JP2003109507A - Manufacturing method of electron emitting element and manufacturing method of electron source - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an electron emitting element that is capable of stabilizing the electron emission characteristics of the electron emitting element by reducing the preparatory drive current If-pre flowing in the electron emitting element at the time of carrying out the preparatory drive process for stabilizing the electron emission characteristics, and a manufacturing method of an electron source. SOLUTION: The manufacturing method comprises a preparatory pre-drive process for impressing a preparatory pre-drive voltage Vpre' having a voltage wave peak value which is lower than the voltage wave peak value Vpre of the preparatory drive voltage that is impressed at the time of preparatory drive process, before the preparatory drive process is impressed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electron-emitting device and a method for manufacturing an electron source.

[0002]

2. Description of the Related Art Conventionally, the electron-emitting devices of this type are roughly classified into a thermoelectron-emitting device and a cold cathode electron-emitting device.
Kinds of things are known. A field emission type (hereinafter referred to as "FE type"), metal / insulating layer /
There are a metal type (hereinafter referred to as “MIM type”) and a surface conduction type electron-emitting device type. As an example of the FE type, W. P. Dyk
e & W. W. Dolan, “Field Emiss
Ion ", Advance in Electron
Physics, 8, 89 (1956), C.I. A. Sp
indt, “PHYSICAL Properties”
of thin-film field emiss
ion cathodes with mollybde
nium cones ”, J. Appl. Phys.,
47, 5248 (1976) and the like are known.

An example of the MIM type is C.I. A. Mead,
"Operation of Tunnel-Emis
sion Devices ", J. Apply. Phy
s. , 32,646 (1961) and the like are known. As an example of the surface conduction electron-emitting device,
M. I. Elinson, Radio Eng. Ele
ctron Phys. , 10, 1290, (196
5) etc. have been disclosed.

The surface conduction electron-emitting device utilizes a phenomenon that electron emission occurs in a small-area thin film formed on a substrate by passing an electric current in parallel with the film surface. As this surface conduction electron-emitting device, one using the SnO ₂ thin film by Erinson et al. [M. I. Elinso
n, Radio Eng. Electron Phy
s. , 10, 1290, (1965)], by an Au thin film [G. Dittmer, “Thin Soli
d Films ", 9, 317 (1972)], I
n ₂ O ₃ / SnO ₂ thin film [M. Hartwel
and C. G. F onstad, “IEEE
Trans. ED Conf. ", 519 (1975)
], A carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1, Item 22 (1983)], etc. have been reported.

The above-mentioned FE-type, MIM-type, surface-conduction-type electron-emitting devices have the advantage that a large number of devices can be arrayed and formed on a substrate, and various image display devices applying these have been proposed.

A surface conduction electron-emitting device that emits electrons from an electron-emitting portion formed in a conductive thin film by passing a current through a small-area conductive thin film formed on a substrate in parallel with the film surface. Has a simple structure and is easy to manufacture, so that a large number of elements can be formed over a large area,
For example, application to image display devices has been studied.

Examples of applying the surface conduction electron-emitting device to an image evaluation apparatus include the methods disclosed in USP 5,066,883 and JP-A-6-342636. In these publications, a surface conduction electron-emitting device including a pair of device electrodes provided on a substrate, a conductive film connected to the device electrode pairs, and an electron-emitting portion formed in the conductive film is disclosed. A means for forming an image in accordance with an input signal and a manufacturing method are described, in which a plurality of elements are arranged in a dimensional manner and an electric selection means is provided to individually select the emitted electrons emitted from each electron-emitting device. ing.

Further, in Japanese Patent Laid-Open No. 7-235255, by applying a voltage to a surface conduction electron-emitting device in the presence of an organic substance, a deposit containing carbon as a main component is formed near the electron-emitting portion, A method for improving the electron emission characteristics of the surface conduction electron-emitting device is disclosed.

Further, in Japanese Patent Laid-Open No. 7-235275, the electron emission characteristics are measured by means such as setting the residual partial pressure of organic matter in the environment in which the electron emission portion is formed to 1.3 × 10 ⁻⁶ Pa or less. Techniques for stabilizing are disclosed.

Further, in Japanese Unexamined Patent Publication No. 9-259753, in each of the two-dimensionally arranged surface conduction electron-emitting devices, the partial pressure of the organic gas is 1.3 × 10 ⁻⁶ or less in an atmosphere. Then, by applying a voltage pulse higher than the voltage obtained by adding in advance the maximum value of the normal drive voltage and the noise voltage that can enter the surface conduction electron-emitting device, the temperature characteristics and the disturbance of the drive circuit during normal drive are applied. There is disclosed a method of suppressing the irreversible instability characteristic of the emission current generated by the above and reducing the uneven brightness.

The image evaluation apparatus using the surface conduction electron-emitting device produced by applying the above-mentioned method is expected to have better characteristics than the image evaluation apparatuses of other conventional methods.
For example, even compared to the liquid crystal display devices that have become popular in recent years,
Since it is a self-luminous type, it does not require a backlight and has a wide viewing angle.

As described above, since the surface conduction electron-emitting device has a simple structure and is easy to manufacture and has excellent electron emission characteristics, an image forming apparatus using a phosphor as an image forming member, for example, The electron-emitting device is suitable for forming a large self-luminous flat display.

Further, various analyzers utilizing an electron source,
It is also expected to be applied to processing equipment. As described above, in consideration of application to the image forming apparatus, it is required for the electron-emitting device to stably emit the expected electron beam amount.

Further, in order to provide a highly reliable image forming apparatus, analysis apparatus, etc., it is required to impart more stable electron emission characteristics to the conventional electron emitting element.

For example, Japanese Unexamined Patent Publication No. 2000-243223 discloses pre-driving for stabilizing the electron emission characteristics of a device by applying a voltage pulse having a peak value to the electron emitting device.

[0016]

However, in the case of the above-mentioned conventional technique, the following problems may occur.

When each device resistance was measured after performing the activation process in the manufacturing process of the electron-emitting device, the device resistance of the electron-emitting device, which was about several MΩ after the forming process for forming the electron-emitting portion, was 1 / In the state where the electron-emitting device is reduced to about 1000 or less, and the resistance of the electron-emitting device is lowered, applying the pre-driving voltage Vpre when performing the pre-driving process greatly reduces the resistance of the electron-emitting device. Since such a pre-driving current If-pre flows, the electron-emitting device may be damaged or adversely affected, and the electron-emitting characteristic may be significantly deteriorated.

Further, when a large current flows through the plurality of electron-emitting devices formed on the glass substrate, a large amount of heat is generated, which may cause cracks or cracks in the glass substrate.

The present invention has been made in order to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a preliminary flow to an electron-emitting device at the time of performing a pre-driving process for stabilizing the electron emission characteristics. An object of the present invention is to provide a method of manufacturing an electron-emitting device and a method of manufacturing an electron source, which can reduce the drive current If-pre and stabilize the electron-emitting characteristics of the electron-emitting device.

[0020]

In order to achieve the above object, according to the present invention, a preparatory step for stabilizing the electron emission characteristic by applying a voltage peak value higher than the voltage peak value applied during normal driving is provided. A method of manufacturing an electron-emitting device having a driving step, characterized by further comprising a preliminary pre-driving step of applying a voltage peak value lower than a voltage peak value at the time of the preliminary driving step before performing the preliminary driving step. To do.

It is also preferable that the voltage peak value during the pre-preliminary driving applied in the pre-preliminary driving step is lower than the voltage peak value applied during the normal driving.

A pair of element electrodes facing each other on the substrate, and a conductive thin film for electrically connecting the element electrodes,
It is also preferable that the method is a method of manufacturing a surface conduction electron-emitting device having an electron-emitting portion provided in the conductive thin film.

The voltage peak value during the pre-preliminary driving applied in the pre-preliminary driving step is such that the voltage is applied only to one of the pair of device electrodes and not to the other device electrode. It is also preferable that the voltage peak value is a voltage difference due to the potential difference when the voltage is set to 0V.

The voltage peak value during the pre-preliminary driving applied in the pre-preliminary driving step is such that a positive voltage pulse is applied to one of the pair of device electrodes,
It is also preferable that the other element electrode has a voltage peak value formed by a potential difference caused by applying a negative voltage pulse.

On the substrate, there are a step of forming the pair of opposing device electrodes, and a step of forming the conductive thin film containing carbon or a carbon compound for connecting the pair of device electrodes. It is also preferable to perform the pre-preliminary drive step after these steps.

A step of forming the pair of element electrodes facing each other on the substrate, and the conductive thin film connecting the pair of element electrodes, and a forming step of forming the electron emitting portion on the conductive thin film. And, after the forming step, an activation step of forming carbon or a carbon compound in the electron emission portion, and a stabilization step of removing those organic substances after the activation step, and after these steps, It is also preferable to perform the pre-preliminary driving step.

It is also preferable that the electron emitting device is a cold cathode electron emitting device having carbon or a carbon compound in the electron emitting portion.

Manufacture of an electron source having a pre-driving step in which a plurality of electron-emitting devices are arranged on a substrate and a voltage peak value higher than a voltage peak value applied during normal driving is applied to stabilize electron emission characteristics. The method is characterized by including a preliminary pre-driving step of applying a voltage peak value lower than the voltage peak value at the time of the preliminary driving step before performing the preliminary driving step.

It is also preferable that the voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is lower than the voltage peak value applied during normal driving.

The electron-emitting device includes a pair of device electrodes facing each other on the substrate, a conductive thin film for electrically connecting the device electrodes, and an electron-emitting portion provided in the conductive thin film. It is also preferable that it is a surface conduction electron-emitting device having the same.

Regarding the voltage peak value during the pre-preliminary driving applied in the pre-preliminary driving step, the voltage is applied only to one of the pair of device electrodes and not to the other device electrode. It is also preferable that the voltage peak value is a voltage difference due to the potential difference when the voltage is set to 0V.

The voltage peak value at the time of pre-preliminary driving applied in the pre-preliminary driving step is such that a positive voltage pulse is applied to one of the pair of element electrodes,
It is also preferable that the other element electrode has a voltage peak value formed by a potential difference caused by applying a negative voltage pulse.

On the substrate, there are steps of forming the pair of device electrodes facing each other, and forming the conductive thin film containing carbon or a carbon compound for connecting the pair of device electrodes. It is also preferable to perform the pre-preliminary drive step after these steps.

A step of forming the pair of element electrodes facing each other on the substrate and the conductive thin film connecting the pair of element electrodes, and a forming step of forming the electron emitting portion on the conductive thin film. And, after the forming step, an activation step of forming carbon or a carbon compound in the electron emission portion, and a stabilization step of removing those organic substances after the activation step, and after these steps, It is also preferable to perform the pre-preliminary driving step.

It is also preferable that the plurality of electron-emitting devices are matrix-wired.

It is also preferable that the voltage peak value applied in the pre-driving step is sequentially applied to the plurality of electron-emitting devices by scroll driving.

It is also preferable to perform the preliminary drive step in advance for all of the plurality of electron-emitting devices before performing the preliminary drive step, and then perform the preliminary drive step.

As a result, even when the resistance of the electron-emitting device is extremely small, it is possible to increase the resistance of the electron-emitting device without damaging or adversely affecting the device.

Therefore, it is possible to suppress damage to the electron-emitting device and breakage of the glass substrate during the pre-driving process for stabilizing the electron-emitting characteristics, and to manufacture an electron-emitting device with a stable emission current for a long period of time. Can be done.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be illustratively described in detail below with reference to the drawings. However, the dimensions of the components described in this embodiment,
The material, the shape, and the relative arrangement of them should be appropriately changed depending on the configuration of the device to which the invention is applied and various conditions, and the scope of the invention is not limited to the following embodiments.

FIG. 1 is a diagram showing voltage peak values applied during pre-pre-driving, pre-driving, and normal driving in the method of manufacturing an electron-emitting device (method of manufacturing an electron source) according to the embodiment of the present invention. FIG. 7 is a schematic configuration diagram showing an image display device using the electron source of the simple matrix arrangement manufactured by the method of manufacturing the electron source according to the present embodiment.

As shown in FIG. 7, Ag is deposited on the glass substrate 1.
Wirings formed by the above are arranged in a matrix form as Y wirings 6 in the Y direction and X wirings 7 in the X direction. Y wiring 6,
Element electrodes 2 and 3 made of Pt or the like are formed on the X wiring 7 so as to form a pair, and a conductive thin film 4 is formed to connect between the element electrodes. The glass substrate 1 having the Y wirings 6, the X wirings 7, the element electrodes 2 and 3 and the conductive thin film 4 arranged in a matrix on the glass substrate 1 is hereinafter referred to as a rear plate 10.

Further, the rear plate 10 of the glass substrate 1 having the conductive thin film 4 is a metal back 8 made of Ti or the like, a face plate 11 having a phosphor 9 for displaying an image and a frit 12 by heat treatment. Etc.
A hole is formed in either the rear plate 10 or the face plate 11, and a glass tube 13 for evacuation is used.
, And the glass tube 13 is connected to an evacuation device, so that the inside of the image display device can be evacuated.
The conductive thin film 4 formed in the image display device in the vacuum state as described above is subjected to the following steps.

First, an electron emission portion, which is indispensable for causing electron emission in the above-mentioned conductive thin film, is formed by a forming process.

That is, while the conductive thin film is installed in a vacuum container such as a vacuum exhaust device, a slow leak valve such as a variable leak valve is used while applying a desired forming voltage pulse to each conductive thin film. Hydrogen is introduced into the vacuum pump.

As a result, cracks are formed in the conductive thin film, which serve as electron-emitting portions, which are sites where the structure is locally destroyed, deformed, or altered. In the forming process, the forming voltage can be changed by the resistance between the device electrodes via the conductive thin film.

After the forming process is completed, an activation process is carried out in which carbon or a carbon compound is deposited on the electron emitting portion formed in the conductive thin film.

The activation step is performed in an organic gas atmosphere.
Carbon or a carbon compound can be deposited on the electron-emitting portion by applying a desired activation voltage to the electron-emitting device having the electron-emitting portion formed by the forming process. The activation voltage can be changed similarly to the forming voltage, and the pressure of the organic gas during activation is 1.3 × 10 ^{−4 to} 1.4 × 10 ⁻⁴ P.
About a is preferable, but it is not limited to this and can be changed as necessary.

After the activation process is completed, it is necessary to perform the stabilization process as a means for removing the organic gas and organic substances on the vacuum exhaust device and the electron-emitting device.

As a treatment method of the stabilizing step, the vacuum exhaust can be performed while heating the vacuum exhaust device and the electron-emitting device while continuing the vacuum exhaust. The residual amount of the organic gas and the organic substance is preferably 1.0 × 10 ⁻⁶ Pa or less, and it is possible to reduce the amount of carbon and the carbon compound deposited on the electron emitting portion when the heating is completed and the temperature is room temperature. it can.

After the stabilization process, the element resistance is measured, and when the resistance is smaller than a desired resistance value, pre-pre-driving, which is a feature of this embodiment, is performed.

In the pre-pre-driving step, the voltage is lower than the voltage peak value of the pre-driving voltage Vpre at the time of pre-driving performed next, and
A voltage peak value smaller than the voltage peak value of the drive voltage Vdrv during normal driving is applied to the electron-emitting device.

The voltage peak value as described above is used as the pre-preliminary drive voltage Vpre 'and sequentially applied to each line of the Y wiring 6, and the flowing current value is measured. The pre-preliminary drive voltage applied at this time is a pulse voltage, which is shown in FIG. Period 16.7msec, pulse width 100μs
ec ~ 1 msec, total time of pulse application is 1 msec
Although the above is preferable, the present invention is not limited to this and can be changed as necessary.

By performing the pre-preliminary driving on the electron-emitting devices whose resistance has been lowered in advance before the pre-driving, the resistance of each electron-emitting device is increased, and the electron-emitting devices along the Y wiring are combined. The resistance can also be in a high resistance state.

For this reason, it is possible to reduce the damage due to the damage of the electron-emitting device due to the large amount of the pre-driving current If-pre during the pre-driving, the damage and the breakage of the glass substrate due to the heat generation, and the pre-driving process and driving. A suitable electron-emitting device can be provided.

After the pre-preliminary driving process is completed, the pre-driving process is performed in order to stabilize the electron emission characteristics of the electron-emitting device.

In the pre-driving, the peak value larger than the voltage peak value during the normal driving is set as the pre-driving voltage Vpre and sequentially applied to each line of the Y wiring 6 as in the pre-pre-driving. The pre-driving voltage applied at this time is a pulse voltage having a period of 16.7 msec and a pulse width of 100 μm to 1 ms.
ec, total time of pulse application is 500 μsec to 60 s
ec is preferred. However, the present invention is not limited to this and can be changed as necessary.

Preliminary driving makes it possible to stabilize the electron emission characteristics of the electron-emitting device due to the "memory characteristic" of the surface conduction electron-emitting device.

The "memory characteristic" means that the electric characteristic curve of the surface conduction electron-emitting device (the relation between the emission current and the driving voltage, and the relation between the device current and the driving voltage) is larger than the maximum value of the applied voltage that has been experienced so far. Is newly changed, the characteristic shifts to a different characteristic, and thereafter, the characteristic is maintained until a larger driving voltage is experienced. The memory characteristic is a characteristic remarkably observed in the surface conduction electron-emitting device that has been subjected to the stabilization treatment described above. Due to this "memory characteristic", the electron emission characteristics of the electron emission element to which the pre-driving voltage Vpre, which is the maximum voltage, is applied are stabilized, and the element current If and the emission current Ie can be obtained.

After the completion of the pre-driving, the driving apparatus applies a driving voltage Vdrv to the electron-emitting device while applying a high voltage of about 100 V to 10 kV to the face plate to emit the electron from each surface-conduction electron-emitting device. The emission current Ie elastically scatters and comes into contact with the phosphor on the face plate side to display an image.

The structure of the surface conduction electron-emitting device manufactured by the method for manufacturing the electron-emitting device according to the present embodiment will be described below, and thereafter, the electron emission including the pre-pre-driving step according to the present embodiment will be described. A method for manufacturing the device will be specifically described.

<Structure and manufacturing method of surface conduction electron-emitting device>
The surface conduction electron-emitting device according to the present embodiment will be described with reference to FIG. The basic structure of the surface conduction electron-emitting device to which this embodiment can be applied is roughly classified into two types: a plane type and a vertical type.

FIG. 2 is a schematic diagram showing the structure of a surface conduction electron-emitting device manufactured by the method for manufacturing an electron-emitting device according to the embodiment of the present invention. FIG. The top view which shows the structure of an element, (b) is sectional drawing of (a), (c) has shown an example of a vertical type surface conduction electron-emitting device.

First, the planar surface conduction electron-emitting device will be described with reference to FIGS. 2 (a) and 2 (b).

In FIG. 2, 1 is a substrate, 2 and 3 are a pair of device electrodes provided on the substrate 1, 4 is a conductive thin film provided between the device electrodes 2 and 3, and 5 is a conductive thin film. The electron-emitting portion is formed on the.

The substrate 1 is made of quartz glass, Na or the like.
Glass with reduced net content, soda lime glass, soda
SiO formed on sponge method etc.
₂Laminated glass substrate and ceramics such as alumina
Also, a Si substrate or the like can be used. Opposite device power
Use common conductor materials for the poles 2 and 3.
You can This is, for example, Ni, Cr, Au, Mo,
Metals or alloys such as W, Pt, Ti, Al, Cu, Pd, etc.
And Pd, Ag, Au, RuO₂, Pd-Ag and other metals or
Is a printed conductor composed of metal oxide and glass, I
n₂O₃-SnO ₂Such as transparent conductors and polysilicon, etc.
It can be appropriately selected from semiconductor materials and the like.

The element electrode interval L, the element electrode length W, the shape of the conductive thin film 4 and the like are designed in consideration of the applied form. The element electrode spacing L can be preferably in the range of several hundred nm to several hundred μm, and more preferably several μm.
To several tens of μm. The device electrode length W is several μm in consideration of the electrode resistance value and electron emission characteristics.
To several hundreds of μm. Element electrode 2,
The film thickness d of 3 can be in the range of several tens nm to several μm. In addition to the structure shown in FIG. 2, the conductive thin film 4 and the opposing device electrodes 2 and 3 may be stacked in this order on the substrate 1.

As the conductive thin film 4, it is preferable to use a fine particle film composed of fine particles in order to obtain good electron emission characteristics.

The film thickness is appropriately set in consideration of the step coverage to the device electrodes 2 and 3, the resistance value between the device electrodes 2 and 3, and the forming conditions described later, but usually from several hundred pm. A range of several hundreds nm is preferable,
More preferably, the range is from 1 nm to 50 nm. The resistance value is such that Rs is 10 ² to 10 ⁷ Ω / □. Note that Rs is an amount that appears when the resistance R of a thin film having a thickness of t, a width of w and a length of 1 is R = Rs (l / w).

In the present embodiment, the forming process will be described by taking the energization process as an example.
The forming process is not limited to this, and includes a process of causing a crack in the film to form a high resistance state.

The materials forming the conductive thin film 4 are Pd and P.
t, Ru, Ag, Au, Ti, In, Cu, Cr, F
e, Zn, Sn, Ta, W, Pd and other metals, PdO, S
Oxides such as nO ₂ , In ₂ O ₃ , PbO and Sb ₂ O ₃ , Hf
_{B 2, ZrB 2, LaB 6} , CeB 6, YB 4, GdB borides such as _{4, TiC, ZrC, HfC,} Ta, C, SiC,
Carbides such as WC, nitrides such as TiN, ZrN, HfN,
It is appropriately selected from semiconductors such as Si and Ge and carbon.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and its fine structure has a state in which the fine particles are individually dispersed and arranged, or a state in which the fine particles are adjacent to each other or overlap each other (some fine particles are It also includes the case where they are aggregated to form an island structure as a whole). The particle size of the fine particles is in the range of several times 0.1 nm to several hundred nm, preferably in the range of 1 nm to 20 nm.

The electron-emitting portion 5 is composed of a crack having a high resistance formed in a part of the conductive thin film 4, and depends on the film thickness, film quality, material of the conductive thin film 4 and a method such as energization forming described later. It will be what you did.

In some cases, conductive fine particles having a particle size in the range of several times 0.1 nm to several tens nm are present inside the electron emitting portion 5. The conductive fine particles contain some or all of the elements of the material forming the conductive thin film 4. Electron emitting portion 5 and conductive thin film 4 in the vicinity thereof
It can also have carbon and carbon compounds.

Next, the vertical type surface conduction electron-emitting device will be described with reference to FIG.

FIG. 2C is a schematic diagram showing an example of a vertical surface conduction electron-emitting device according to this embodiment. In FIG. 2 (c), the same parts as those shown in FIG. 2 (a) and FIG. 2 (b) are assigned the same reference numerals as those shown in FIG. 2 (a) and FIG. 2 (b).

Reference numeral 21 is a step forming portion. The substrate 1, the device electrodes 2 and 3, the conductive thin film 4, and the electron emitting portion 5 can be made of the same materials as in the case of the planar surface conduction electron emitting device described above.

The step forming portion 21 is formed by a vacuum vapor deposition method, a printing method,
It can be made of an insulating material such as SiO ₂ formed by a sputtering method or the like. The film thickness of the step forming portion 21 corresponds to the device electrode interval L of the flat surface conduction electron-emitting device described above, and can be set in the range of several hundred nm to several tens μm. This film thickness is set in consideration of the manufacturing method of the step forming portion and the voltage applied between the element electrodes, but is preferably in the range of several tens nm to several μm.

The conductive thin film 4 is laminated on the device electrodes 2 and 3 after the device electrodes 2 and 3 and the step forming portion 21 are formed.

The electron emitting portion 5 is shown in FIG.
Although formed on the step forming portion 21, the shape and the position are not limited to this, depending on the forming conditions, the forming conditions, and the like.

There are various methods for manufacturing the above-mentioned surface conduction electron-emitting device, and one example thereof is schematically shown in FIG. Hereinafter, an example of a method of manufacturing the electron-emitting device according to the present embodiment will be described with reference to FIGS. 2 and 3. Also in FIG. 3, the same parts as those shown in FIG. 2 are designated by the same reference numerals as those shown in FIG.

(1) The substrate 1 is thoroughly washed with a detergent, pure water, an organic solvent, etc., and after the device electrode material is deposited by the vacuum deposition method, the sputtering method, etc., the substrate 1 is deposited on the substrate 1 by, for example, the photolithography technique. Element electrodes 2 and 3 are formed on the substrate (FIG. 3A).

(2) Next, an organic metal solution is applied to the substrate 1 provided with the device electrodes 2 and 3 to form an organic metal thin film. As the organic metal solution, a solution of an organic metal compound containing the metal of the material of the conductive film 4 described above as a main element can be used. The organometallic thin film is heated and baked, and the conductive thin film 4 is formed by patterning by, for example, a method of performing lift-off using a mask corresponding to the shape of the conductive thin film, etching, or the like (FIG. 3C).

Although the method of coating the organic metal solution has been described here, the method of forming the conductive thin film 4 is not limited to this, and the vacuum deposition method, the sputtering method, the chemical vapor deposition method, etc. Alternatively, a dispersion coating method, a dipping method, a spinner method, or the like can be used, and direct patterning can also be performed by an inkjet method or the like.

(3) Subsequently, a forming process is performed.
As an example of the method of this forming step, a method of energizing in a vacuum container will be described with reference to FIG.

In FIG. 4, reference numeral 55 denotes a vacuum container, which is evacuated through a gate valve 57 by a vacuum pump 56 including a turbo molecular pump, a sputter ion pump, a cryopump and the like. In addition, an auxiliary pump such as a scroll pump, a rotary pump, or a sorption pump may be provided as needed.

Reference numeral 58 is a container for containing the activated gas used in the activation process described below, and is connected to the vacuum container 55 through a control valve 59 composed of a slow leak valve such as a variable leak valve or a needle valve.

Voltage applying means is connected to the device electrodes 2 and 3. For example, as shown in FIG. 4, the element electrode 2 is connected to the ground potential, and the element electrode 3 is connected to the power supply 51 through the current introduction terminal. An ammeter 50 is provided to monitor the current value flowing between the element electrodes 2 and 3. 54
Is an anode electrode used in the subsequent process, and is connected to a high voltage power source 53 through an ammeter 52.

The forming is performed by evacuating the inside of the vacuum container 55 and energizing the element electrodes 2 and 3 with a power source 51. As a result, the electron emitting portion 5 having a changed structure is formed at the portion of the conductive thin film 4 (FIG. 3).
(C)). According to this energization forming, the conductive thin film 4
A site with a structural change such as local destruction, deformation or alteration is formed in the area.

FIG. 5 shows an example of a voltage waveform applied in energization forming.

As shown in the figure, the voltage waveform is preferably a pulse waveform. For this, the method shown in FIG. 5 (a) in which a pulse having a pulse peak value is a constant voltage is continuously applied, and the voltage pulse is applied while increasing the pulse peak value in FIG.
There is a method shown in (b).

T1 and T2 in FIG. 5A are the pulse width and pulse interval of the voltage waveform. Normally T1 is 1 μse
c to 10 msec, T2 is 10 μsec to 10 mse
It is set in the range of c. The peak value of the pulse 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 of minutes.
The pulse waveform is not limited to the rectangular wave, and a desired waveform such as a triangular wave can be adopted.

T1 and T2 in FIG. 5B are the same as those in FIG.
It can be similar to that shown in (a). The peak value of the pulse can be increased, for example, in steps of about 0.1V.

The end of the energization forming process can be judged by, for example, reading the change in the resistance value caused by the local destruction and deformation of the conductive thin film 4. As an example, during the pulse interval T2, a voltage that does not locally break or deform the conductive thin film 4 can be applied, and the current can be measured and detected. For example, the device current flowing by applying a voltage of about 0.1 V is measured, the resistance value is obtained, and when the resistance is 1 MΩ or more, the energization forming is terminated.

(4) It is preferable to perform a process called an activation process on the element which has completed the forming. The activation process includes the device current If and the emission current Ie.
Is a process that changes significantly.

The activation step can be performed, for example, by repeating the application of the pulse in the atmosphere containing the gas of the organic substance, similarly to the energization forming. As the pulse voltage, in addition to the voltage pulse shown in FIG.
A bipolar voltage pulse shown in can be used.

The atmosphere in the vacuum container during the activation step can be formed by using the organic gas remaining in the atmosphere when the vacuum container is evacuated by using, for example, an oil diffusion pump or a rotary pump. Alternatively, it can be obtained by introducing a gas of an appropriate organic substance into a vacuum that has been sufficiently evacuated by an ion pump or the like. The preferable gas pressure of the organic substance at this time is different depending on the form of application, the shape of the vacuum container, the type of the organic substance, and the like, and is appropriately set depending on the case.

Suitable organic substances include alkanes, alkenes, alkynes, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, phenols, carvone, sulfonic acid and other organic acids. And the like, and specifically, saturated hydrocarbons such as methane, ethane and propane, unsaturated hydrocarbons such as ethylene and propylene, butadiene, n-hexane, 1-hexene, benzene, toluene and O-xylene. , Benzonitrile, tolunitrile, chloroethylene, trichloroethylene, methanol, ethanol, isopropanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl amine, ethyl amine, acetic acid, propionic acid and the like or a mixture thereof can be used.

By the activation 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 termination of the activation process is appropriately determined while measuring the device current If and the emission current Ie. The pulse width,
The pulse interval, pulse peak value, etc. are set appropriately.

(5) It is preferable to perform a stabilization process on the electron-emitting device obtained through the above process.
This step is a step of exhausting the organic substance in the vacuum container.

The vacuum evacuation device for evacuating the vacuum container preferably uses no oil so that an organic substance such as oil generated from the device does not affect the characteristics of the element. Specifically, a magnetic levitation turbo molecular pump,
A vacuum exhaust device such as a cryopump, a sorption pump, or an ion pump can be used.

When an oil diffusion pump or a rotary pump is used as an exhaust device in the activation step and an organic gas derived from an oil component generated from the oil diffusion pump is used, the partial pressure of this component must be kept as low as possible. . The partial pressure of the organic component in the vacuum container is preferably 1 × 10 ⁻⁶ Pa or less, more preferably 1 × 10 ⁻⁸ Pa or less, in ^{terms of the} partial pressure at which the above carbon and carbon compound are not newly deposited. When exhausting the inside of the vacuum container further, heat the entire vacuum container,
It is preferable to easily exhaust the organic substance molecules adsorbed on the inner wall of the vacuum container or the electron-emitting device. The heating conditions at this time are 80 to 300 ° C., preferably 150 ° C. or higher, and it is desirable to perform the treatment for as long as possible, but it is not particularly limited to this condition, and the size and shape of the vacuum container,
It is carried out under conditions appropriately selected according to various conditions such as the structure of the electron-emitting device. It is necessary to make the pressure in the vacuum container as low as possible, preferably 1 × 10 ⁻⁵ Pa or less, and further 1
Particularly preferably, it is not more than × 10 ^-6 Pa.

It is preferable that the atmosphere at the time of driving after the stabilization process is maintained at the atmosphere at the end of the stabilization process, but it is not limited to this, and if the organic substance is sufficiently removed. Even if the pressure in the vacuum container is slightly increased, it is possible to maintain stable characteristics to some extent.

By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed,
Further, H ₂ O, O _2, etc. adsorbed on the vacuum container or the substrate can be removed, and as a result, the device current If and the emission current Ie are stabilized.

After carrying out the above-mentioned stabilization process, and before carrying out the pre-driving process for stabilizing the electron emission characteristics of the electron-emitting device, the pre-pre-driving voltage pulse is applied between the device electrodes 2 and 3. Perform a preliminary drive step. After the stabilization process, the resistance of the electron-emitting device is very small, for example, 1/1000 of the device resistance at the end of the forming process.
Voltage pulse (V
and a voltage pulse lower than the voltage pulse (Vdrv) during normal driving is applied to each electron-emitting device.

As a result, the resistance of the electron-emitting device can be increased, and generation of a large current during pre-driving and normal driving can be suppressed. At this time, the pre-preliminary drive voltage Vpre ′ applied to each electron-emitting device preferably has a pulse width of 100 to 1 ms and a period of 16.7 ms, but the present invention is not limited to this. The conditions are appropriately selected.

[0107]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples, and within the scope of achieving the object of the present invention, each element It includes those that have been replaced or changed in design.

[Embodiment 1] As shown in FIG. 7, Y wirings 6 and X wirings 7 made of Ag and arranged in a matrix of 480 rows × 2556 columns are formed on a glass substrate 1, respectively. And those Y wiring 6 side X
The conductive thin film 4 of the surface conduction electron-emitting device was formed in a matrix arrangement so as to electrically connect to the device electrodes 2 and 3 in which both electrodes on the wiring 7 side were paired.

Similarly to the rear plate 10 having them, the face plate 11 having the metal back 8 formed by sputtering Ti or the like on the glass substrate 1 and the phosphor 9 for image display was welded by the frit.

Further, a hole having substantially the same size as the inner diameter of the glass tube was made in the rear plate 10, and the glass tube was connected by a frit. In addition, 2556 elements are connected in parallel for each line of the Y wiring.

The image display device constructed by welding the face plate 11 and the rear plate 10 is connected to a vacuum exhaust device through a glass tube, as shown in FIG. 4, and a vacuum pump such as a scroll pump or a turbo pump is used. Evacuation was performed.

Next, while applying the forming voltage pulse Vform = 12V to the electron-emitting device formed inside the image display device through the matrix wiring, nitrogen containing 2% of hydrogen was supplied from the glass tube to 400 Torr (5.32 × 1).
By introducing up to 0 ⁴ Pa), MTX (matrix)
Electron emitting portions were formed on all the surface conduction electron-emitting devices arranged on the wiring. The voltage applied at this time is a pulse width of 1 m
sec, and the period was 16.7 msec.

Element resistance after forming is 2 to 5M
Ω or more, and 1 to 2 kΩ or more per line.

After the forming process for forming the electron emission portion, the pressure inside the image display device is adjusted to 1.33 while introducing the organic gas through the glass tube while adjusting the variable leak valve.
After the pressure is set to about 10 ⁻⁴ Pa, the activation voltage pulse Va is applied to the electron-emitting device having the electron-emitting portion through the matrix wiring.
Continuing to apply ct, a carbon compound containing carbon as a main component was deposited.

The activation voltage pulse has a voltage peak value V
act = 18V, pulse width 1 msec, cycle 16.7 m
sec, and the activation voltage application time was 60 min. After the activation was completed, the resistance was measured for each line, and the combined resistance of 2556 elements per line was 100.
It became less than Ω and the resistance of the electron-emitting device was lowered. The reduction in resistance occurred in all of the Y wiring lines 1 to 480.

After the activation step, in order to remove organic substances and residual gas in the image display device, the entire image display device was evacuated by a vacuum pump and the inside of the image display device was evacuated at 300 ° C. for 10 hours. By heating, the vacuum degree in the image display device at room temperature is 1.0 × 10 ^-6
Although it could be reduced to Pa or less, the line resistance was still reduced and pre-driving and driving were impossible.

After the stabilization process is completed, the glass tube is closed, the inside of the image display device is kept in vacuum and removed from the vacuum exhaust device, and then the manufacturing method of this embodiment is characterized in order to increase the resistance of the electron-emitting device. Preliminary pre-driving was performed for each line of Y wiring. The drive voltage Vd in this embodiment is
The rv is 15.5V.

First, as shown in FIG. 1, the pre-preliminary drive voltage Vpre 'was set to 10 V, the pulse width was 1 msec, the period was 16.7 msec, and the total pulse application time for each line was 10 sec. Crest value = -10
Voltage was applied at V.

By the pre-preliminary driving step, the combined resistance of 1 line of the Y wiring (2556 elements) was 1 kΩ or more, and it was confirmed that the resistance of the electron-emitting device was increased.

After that, when the pre-driving was carried out with the pre-driving voltage Vpre = 17V, the pre-driving current I during the pre-driving was obtained.
The f-pre became a desired value, and the pre-driving and the normal driving could be performed without damaging the electron-emitting device and without causing the glass substrate to crack.

On the other hand, as a comparative example, an element manufactured by the completely same manufacturing method and having a low resistance like the above-mentioned electron-emitting element was preliminarily driven without preliminarily driving.

As compared with the electron-emitting device of this example, the pre-pre-driving device was able to be pre-driving as described above, but the pre-pre-driving device was not. , A pre-driving current I of a desired value or more
The f-pre flowed to the electron-emitting device, damaging the electron-emitting device, and the glass substrate was cracked.

Further, the electron-emitting device which was driven in the pre-preliminary driving of the present example had a small decrease and fluctuation of the device current when it was normally driven, and a stable electron-emitting characteristic was obtained.

[Embodiment 2] Preliminary driving and normal driving are performed on the electron-emitting device according to Embodiment 2 which is prepared in the same manner as in Embodiment 1 except that the voltage application conditions during pre-preliminary driving are different. It was Note that the electron-emitting device applied in this example had a low resistance as in Example 1.

The voltage application condition during pre-preliminary driving in this embodiment is that pre-preliminary driving voltage Vpre '= 10V is applied asymmetrically to the Y wiring and the X wiring, and -6 is applied to the Y wiring.
+ 4V was applied to the V and X wirings, respectively. The pulse width was 1 ms, the period was 16.7 ms, and the total pulse application time for each line was 10 sec.

By the pre-preliminary driving step, the combined resistance of one line of Y wiring (2556 elements) was 1 kΩ or more, and it was confirmed that the resistance of the electron-emitting device was increased. Then, Example 1
Pre-driving and normal driving were performed in the same manner as in.

On the other hand, as a comparative example, an element which was manufactured by the completely same manufacturing method and whose resistance was lowered similarly to the above-mentioned electron-emitting element was subjected to pre-driving and normal driving without pre-pre-driving. .

As compared with the electron-emitting device of this example, the device of this example, which was preliminarily driven, had a desired If-pre value at the time of pre-driving, which caused damage to the electron-emitting device. It was possible to perform the pre-driving and the normal driving without adversely affecting the above, and without causing the glass substrate to crack.

However, when the pre-driving was not performed, the pre-driving was performed at the pre-driving voltage Vpre = 17V. As a result, the pre-driving current If-pre of a desired value or more flowed to the electron-emitting device, so that the electron emission was performed. The element was damaged and the glass substrate was cracked.

Further, the electron-emitting device which was driven in the pre-preliminary driving of the present example showed a small decrease and fluctuation of the device current during the normal driving, and stable electron-emitting characteristics were obtained.

[Embodiment 3] Preliminary driving and normal driving are performed on the electron-emitting device according to Embodiment 3 which is prepared in the same manner as in Embodiment 1 except that the voltage application conditions during pre-preliminary driving are different. It was Note that the electron-emitting device applied in this example had a low resistance as in Example 1.

The voltage application conditions during pre-preliminary driving in this embodiment are as follows: pre-preliminary driving voltage Vpre ′ = 10 V is applied to the Y wiring at −6 V, and X wiring is +4 V, and the Y wiring 48 is applied.
The 0 line was sequentially scroll-driven. In addition, the pulse width was 1 ms for each line, the period was 480 ms, and the total pulse application was 600 shots. By this preliminary drive step, Y
The combined resistance of one line of wiring (2556 elements) was 1 kΩ or more, and it was confirmed that the resistance of the electron-emitting device was increased. After that, pre-driving and normal driving were performed as in the first embodiment.

On the other hand, as a comparative example, an element which was manufactured by the completely same manufacturing method and whose resistance was lowered similarly to the above-mentioned electron-emitting element was subjected to pre-driving and normal driving without pre-driving. .

As compared with the electron-emitting device of this example, the device of this example, which was preliminarily driven, had If-pre at the time of pre-driving to a desired value, and the electron-emitting device was damaged. It was possible to perform the pre-driving and the normal driving without adversely affecting the above, and without causing the glass substrate to crack.

However, when the pre-driving was not performed, the pre-driving was performed at the pre-driving voltage Vpre = 17V. As a result, the pre-driving current If-pre of a desired value or more flowed to the electron-emitting device, so that the electron emission was performed. The element was damaged and the glass substrate was cracked.

Further, the electron-emitting device which was driven in the pre-preliminary drive according to the present example had a small decrease and fluctuation in the device current when it was normally driven, and a stable electron-emitting characteristic was obtained.

As a result, the element of the present example, which was subjected to the pre-preliminary driving voltage, was
Pre-driving current If flowing through each electron-emitting device during pre-driving
-Pre became about the desired value, and the pre-driving and the normal driving could be performed without adversely affecting the electron-emitting device such as damage and without causing the glass substrate to crack.

[0138]

As described above, according to the present invention,
Before performing the pre-driving process for stabilizing the electron emission characteristics, the pre-emission driving process for applying a voltage crest value lower than the voltage crest value during the pre-driving process is used to increase the electron-emitting device Resistance can be achieved, pre-driving and normal driving can be performed without adversely affecting the electron-emitting device such as damage or breaking of the glass substrate, and the emission current is stable over a long period of time. It becomes possible to manufacture an electron-emitting device.

[Brief description of drawings]

FIG. 1 is a diagram showing voltage peak values applied during pre-pre-driving, pre-driving, and normal driving in a method for manufacturing an electron-emitting device (method for manufacturing an electron source) according to an embodiment of the present invention. .

FIG. 2 is a schematic diagram showing a configuration of a surface conduction electron-emitting device manufactured by a method for manufacturing an electron-emitting device according to an embodiment of the present invention, FIG. The top view which shows a structure, (b) is sectional drawing of (a), (c) has shown an example of a vertical type surface conduction electron-emitting device.

FIG. 3 is a diagram illustrating a method of manufacturing the surface conduction electron-emitting device.

FIG. 4 is a diagram for explaining a method of energizing in a vacuum container as an example of a forming process method.

FIG. 5 is a diagram showing an example of a voltage waveform applied in energization forming.

FIG. 6 is a diagram showing an example of a voltage waveform applied in an activation step.

FIG. 7 is a schematic configuration diagram showing an image display device using an electron source with a simple matrix arrangement manufactured by the method for manufacturing an electron source according to an embodiment.

[Explanation of symbols]

1 glass substrate 2,3 element electrodes 4 Conductive thin film 5 Electron emission part 6 Y wiring 7 X wiring 8 metal back 9 Phosphor 10 Rear plate 11 face plate 12 frit 13 glass tubes 21 Step forming part 50 ammeter 51 power supply 52 Ammeter 53 High-voltage power supply 54 Anode electrode 55 Vacuum container 56 vacuum pump 57 Gate valve 58 containers 59 Control valve

Claims (18)

[Claims] 1. A method of manufacturing an electron-emitting device having a preliminary driving step of stabilizing a electron emission characteristic by applying a preliminary driving voltage having a voltage peak value higher than a voltage peak value of a driving voltage applied during normal driving. A pre-preliminary driving step of applying a pre-preliminary driving voltage having a voltage peak value lower than a voltage peak value of the preliminarily driving voltage applied in the preliminarily driving step before performing the preliminarily driving step. Method for manufacturing electron-emitting device. 2. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is lower than the voltage peak value applied during normal driving. A method for manufacturing the electron-emitting device according to claim 1. 3. A surface conduction electron having a pair of device electrodes facing each other on a substrate, a conductive thin film for electrically connecting the device electrodes, and an electron emission portion provided in the conductive thin film. The method for manufacturing an electron-emitting device according to claim 1, which is a method for manufacturing an electron-emitting device. 4. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is such that a voltage is applied to only one of the pair of device electrodes and the voltage to the other device electrode. 4. The method for manufacturing an electron-emitting device according to claim 3, wherein the voltage is a voltage peak value that is a potential difference when the voltage is 0V. 5. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is such that a positive voltage pulse is applied to one of the pair of device electrodes,
4. The method of manufacturing an electron-emitting device according to claim 3, wherein the voltage peak value is a potential difference caused by applying a negative voltage pulse to the other device electrode. 6. A step of forming the pair of opposing device electrodes on the substrate, and a step of forming the conductive thin film having carbon or a carbon compound for connecting the pair of device electrodes. The method for manufacturing an electron-emitting device according to claim 3, wherein the preliminary pre-driving step is performed after these steps. 7. A step of forming the pair of element electrodes facing each other on the substrate, and the conductive thin film connecting the pair of element electrodes, and forming the electron emitting portion in the conductive thin film. A forming step, an activating step of forming carbon or a carbon compound in the electron emitting portion after the forming step, and a stabilizing step of removing those organic substances after the activating step, and these steps. The method of manufacturing an electron-emitting device according to claim 3, wherein the pre-preliminary driving step is performed after the step. 8. The electron emitting device according to claim 3, wherein the electron emitting device is a cold cathode electron emitting device having carbon or a carbon compound in an electron emitting portion. Production method. 9. A plurality of electron-emitting devices are arranged on a substrate, and a preliminary driving voltage having a voltage peak value higher than a voltage peak value of a driving voltage applied during normal driving is applied to stabilize the electron-emitting characteristics. In the method of manufacturing an electron source having a pre-driving step, before performing the pre-driving step, a pre-preliminary driving voltage having a voltage peak value lower than the voltage peak value of the pre-driving voltage applied in the pre-driving step is applied. A method of manufacturing an electron source, comprising: 10. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is lower than the voltage peak value applied during normal driving. A method for manufacturing the described electron source. 11. The electron-emitting device includes a pair of device electrodes facing each other on the substrate, a conductive thin film for electrically connecting the device electrodes, and an electron-emitting portion provided in the conductive thin film. 11. The method for manufacturing an electron source according to claim 9, wherein the electron source is a surface conduction electron-emitting device having: 12. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step is a voltage applied to only one element electrode of the pair of element electrodes and a voltage applied to the other element electrode. The method of manufacturing an electron source according to claim 11, wherein the voltage is a voltage peak value that is a potential difference when the voltage is 0V. 13. The voltage peak value during pre-preliminary driving applied in the pre-preliminary driving step has a positive voltage pulse applied to one of the pair of device electrodes,
12. The method of manufacturing an electron source according to claim 11, wherein the voltage peak value is a potential difference caused by applying a negative voltage pulse to the other element electrode. 14. A step of forming the pair of opposing device electrodes on the substrate, and a step of forming the conductive thin film containing carbon or a carbon compound, which connects the pair of device electrodes. 14. The method of manufacturing an electron source according to claim 11, wherein the preliminary pre-driving step is performed after these steps. 15. A step of forming the pair of device electrodes facing each other on the substrate, and the conductive thin film connecting the pair of device electrodes, and forming the electron emitting portion in the conductive thin film. A forming step, an activating step of forming carbon or a carbon compound in the electron emitting portion after the forming step, and a stabilizing step of removing those organic substances after the activating step, and these steps. 14. The method of manufacturing an electron source according to claim 11, wherein the pre-preliminary driving step is performed after the step. 16. The method of manufacturing an electron source according to claim 9, wherein the plurality of electron-emitting devices are arranged in matrix. 17. The voltage crest value applied in the pre-driving step is sequentially applied to the plurality of electron-emitting devices by scroll driving, according to claim 9. Method for manufacturing electron source. 18. The pre-driving step is performed after performing the pre-pre-driving step on all of the plurality of electron-emitting devices in advance before performing the pre-driving step. 17. The method for manufacturing an electron source according to any one of items 17.