional surface conduction electron-emitting device described above will be described with reference to FIG. 26. In the conventional electron-emitting device, emitted electrons have a constant device voltage (device). The applied voltage V.sub.e can be rapidly increased, and at the element voltage Vd, for example, an electron beam sufficient for forming an image in the image forming apparatus can be emitted. Also,
The element current (current flowing in the element) If increases as the element voltage rises, and the rate of increase increases from around the element voltage Ve. Generally, in these conventional devices, a current irrelevant to electron emission, that is, a large reactive current shown in the figure flows, but the ratio of the reactive current to the device current If is:
It may reach up to 50%. Such an increase in the reactive current causes an increase in power consumption when the electron-emitting device is driven and a deterioration in electron emission characteristics (electron emission efficiency, stability of emitted electrons, etc.) due to heat generation of the electron-emitting device. In addition, the increase of the reactive current also causes the following problems. That is, when an electron-emitting device having a large reactive current is used for an electron source such as an image forming apparatus, (1). Since the reactive current flows in the wiring current and a voltage drop occurs, the amount of electron emission varies depending on the electron-emitting device. (2). Since the reactive current changes depending on the type of image formed (that is, the difference in the input information signal), the voltage drop at the wiring electrode changes, and the amount of electrons emitted from the element also changes.

The above problems result in deterioration of the contrast and sharpness of the formed image, and particularly when the formed image is a fluorescent image, the brightness of the fluorescent image varies and the brightness changes, resulting in high image forming apparatus. It becomes difficult to make the screen finer and the screen larger, and it also leads to an increase in power consumption.

In view of the above problems, the inventors of the present invention have proposed in Japanese Patent Application No. 4-268714 excellent electron emission characteristics such as electron emission efficiency and stability of emitted electrons, and have extremely low power consumption and reactive current. The present invention has disclosed a novel electron-emitting device having excellent contrast and sharpness of a formed image when used as an electron source of an image forming apparatus.

The electron-emitting device will be described in detail below. First, the main characteristic portion of this electron-emitting device will be described with reference to FIG. 27 (plan view), FIG. 28 (AA ′ cross-sectional view of FIG. 27) and FIG. 29 (BB ′ cross-sectional view of FIG. 28). To do. In these figures, 1 is an insulating substrate, 2 and 3 are electrodes, 5 is an electron emission region, 4 is a fine particle film having a resistance lower than that of the electron emission region 5, and 6 is fine particles dispersed in the electron emission region 5. Show. In such an electron-emitting device, first, the electron-emitting region 5 in which the fine particles 6 are dispersed and the electrodes 2 and 3 for applying a voltage to the inside of the region 5 are essential constituent elements. That is, in the electron-emitting device, electrons (current) flow in the electron-emitting region 5 by the voltage applied between the electrodes 2 and 3, and the electrons are formed by the fine particles 6 inside the region (gap between fine particles). It is an element having a mechanism of being released to the outside of the region by. The low resistance fine particle film 4 is arranged for the purpose of further improving the electrical contact between the electron emission region 5 and the electrodes 2 and 3. In addition, a conductive material is used for both the fine particles forming the electron emission region 5 and the fine particle film 4.

Further, the above electron-emitting device has the following two modes in addition to the above essential constituent elements.

First, in the first mode, the area occupancy of the fine particles 6 in the electron emission region 5 is 20% to 75%.
Is within the range of. 30 and 31 are SEM (scanning electron microscope) photographs of the electron-emitting device described above, and FIG. 30 is a plan view of the area AA ′ in FIG. 28 observed from above. 31 is a plan view of the BB ′ region of FIG. 29 observed from above, and the dotted line region of FIG. 31 is an enlarged view of the electron emission region 5 observed by SEM at a higher magnification. Equivalent to. The area occupancy of the fine particles means a value measured as follows. First, FIG.
As shown by the dotted line region, a SEM image (or STM (scanning tunneling microscope) image may be used) of the inside of the electron emission region 5 of the device is taken at a magnification such that 10 to 1000 fine particles can be observed. From the SEM image, the ratio of the area of all the fine particles to the total area is measured. This measurement is performed over the entire area of the electron emission area 5, the average value of the obtained measurement values is calculated, and this is taken as the area occupancy of the fine particles.

In the electron-emitting device described above, the relationship between the area occupancy ratio of the particles and the above-mentioned reactive current, and further the relationship with the electron-emitting characteristics are considered as follows. That is, when the area occupancy of the fine particles is too large, the ratio of the gap (gap between the fine particles) to the entire electron emission region becomes too small, and therefore the electron emission region exhibits a property as a continuous film. As the amount of electrons flowing through the film increases, the amount of emitted electrons also decreases, which eventually increases the reactive current of the device. On the other hand, if the area occupied by the fine particles is too small, the ratio of the gap becomes too large, so that the applied voltage for electron emission becomes large, so that the phenomenon that once emitted electrons are pulled back to the electrode occurs. Also in this case, it is considered that the reactive current of the device also becomes large and the amount of emitted electrons also becomes small.

Further, in the first aspect, the average particle size of the fine particles dispersedly arranged in the electron emission region is 5Å to 3
It is preferably set in the range of 00Å, particularly preferably in the range of 5Å to 80Å. That is, by setting it in the above range, it is possible to prevent the reactive current flowing through the particles themselves having an extremely large particle diameter, further reduce the reactive current of the entire device, and further improve the electron emission efficiency. Also, the stability of the emitted electrons (in particular, the fluctuation of the emitted electrons) can be further reduced.

Next, in the second mode, the fine particle spacing of the fine particles 6 in the electron emission region 5 is in the range of 5Å to 100Å. The fine particle spacing means the gap width between the fine particles as shown by S in FIG. 29, and is a value measured as follows. First, as shown by the dotted line area in FIG. 31, an SEM image (or STM (scanning tunneling microscope) image may be used) of the inside of the electron emission region 5 of the device shows that the number of fine particles is 10
This SEM is taken at a magnification that allows observation of 1 to 1000 pieces
From the image, measure all particle spacing. This measurement is performed over the entire area of the electron emission region 5, the average value of the obtained measurement values is calculated, and this is set as the above-mentioned fine particle interval.

In the above-mentioned electron-emitting device, the relationship between the particle spacing and the above-mentioned reactive current and the relationship with the electron-emitting characteristic are considered as follows, as in the first aspect. That is,
If the spacing between the fine particles is too small, the ratio of the gap (the gap between the fine particles) to the entire electron emitting region becomes too small, so that the electron emitting region has a property as a continuous film. On the other hand, if the distance between the fine particles is too large, the ratio of the gap becomes too large, and the applied voltage for electron emission increases, so that the once-emitted electron is pulled back to the electrode.

Further, also in the second aspect, for the same reason as in the first aspect, the average particle size of the fine particles dispersedly arranged in the electron emission region is set in the range of 5Å to 300Å. It is preferable, and particularly preferable that the range from 5Å to
It is desirable to set it in the range of 80Å.

Further, in the above-mentioned Japanese Patent Application No. 4-268714, the heat treatment of the organometallic compound is carried out in order to obtain the area occupancy rate of fine particles in the electron emission region or the fine particle spacing and the fine particle diameter. There is.

[0017]

As described above, in the surface conduction electron-emitting device in which the film made of the fine particles serving as the electron-emitting material is formed in the electron-emitting region, the area occupancy of the fine particles in the electron-emitting region is occupied. It is possible to improve the electron emission efficiency and the electron emission characteristics by controlling the rate, the interval between the fine particles, and the particle size of the fine particles. However, stable control is always performed in the conventional heat treatment method of the organometallic compound. It doesn't mean that.

Therefore, an object of the present invention is to improve the uniformity (film thickness, particle diameter, etc.) and reproducibility of an electron emission film made of fine particles, and to control the film resistance of the electron emission film. To provide a method for producing an electron-emitting device, which is used as an electron source for an electron beam generator, an image forming apparatus, and the like, and which has excellent electron emission efficiency and electron emission characteristics, with good reproducibility. It is in.

[0019]

The present invention, which has been made to achieve the above object, provides a method for producing an electron emission film by heat-treating an organometallic film formed on a substrate. When the temperature is raised to a temperature Tb which is equal to or higher than the decomposition temperature of the organic metal, a temperature Ta which is equal to or higher than the melting point of the organic metal ± 10 ° C. and lower than the decomposition temperature of the organic metal is maintained for a certain period of time. A method for producing an electron-emitting device by heat-treating an organometallic film formed between electrodes on a substrate, which is the above-mentioned method for producing an electron-emitting film. Is used to fabricate an electron-emitting device.

As a method for producing an electron emission film made of fine particles as described above, there are a vacuum vapor deposition method by differential evacuation, a thermal decomposition method of an organic metal film and the like, but a fine particle film having a uniform and uniform particle size is used. The latter method is preferable for obtaining the same, and the latter method is also used in the present invention.

The organometallic film according to the present invention is prepared by dissolving and dispersing an organometallic complex in, for example, an organic solvent or an organic binder,
After controlling the content of the organometallic complex in the solution, it can be formed on the substrate by a spinner method, a dipping method, a spray method or the like. In addition, if the amount of the organometallic complex formed on the substrate can be controlled, the solvent can be directly used without using the solvent.
It may be formed on the substrate.

By controlling the amount of the above-mentioned organometallic complex formed, the particle size of the fine particles in the electron emission film produced in the heat treatment described later can be controlled to some extent.

The organic metal film thus formed is heat-treated to produce an electron emission film (fine particle film) made of fine particles to be an electron emission material. According to the research conducted by the present inventors, Shape of fine particle film (thickness, fine particle diameter, etc.)
Turned out to be very important to.

That is, in the present invention, when the temperature is raised to the temperature Tb which is higher than the decomposition temperature of the organic metal during the heat treatment, it is constant at the temperature Ta which is higher than the melting point of the organic metal ± 10 ° C. and lower than the decomposition temperature of the organic metal. Hold for a period. As a result, the organic metal formed on the substrate is uniformly spread on the substrate and becomes uniform. Then, when heat treatment is performed at a temperature Tb that is equal to or higher than the decomposition temperature of the organic metal, the organic metal is formed into fine particles and is formed on the substrate. It is formed two-dimensionally in a single layer. The minimum required time for the temperature holding period at the temperature Ta is slightly different depending on the amount of the organic metal material and the amount formed on the substrate, but it is preferably 1 minute or more, and if it is less than 1 minute, Also, depending on the amount of formation, it may not be possible to sufficiently spread it evenly on the substrate, and the film thickness (number of layers, particle size, etc.) of the fine particle film formed thereafter may become uneven.

Further, according to the research conducted by the present inventors, the fact that the temperature Tb is 20 ° C. to 100 ° C. higher than the decomposition temperature of the organic metal further improves the uniformity of fine particle gaps and the fine particle thickness. It was found to be important for homogenization.

If the temperature Tb is less than the above range, efficient forming cannot be performed, and if the temperature Tb exceeds the above range, the particle diameter of the fine particles becomes nonuniform, and in any case, formation of a fine particle film having an extremely uniform shape is excluded. To do.

Further, in order to form a fine particle film having a uniform shape, it is preferable to maintain the temperature Tb at a constant level for 1 minute or more, and furthermore, the rate of temperature increase up to the temperature Ta is 1.
It is preferable that the temperature is not less than ° C / min, and that the rate of temperature rise up to the temperature Ta is not less than the rate of temperature rise from the temperature Ta to the temperature Tb.

Examples of the electron emission film formed by the heat treatment process as described above include a film formed of conductive fine particles, a carbon thin film in which these conductive fine particles are dispersed, and the like. Among them, Pd, Nb, Mo, Rh, Hf, Ta, W, Re, and
Ir, Pt, Ti, Au, Ag, Cu, Cr, Al, C
Metals such as o, Ni, Fe, Pb, Cs and Ba, LaB
Boride such as ₆ , CeB ₆ , HfB ₄ , GdB ₄ , etc., Ti
Carbides such as C, ZrC, HfC, TaC, SiC and WC, nitrides such as TiN, ZrN and HfN, PdO and Ir
₂ O ₃ , SnO ₂ , Sb ₂ O _{3 and} other metal oxides, Si,
Semiconductors such as Ge, carbon, AgMg, NiCr, Pb
Sn and the like. The sheet resistance of the electron emission film is 1 × 1.
It is preferably in the range of 0 ³ Ω / □ to 1 × 10 ¹⁰ Ω / □.

Since the structure of the electron-emitting device according to the present invention is basically the same as that shown in FIGS. 27 to 29, a specific example of the manufacturing method will be described with reference to these drawings.

First, the electrodes 2 and 3 are formed on the insulating substrate 1 made of a quartz substrate or the like. At this time, the electrode interval (G in FIG. 27) is preferably in the range of 0.2 μm to 5 μm.

As the insulating substrate 1, besides a quartz substrate, a glass substrate such as a blue plate and a white plate, Al ₂ O ₃ , SiO ₂ , S, etc.
Any material may be used as long as it has an insulating property, such as an insulating film made of iN or the like, an insulating film made of SiO _x or SnO _x by vacuum film formation, or the like.

Next, a solvent in which the above-mentioned organometallic complex is dissolved is applied between the electrodes, and the heat treatment according to the method for producing the electron emission film of the present invention is performed to form the fine particle film 4 made of the electron emission material. .

The fine particle film 4 thus formed is two-dimensionally formed in a single layer on the substrate 1. The fine particle film formed as described above can be easily identified by an analysis method such as a scanning electron microscope. Further, the particle size of the fine particles forming the fine particle film can be controlled by the amount of the organometallic complex formed on the substrate before the heat treatment. Further, the variation in the particle size of the fine particles can be controlled by controlling the temperature raising process in the heat treatment step described above.

By using the method for producing an electron-emitting film of the present invention, the particle diameter of the fine particles in the electron-emitting film is 5Å to 500.
Within the range of Å and the variation of the average particle size can be easily controlled within the range of ± 20%.

When the particle diameter of the fine particles is in the range of 5Å to 500Å, the fine particle film 4 is formed in the electron emitting portion (region) 5 when the electron emitting portion (region) 5 is formed by conducting the electric current treatment described later. The particle size of the fine particles and the interval between the particles act so that the particle size and the interval suitable for electron emission are formed. Furthermore, the variation in the average particle size of the particles of the particle film 4 is ± 20.
Within the range of%, when the fine particle film 4 is energized and the electron emitting portion (region) 5 is formed, the electron emitting portion (region) 5 is formed.
It acts so as to reduce variations in the particle size of the fine particles formed inside and the intervals between the fine particles.

In the energization process, by applying a voltage between the electrodes 2 and 3, the electron emission portion (region) 5 is formed on the fine particle film 4.
Is formed. The method of energization treatment is to form the electron-emitting portion (region) 5 by electrically heating the fine particle film 4 containing an electron-emitting material to partially increase its resistance.
By energizing the fine particle film 4 containing the electron emitting material,
Some of them have a low resistance to form the electron emitting portion (region) 5, but any of them may be used.

The voltage waveform applied between the electrodes 2 and 3 during the energization process is appropriately set depending on the shape of the electrode, the material of the fine particle film, and the material of the substrate.

The above-mentioned energization treatment causes the fine particle film 4 to undergo a structural change to form an electron emitting portion (region). The fine particle film formed by the method for producing an electron emitting film of the present invention is Since it is two-dimensionally formed in a single layer on the surface of the substrate, the power consumption during energization processing is extremely small and the variation in energization processing voltage is extremely small. Discharge part (area)
Since the width is uniform and the power consumption is small, the amount of heat generated during energization processing is extremely small and is not affected by heat, so that there is no thermal destruction of the substrate and no deterioration of the electron emitting portion.

As described above, according to the method of manufacturing the electron-emitting device of the present invention, the width of the electron-emitting portion (region) formed by the energization process, the particle size of the fine particles in the electron-emitting portion (region), The space is suitable for electron emission, and the particle size is
Since the intervals are formed uniformly, it is possible to provide an electron-emitting device having excellent electron emission efficiency and uniform electron emission characteristics.

When the electron-emitting device obtained by the present invention is applied to an electron beam generator and an electron source of an image forming apparatus,
Since there is no variation in the electron emission portion (region) between the elements, it is possible to obtain not only an electron beam generator having uniform electron emission characteristics, but also to form an image with little unevenness in brightness and flickering in display during image formation. be able to.

In the present invention, in the case of heat-treating an organometallic complex to form an electron emission film, the fine particle film is most preferably made of a metal or a compound of metal. If the composition (particle size, variation in particle size, etc.) can be formed, the same effect can be obtained even if the fine particles made of the electron-emitting material are dispersed and dissolved in the organometallic complex.

Further, by controlling the atmosphere during the heat treatment of the organometallic complex, it is possible to arbitrarily produce fine particles made of materials such as metals, metal oxides and metal nitrides.

Further, in the present invention, in order to improve the adhesion between the fine particle film and the substrate, an insulating layer such as low softening point glass is formed on the substrate, and then an organometallic film is formed thereon.
After that, the heat treatment according to the present invention is performed, and further the treatment is performed at a temperature equal to or higher than the softening point of the insulating layer, so that the fine particles can be partially embedded in the insulating layer. Accordingly, even if a large voltage required to obtain a sufficient electron emission amount is applied, it is possible to obtain an electron-emitting device in which the variation of the electron emission amount is extremely small and the device is not destroyed.

Specifically, if the insulating layer is, for example, a lead oxide-based low softening point glass, it is heated to 450 ° C. and heated to about 2 ° C.
By performing the baking for about 0 minutes, the fine particles arranged on the low softening point glass penetrate into the low softening point glass, and are completely buried or at least partially buried therein. Due to the so-called anchor effect, it is fixed to the substrate and the adhesion is greatly improved.

Whether the fine particles are completely buried in the insulating layer or only a part thereof is buried can be adjusted by setting the firing temperature. That is, as the firing temperature is higher, the fine particles are more likely to penetrate deeper into the insulating layer and be embedded therein. On the other hand, as the firing temperature is lower, the fine particles are less likely to enter the insulating layer, and the remaining portion is filled with the exposed portion.

In this case, at least a part of the fine particles on the outermost surface of the insulating layer must be exposed, but completely buried fine particles may be present in the lower layer.

The depth of the deepest part of the fine particles embedded in the insulating layer is preferably 0.2 to 3 times, more preferably 0.5 to 1.5 times the particle diameter of the fine particles. Is desirable. This is because, if the fine particles are present deeper in the insulating layer beyond this range, a very large current will flow during the current-carrying process when the electron-emitting portion is formed by the current-carrying process because the thickness of the fine particles is large. This is because heat is generated, and the electron emitting portion is deteriorated due to the destruction of the substrate.
On the contrary, when the depth is shallower, the so-called anchor effect is not recognized, and the adhesiveness is not significantly improved.

Further, after the fine particles are completely buried in the insulating layer, etching treatment may be performed to expose a part of the fine particles on the surface of the insulating layer.

[0049]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples.

Example 1 In this example, the heat treatment of the organic metal film according to the present invention is performed as shown in FIG.
The temperature profile shown in FIG.
~ An electron-emitting device having the structure shown in Fig. 29 was produced.

The manufacturing process in this embodiment will be described with reference to FIGS. A quartz substrate is used as the insulative base 21, and after thoroughly cleaning it with an organic solvent, the electrode 2 is formed on the surface of the base 21.
2 and 23 were formed (see FIG. 2A). Au metal was used as the material of the electrodes. The electrode interval G was 2 μm, the length of the electrodes (in the depth direction of the paper surface) was 500 μm, and the thickness thereof was 1000 Å. Organic palladium complex (melting point: 100
℃, decomposition temperature: 220 ℃ butyl acetate solution (Pd1w
After containing t%) by spinner coating, heat treatment was performed in air according to the temperature profile shown in FIG. 1 to form a fine particle film 24 made of palladium oxide fine particles (average particle size 60Å). Here, the length of the fine particle film 24 (the depth direction of the paper surface) is set to 3
The thickness was set to 00 μm, and the electrodes 22 and 23 were arranged substantially in the center (see FIG. 2B). Next, a voltage was applied between the electrode 22 and the electrode 23 to energize the fine particle film 24 (forming process) to form the electron emission region 25 (see FIG. 2C).
FIG. 3 shows the voltage waveform of the forming process.

In FIG. 3, T ₁ and T ₂ are the pulse width and pulse interval of the voltage waveform. In this embodiment, T ₁ is 1.0 ms and T ₂ is 10 ms. The forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ torr.

When the electron emission region 25 thus formed was observed by a scanning electron microscope, palladium fine particles having an average particle diameter of 30Å were formed between the fine particle films 24 made of palladium oxide fine particles.

In the above process, 500 similar devices were manufactured, and the electron emission characteristics were measured by using the evaluation apparatus shown in FIG.

In FIG. 4, 31 is a power supply for applying a voltage to the element, 30 is an ammeter for measuring the element current If, 34 is an anode electrode for measuring the emission current Ie generated from the element, 33 Is a high voltage power supply for applying a voltage to the anode electrode 34, and 32 is an ammeter for measuring the emission current. Here, the element current is the amount of current measured by the ammeter 30, and the emission current is the amount of current measured by the ammeter 32.
To measure the device current and the emission current of the electron-emitting device, a power supply 31 and an ammeter 30 are connected to the device electrodes 22 and 23, and a power supply 33 and an ammeter 32 are provided above the electron-emitting device.
Arrange the anode electrode 34 connected to and vacuum degree 1 × 1
It is performed in an environment of 0 ^-7 torr.

In this embodiment, the element voltage (Vf) = 14
Device current (If), emission current (Ie), and electron emission efficiency (η) of each device under V, anode voltage (Va) = 2 kV
= Ie / If) frequency distribution was measured. The result is shown in Fig. 5.
Shown in. 5A is a frequency distribution of the device current,
FIG. 5B shows the frequency distribution of the emission current, and FIG. 5C shows the frequency distribution of the electron emission efficiency.

Comparative Example 1 In Example 1, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 electron-emitting devices were manufactured in exactly the same manner except that the temperature profile shown in 1 was used, and the electron-emitting characteristics were measured in the same manner as in Example 1. The result is shown in FIG. 7. As is clear from a comparison between FIG. 7 and FIG. 5 of the measurement results of Example 1, it is understood that by maintaining the melting point temperature of the organopalladium complex for a certain period during the heat treatment, it is possible to reduce variations in electron emission characteristics between devices. To be done.

Further, in many experiments conducted by the inventors, regardless of the material of the organic metal or the amount of the organic metal formed on the substrate, if the temperature holding period is 1 minute or more, a substantially uniform element is obtained. The characteristics were obtained.

Comparative Example 2 In Example 1, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 electron-emitting devices were manufactured in exactly the same manner except that the temperature profile shown in 1 was used, and the electron-emitting characteristics were measured in the same manner as in Example 1. The result is shown in FIG.

As is clear from the comparison between FIG. 9 and FIG. 5 showing the measurement results of Example 1, the higher the rate of temperature increase from room temperature to the melting point of the organopalladium complex during heat treatment, the better the uniformity of the device. It is understood that it works even more effectively.

In many experiments conducted by the present inventors, the melting point of the organic metal is ± 10 ° C. regardless of the material of the organic metal.
At a temperature of 1 ° C./min or more to a temperature Ta which is equal to or higher than the temperature of the organic metal and lower than the decomposition temperature of the organic metal, and more preferably from the temperature Ta to a temperature Tb higher than the decomposition temperature of the organic metal. If the heating rate is higher than the heating rate, more uniform device characteristics can be obtained.

Example 2 The electron-emitting device of this example was manufactured by the following method. A pair of electrodes was prepared on the insulating substrate in the same manner as in Example 1. In the same manner as in Example 1, a butyl acetate solution of an organopalladium complex was applied onto the substrate by spinner, and then heat treatment was performed in a reducing atmosphere (a mixed gas of hydrogen gas and N ₂ gas) using the temperature profile shown in FIG. Was carried out to form a fine particle film made of fine metal palladium particles (average particle size 30Å). The sheet resistance of the fine particle film was 3 × 10 ³ Ω / □. An electron-emitting device of this example was produced by subjecting the metal palladium fine particle film produced above to a forming process with a voltage waveform as shown in FIG.

When 500 similar devices were manufactured in the above process and evaluated in the same manner as in Example 1, the device current, emission current, and electron emission efficiency all had frequency distributions substantially equal to those in FIG.

Example 3 The electron-emitting device of this example was manufactured by the following method. A pair of electrodes was prepared on the insulating substrate in the same manner as in Example 1. In the same manner as in Example 1, a substrate was spin coated with a solution of an organopalladium complex in butyl acetate, and then N was placed in a vacuum chamber.
₂ gas was introduced at 4 × 10 ^-2 torr, and RF discharge was induced to generate nitrogen plasma. In the N ₂ plasma atmosphere, heat treatment was performed using the temperature profile shown in FIG. 1 to form a fine particle film made of palladium nitride fine particles. The sheet resistance of the fine particle film was 2 × 10 ⁵ Ω / □. An electron-emitting device of this example was manufactured by subjecting the above-prepared fine particle film to a forming process with a voltage waveform as shown in FIG.

In the above process, 500 similar devices were produced and evaluated in the same manner as in Example 1. The device current,
Both the emission current and the electron emission efficiency have almost the same frequency distribution as in FIG.

Example 4 The electron-emitting device of this example was manufactured by the following method (refer to FIG. 2 for manufacturing process). A pair of electrodes 22 and 23 were formed on the insulating substrate 21 in the same manner as in Example 1. Organic platinum complex (melting point: 190 ° C, decomposition temperature: 400
C.) butyl acetate solution was applied by a spinner and then heat-treated in air according to the temperature profile shown in FIG. 10 to form a fine particle film 24 of platinum fine particles (particle diameter 20Å to 100Å). Here, the length of the fine particle film 24 (the depth direction of the paper surface)
Was set to be 300 μm, and the electrodes 22 and 23 were arranged substantially in the center. Next, a voltage was applied between the electrode 22 and the electrode 23, and the fine particle film 24 was subjected to a forming treatment to form the electron emission region 25.

The forming process is about 1 × 10 ^-6 torr
In a vacuum atmosphere of, a DC voltage of 10 V was continuously applied.

When 500 similar devices were manufactured in the above process and evaluated in the same manner as in Example 1 under a vacuum of 1 × 10 ⁻⁷ torr, the results shown in FIG. 11 were obtained. . Incidentally, FIG. 11A shows the frequency distribution of the device current,
1 (b) shows the frequency distribution of the emission current, and FIG. 11 (c) shows the frequency distribution of the electron emission efficiency.

From the above results, each element of this example has almost uniform element characteristics.

Example 5 The electron-emitting device of this example was produced by the following method (see FIG. 2 for production steps). A pair of electrodes 22 and 23 were formed on the insulating substrate 21 in the same manner as in Example 1. A solution of an organic ruthenium complex (melting point: about 310 ° C., decomposition temperature: about 420 ° C.) in butyl acetate was applied by spinner, and then heat-treated in air according to the temperature profile shown in FIG. 12, ruthenium fine particles (particle size 20Å to 100Å) A fine particle film 24 of was formed. 1 × 10 ⁻⁶ torr on the fine particle film 24 produced above
An electron-emitting device was manufactured by performing a forming process by continuously applying a DC voltage of 10 V in a vacuum atmosphere of r.

In the above process, 500 similar devices were produced, and the same evaluation as in Example 4 was carried out.
Both the emission current and the electron emission efficiency have almost the same frequency distribution as in FIG.

Example 6 In this example, the uniformity of the electron emission film (fine particle film) produced according to the present invention was evaluated.

A method of manufacturing the fine particle film in this embodiment will be described with reference to the manufacturing process chart of FIG. A quartz substrate is used as the insulative substrate 131, and the quartz substrate is thoroughly washed with an organic solvent.
It was vapor-deposited with a thickness of Å (see FIG. 13 (a)). After that, a 200 μ × 300 μ pattern is formed with a positive resist, the Cr is wet-etched, and then the resist is peeled off.
A chrome mask 132 ′ having a hole of 0 μ × 300 μm was formed. After spin coating a butyl acetate solution of an organic palladium complex on the base 131, heat treatment was performed in air according to the temperature profile shown in FIG. This operation was repeated twice to form a fine particle film 133 made of fine palladium oxide particles (see FIG. 13C). Then, Cr was etched out to form patterned palladium oxide fine particles 133 ′.

The thickness of the patterned palladium oxide fine particle film thus produced was measured by a stylus type film thickness meter α-step 25.
When measured with 0 (manufactured by TENCOR), the result is as shown in FIG. In FIG. 14, those having a value of d of 20 Å or more are referred to as “waviness”, and the number of “waviness” in a 40 μm scan is measured for 500 patterned palladium oxide fine particle films produced in the same manner as in the above production method. Measure
The frequency is shown in FIG.

Comparative Example 3 In Example 6, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 patterned palladium oxide fine particle films were prepared in exactly the same manner except that the temperature profile shown in FIG. 5 was used, and the frequency of “waviness” per 40 μm scan was measured in the same manner as in Example 6.

The results are shown in FIG. 15 (b).

Comparative Example 4 In Example 6, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 patterned palladium oxide fine particle films were prepared in exactly the same manner except that the temperature profile shown in FIG. 5 was used, and the frequency of “waviness” per 40 μm scan was measured in the same manner as in Example 6.

The results are shown in FIG. 15 (c).

As is clear from the results of Example 6 and Comparative Examples 3 and 4, the fine particle film produced according to the present invention has excellent smoothness and is formed to have a substantially uniform film thickness. Sex is retained.

Example 7 In the manufacturing method of Examples 2 to 5, the fine particle film made of a metal or a metal compound was patterned in the same manner as in Example 6 to prepare 500 patterned fine particle films, and the same as in Example 6. When the frequency of “waviness” per 40 μm was measured, the same uniformity as in Example 6 was obtained.

Example 8 The fine particle film of this example was produced by the following method. A chrome mask was formed on the insulating substrate in the same manner as in Example 6. A butyl acetate solution of an organic palladium complex was applied onto the substrate by a spinner, and then heat treatment was performed in the air according to the temperature profile shown in FIG. In this embodiment, the above operations are
By carrying out four times, four kinds of fine particle films were formed, and then Cr was etched out to obtain a patterned palladium oxide fine particle film.

When the four types of patterned palladium oxide fine particle films thus produced were observed by SEM and STM, each fine particle film was a single layer, but the film thickness was as shown in FIG. became. From FIG.
It was confirmed that the particle size of the fine particles can be increased and the particle size can be controlled by repeating the application of the organic palladium complex and the heat treatment.

Embodiment 9 FIG. 17 shows a plan view and a cross-sectional view of the electron-emitting device of this embodiment before the energization process is performed, and FIG. 18 is a plan view after the energization process and a cross-sectional view thereof. 17 and 18, 171 is an insulating substrate, 172 and 173 are electrodes, 174 is a fine particle film, and 175 is an electron emitting portion (region). The electron-emitting device of this example was manufactured as follows. A quartz substrate was used as the insulating base 171 and was sufficiently washed with an organic solvent or the like, and electrodes 172 and 173 were formed by a vacuum deposition technique and a photolithography technique. Any material may be used as the material of the electrodes as long as it has conductivity, but in the present embodiment, nickel (N
i) Formed using a metal. The electrode interval was 2 μm, the electrode length was 300 μm, and the film thickness was 1000 Å. Next, the organic ruthenium complex was added to a solvent of n-butyl acetate to prepare 1
Use a solution that is dispersed and dissolved at a ratio of 0 wt% and use a tape on a place where the organic ruthenium complex solution is not desired to be applied.
Alternatively, a resist film is provided and then coated on the insulating base 171 by a spinner method. Next, the tape or the resist film is peeled off to form an organic ruthenium film at a predetermined position. Next, as shown in the temperature profile shown in FIG. 12, since the melting point of the organic ruthenium complex is about 310 ° C. and the decomposition temperature is about 420 ° C., the temperature from the melting point to the decomposition temperature or lower and the holding time are 350 ° C.-30 min. Ruthenium (Ru) fine particles (particle size 60Å to 80
Å, average particle size 70 Å, average particle size variation ± 14%) was formed. Next, a voltage is applied between the electrodes 172 and 173 to energize the fine particle film 174, and an electron emitting portion (region) 175 is applied.
The width of the electron emitting portion (region) 175 was about 0.1 μm, the particle diameter of the fine particles formed in the electron emitting portion (region) 175 was 30 Å to 40 Å, and the space between the fine particles was 5 Å to 20.
Formed by Å. Next, when a voltage of 14 V was applied between the electrodes 172 and 173 of the electron-emitting device under a vacuum of 1 × 10 ⁻⁵ torr, good electron-emitting characteristics were confirmed in a plurality of devices, and further, The variation of the electron-emitting devices among the devices was very small.

As described above, in the electron-emitting device of this embodiment manufactured according to the present invention, the particles in the electron-emitting film (particle film) are controlled to have a particle size and interval suitable for electron emission. Since the variation in the average particle size is small, the variation in the energization processing voltage is extremely small, the width of the electron emitting portion is uniform, excellent electron emission characteristics are obtained, and the characteristics are uniform among a plurality of elements. Become.

Example 10 The electron-emitting device of this example is different from that of Example 9 in that the fine particle film 174 was formed by using a solution in which an organic ruthenium complex was dispersed and dissolved in a solvent of n-butyl acetate at a ratio of 20 wt%. Was manufactured in the same manner as in Example 9.

The electron-emitting device of this embodiment has a fine particle film 174.
The particle size of the ruthenium (Ru) particles is 130Å-18
0Å (average particle size 155Å, average particle size variation ± 16
%), The width of the electron-emitting portion (region) 175 formed by the energization process is about 0.2 μm, and the electron-emitting portion (region) 17 is about 0.2 μm.
The fine particles formed in No. 5 had a particle size of 60 Å to 90 Å and an interval of the fine particles of 5 Å to 30 Å. When the electron-emitting device of this example was made to emit electrons in the same manner as in Example 9, good results were obtained as in Example 9.

Comparative Example 5 In Example 9, the fine particle film was formed by the gas deposition method, and the particle diameter of ruthenium (Ru) fine particles was 30Å to 300Å.
An electron-emitting device was produced in the same manner as in Example 9 except that a plurality of layers were formed in the range of (average particle size 165Å, average particle size variation ± 80%).

FIG. 19 shows a sectional view of the electron-emitting device manufactured in this comparative example.

In this device, the width of the electron emission portion (region) varies from about 0.1 μm to about 0.25 μm due to the energization process, and the particle diameter of the fine particles formed in the electron emission portion (region) is 10 Å to 160 Å. The fine particles were formed with an interval of 5Å to 60Å.

When electrons were emitted from this device in the same manner as in Example 9, although emission of electrons was obtained, good characteristics could not be obtained.

As described above, it is understood that a good electron emission film (fine particle film) cannot be obtained even if the heat treatment according to the present invention is performed without using the organometallic film.

Example 11 A palladium oxide fine particle film was prepared by using an organic palladium complex as the electron emission film (fine particle film) of this example.
The manufacturing procedure will be described below. Reflux a mixture of acetic acid, nitric acid and palladium black until all of the nitric acid is consumed. Thereafter, the reaction palladium was removed by filtration, acetic acid was distilled off under reduced pressure, and the residue was recrystallized from dichloromethane-hexane to give red fine crystals [Pd
(OAc) ₂ ] ₆ H ₂ O was obtained. The decomposition temperature measured by DTA was 235 ° C. The microcrystals obtained in 1. were dissolved in n-butyl acetate to prepare an organopalladium solution having a Pd content of about 10 g / l. After spin-coating the solution of (1) on an insulating substrate, it was heat-treated in air according to the temperature profile shown in FIG. 1 to form a fine particle film composed of palladium oxide fine particles (average particle size 60 Å).

FIG. 20 is a schematic view of an SEM (scanning electron microscope) photograph of a cross section of the PdO fine particle film produced by the above-described production procedure.

In the figure, 201 is a quartz substrate which is an insulating substrate, and 202 is PdO fine particles. Pd
Judging from FIG. 20, the particle size of O fine particles is 50Å ~
It was 70Å.

The thickness and shape of the fine particle film produced in this example was measured by a stylus type film thickness meter α-step 250 (TENCOR).
21), the results shown in FIG. 21 were obtained. In the figure, the scan width of 25 μm or later indicates the fine particle film portion. The sheet resistance of the fine particle film by the four-terminal method was 5.0 × 10 ⁴ Ω / □.

Example 12 In Example 11, the heat treatment in air was carried out by changing the holding temperature above the decomposition temperature (235 ° C.) of organopalladium to 300 ° C. in the temperature profile shown in FIG.
A fine particle film was produced in the same manner as in Example 11 except that the operation was performed at 0 ° C.

When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, it was almost the same as in Example 11.

The sheet resistance of the fine particle film is 5.8 × 1.
It was 0 ⁴ Ω / □.

Example 13 In Example 11, except that during the heat treatment in air, the temperature profile shown in FIG. 1 was followed by a heat treatment at 300 ° C. and then standing in air at 330 ° C. for 20 minutes. A fine particle film was prepared in the same manner as in Example 11.

When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, it was almost the same as in Example 11.

The sheet resistance of the fine particle film is 3.4 × 1.
It was 0 ⁴ Ω / □.

Comparative Example 6 In Example 11, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature of the organopalladium (220 ° C.) or higher to 300 ° C.
A fine particle film was produced in the same manner as in Example 11 except that the operation was performed at 0 ° C.

When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, the results shown in FIG. 22 were obtained. In the same figure, the scan width of 37 μm or later indicates the fine particle film portion.

The sheet resistance of the fine particle film is 9.5 × 1.
It was 0 ⁴ Ω / □.

From the results of Examples 11 to 13 and Comparative Example 6,
It can be seen that in the heat treatment of the organopalladium, the temperature during the decomposition treatment above the decomposition temperature greatly affects the uniformity of the fine particle film formed thereby.

Example 14 The fine particle film of this example was prepared by the following method. Synthesized in Example 11 [Pd (OAc)
The mother liquor of ₂ ] ₆ H ₂ O was concentrated to obtain fine yellow needle-like crystals [Pd (OAc) ₂ ] ₃ .CH ₂ Cl ₂ . DTA
The decomposition temperature was measured to be 205 ° C. The microcrystals obtained in 1. were treated in the same manner as in Example 11 to prepare an organic palladium solution. After coating the above-mentioned organopalladium solution on the substrate by the same method as in Example 11, heat treatment was performed in the air in the temperature profile shown in FIG. 1 to form a fine particle film.

The film thickness and shape of the fine particle film produced by the above-described production procedure were as shown in FIG. 21, almost the same as in Example 11, and the sheet resistance was 5.4 × 10 ⁴ Ω / □. .

The results of the same heat treatment as in Example 12 after applying the above organic palladium were also the same.

Comparative Example 7 In Example 14, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature (205 ° C.) or higher of the organopalladium to 300 ° C.
A fine particle film was produced in the same manner as in Example 14 except that the operation was performed at 0 ° C.

When the thickness and shape of the fine particle film thus produced were measured, the results shown in FIG. 22 were obtained as in Comparative Example 6.

The sheet resistance of the fine particle film is 4 × 10 ^5.
It was Ω / □.

Example 15 The fine particle film of this example was prepared by the following method. A commercially available organic palladium-n-butyl acetate solution (CCP-4230 manufactured by Okuno Chemical Industries Co., Ltd.) was spinner-coated on the insulating substrate. The decomposition temperature of the organic palladium solution is about 230 ° C. The above substrate was heat-treated in air according to the temperature profile shown in FIG. 1 to form a fine particle film.

The film thickness and shape of the fine particle film produced by the above-mentioned production procedure were as shown in FIG. 21, almost the same as in Example 11, and the sheet resistance was 5.0 to 6.0 × 10 ⁴ Ω.
The range was / □.

[0114] Further, the results of the same heat treatment as in Example 12 after applying the above organic palladium were the same.

Comparative Example 8 In Example 15, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature of the organopalladium (about 230 ° C.) or higher to 300 ° C.
A fine particle film was prepared in the same manner as in Example 15 except that the operation was carried out at 00 ° C.

When the thickness and shape of the fine particle film thus produced were measured, the results shown in FIG. 22 were obtained as in Comparative Example 6.

The sheet resistance of the fine particle film is 3 × 10 ^5.
It was Ω / □.

In addition to Examples 11 to 15 and Comparative Examples 6 to 8, according to many experiments conducted by the present inventors, the temperature at the time of the above decomposition treatment was 20 ° C. higher than the decomposition temperature of the organic metal. 1
It has been found that a higher temperature of 00 ° C. is very favorable for the uniformity of the particulate film.

Example 16 In this example, the adhesion between the fine particle film of the present invention and the substrate was improved.

FIG. 23 is a plan view of the electron-emitting device of this example.
It is shown in (a) and the AA 'cross section figure was shown in FIG.23 (b). In the figure, 231 is a soda lime glass substrate, 232 is a lead oxide-based low softening point glass coating film,
233 and 234 are electrodes, and 235 is a fine particle film. The electron-emitting device of this example was manufactured as follows. Insulating layer 232 on soda lime glass substrate 231
As a lead oxide-based low softening point glass film, a film having a thickness of about 30 μm was formed by coating.

Further, electrodes 233, 23 are formed on the insulating layer 232.
4 was formed. In addition, Ni metal was used as the material of the electrode. The electrode interval (G in FIG. 23 (a)) was 4 μm, and the film thickness was 1000 Å. Next, after applying organopalladium (CCP-4230 manufactured by Okuno Chemical Industries Co., Ltd.) at a desired position by a spinner method, heat treatment is performed in the air in the temperature profile shown in FIG. 1 to obtain palladium oxide (PdO). ) A fine particle film 235 made of fine particles (average particle size 60Å) was formed. Subsequently, when the fine particles 237 were embedded in the surface of the insulating layer 232 by performing atmospheric baking at 450 ° C. for 20 minutes,
As shown in FIG. 23B, a part of the fine particles 237 was exposed on the surface and the rest was buried. After that, when an energization process, that is, a forming process by applying a voltage between the electrodes 233 and 234 was performed, an electron emitting portion 236 was formed as shown in FIG. 23C.

In the device thus produced, the adhesion between the fine particles and the substrate was extremely improved, and a sufficient electron emission amount was obtained between the electrodes 233 and 234 under a vacuum of 1 × 10 ⁻³ Pa. It was confirmed that when the voltage for obtaining was applied, the variation amount of the electrons emitted from the electron emitting portion 236 was extremely small.

As a method of forming the film made of low softening point glass to be the insulating layer 232, a printing baking method, a vacuum deposition method or the like can be used in addition to the liquid coating baking method.

Further, as the low softening point glass material, it is preferable that the softening point temperature thereof is lower than the strain point temperature of the material of the substrate 231, and the thermal expansion coefficient thereof is close to that of the substrate.
Generally, a lead oxide-based low softening point glass has a softening point of around 400 ° C. and a thermal expansion coefficient similar to that of a commonly used soda lime glass substrate.

[0125]

As explained above, according to the present invention, the substrate is kept at the temperature Ta which is equal to or higher than the melting point of the organometallic film ± 10 ° C. and lower than the decomposition temperature for a certain period, preferably 1 minute or more. Spread the organic metal evenly on top, then
Decomposition temperature or higher, preferably 20 ° C to 10 ° C higher than decomposition temperature
By performing the heat treatment at a temperature Tb higher by 0 ° C., the film thickness and shape of the electron emission film (fine particle film) can be made uniform, and the particle size and particle interval of the particles can be controlled to a region suitable for electron emission, resulting in electron emission efficiency. Further, it is possible to stably provide an electron emitting film and an electron emitting device having excellent electron emitting characteristics with good reproducibility.

Further, the temperature rising rate up to the temperature Ta is 1 ° C.
/ Minute or more, and more preferably, by setting the temperature rising rate to be the temperature rising rate from the temperature Ta to the temperature Tb or more, more uniform element characteristics can be obtained.

When the electron-emitting device obtained by the present invention is applied to an electron beam generator and an electron source of an image forming apparatus,
Since there is no variation in the electron emission portion (region) between the elements, it is possible to obtain not only an electron beam generator having uniform electron emission characteristics, but also to form an image with little unevenness in brightness and flickering in display during image formation. be able to.

[Brief description of drawings]

FIG. 1 is an example of a temperature profile used for heat treatment of an organometallic film according to the present invention.

FIG. 2 is an example of a manufacturing process diagram of an electron-emitting device according to the present invention.

FIG. 3 is a voltage pulse waveform diagram used in the forming process in the example.

FIG. 4 is a schematic configuration diagram of an apparatus used for measuring an electron emission characteristic of an electron emitting element in an example.

FIG. 5 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in Examples.

FIG. 6 is a temperature profile used for heat treatment of an organic metal film in a comparative example.

FIG. 7 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in a comparative example.

FIG. 8 is a temperature profile used for heat treatment of an organic metal film in a comparative example.

FIG. 9 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in a comparative example.

FIG. 10 is an example of a temperature profile used for heat treatment of the organometallic film according to the present invention.

FIG. 11 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in Examples.

FIG. 12 is an example of a temperature profile used for heat treatment of the organometallic film according to the present invention.

FIG. 13 is a manufacturing process diagram when a patterned palladium oxide fine particle film is manufactured in an example.

FIG. 14 is a view showing the results of measuring the shape of the patterned palladium oxide fine particle film produced in the example with a stylus type film thickness meter.

FIG. 15 is a diagram showing the uniformity (frequency of waviness) of patterned palladium oxide fine particle films produced in Examples and Comparative Examples.

16 is a diagram showing the relationship between the particle size and the number of times of coating and baking of the particle film produced in Example 8. FIG.

17A and 17B are a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 9.

FIG. 18 is a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 9.

FIG. 19 is a plan view and a cross-sectional view of an electron-emitting device manufactured in Comparative example 5.

FIG. 20 is an SE of a cross section of the fine particle film produced in Example 11.
It is a schematic diagram of M image.

FIG. 21 is a diagram showing the results of measuring the shape of the fine particle film produced in the example with a stylus type film thickness meter.

FIG. 22 is a diagram showing a result of measuring the shape of a fine particle film produced in Comparative Example by a stylus type film thickness meter.

23A and 23B are a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 16.

FIG. 24 is a schematic configuration diagram (plan view) showing an electron-emitting device of a conventional example.

FIG. 25 is a schematic configuration diagram (plan view) showing a conventional electron-emitting device.

FIG. 26 is a diagram showing current-voltage characteristics of a conventional electron-emitting device.

FIG. 27 is a schematic configuration diagram (plan view) of an electron-emitting device.

28 is a cross-sectional view taken along the line A-A ′ in FIG. 27.

29 is a cross-sectional view taken along the line B-B ′ of FIG. 28.

FIG. 30 is a copy (plan view) of an electron micrograph of an electron-emitting device.

31 is a copy (plan view) of an enlarged electron micrograph of an electron emission region of the electron emission device of FIG. 30. FIG.

[Explanation of symbols]

 21 Insulating Substrate 22,23 Electrode 24 Fine Particle Film 25 Electron Emitting Region 30 Ammeter 31 Power Supply 32 Ammeter 33 Power Supply 34 Anode Electrode 131 Insulating Substrate 132 Chromium 132 'Chromium Mask 133 Palladium Oxide Fine Particles 171 Insulating Substrate 172,173 Electrodes 174 Fine Particle Film 175 Electron Emitting Region 201 Insulating Substrate 202 PdO Fine Particle 231 Soda Lime Glass Substrate 232 Lead Oxide Low Softening Point Glass 233, 234 Electrode 235 Fine Particle Film 236 Electron Emitting Region 237 Fine Particle 1 Substrate 2, 3 Electrode 4 Electron Emitting Part 5 Thin film 6 Fine particles

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichi Kawate 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuhiro Michi 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Ichiro Nomura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (8)

[Claims] 1. A method for producing an electron emission film by heat-treating an organometallic film formed on a substrate, wherein when the temperature is raised to a temperature Tb higher than the decomposition temperature of the organometallic during the heat treatment, the melting point of the organometallic film. A method for producing an electron-emitting film, which is characterized by holding at a temperature Ta which is equal to or higher than ± 10 ° C. and lower than a decomposition temperature of an organic metal for a certain period. 2. The method for producing an electron emission film according to claim 1, wherein the temperature holding period at the temperature Ta is 1 minute or more. 3. The temperature Tb is 2 above the decomposition temperature.
The method for producing an electron-emitting film according to claim 1 or 2, wherein the temperature is higher by 0 ° C to 100 ° C. 4. The method for producing an electron emission film according to claim 1, wherein the temperature Tb is maintained for a certain period of time. 5. The method for producing an electron emission film according to claim 4, wherein the temperature holding period at the temperature Tb is 1 minute or more. 6. The temperature rising rate up to the temperature Ta is 1 ° C. /
It is more than a minute, The manufacturing method of the electron emission film in any one of Claims 1-5 characterized by the above-mentioned. 7. The electron emission film according to claim 1, wherein the temperature rising rate up to the temperature Ta is equal to or higher than the temperature rising rate from the temperature Ta to the temperature Tb. Method. 8. A method for producing an electron-emitting device by heat-treating an organometallic film formed between electrodes on a substrate, wherein the method for producing an electron-emitting film according to claim 1. A method for manufacturing an electron-emitting device, characterized by using.