CN1996538A

CN1996538A - Method of fabricating electron-emitting device and method of fabricating image display apparatus as well as electron source therewith

Info

Publication number: CN1996538A
Application number: CN 200610168442
Authority: CN
Inventors: 竹上毅
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2005-12-13
Filing date: 2006-12-13
Publication date: 2007-07-11
Anticipated expiration: 2026-12-13
Also published as: CN100565756C

Abstract

An object hereof is to provide a method of making, a gap, which can provide good electron-emitting properties, simply, with low electric power and in short time. A method of fabricating an electron-emitting device, including a process of flowing a current in electroconductive film containing first particles and second particles including resistance lower than resistance of the first particle and thereby forming a gap in a portion of the above described electroconductive film, wherein the ratio of the above described first particle contained in the above described film is not less than 2% and not more than 30% and the ratio of resistance of the above described first particle to resistance of the above described second particle is not less than 5 and not more than 1000.

Description

Make the method for electron emission device and the method for manufacturing image display and electron source

Technical field

The present invention relates to electron emission device and image display and electron source.In addition, the information that the invention still further relates to such as television set shows and reproducer that they are used to receive the signal of the broadcasting such as television broadcasting, and is used for the video information, text message and the audio-frequency information that show and reproduce that broadcast singal comprises.

Background technology

Traditionally, known a kind of electron emission device is the surface conductive electron emission device, as illustrated in Japanese Patent Application Publication publication No.2000-231872, Japanese Patent Application Publication publication No.H01-112633, Japanese Patent Application Publication publication No.H01-093024, Japanese Patent Application Publication publication H10-050208 and Japanese Patent Application Publication publication No.H09-330649.The example of the process of making the surface conductive electron emission device is described to Figure 15 D below with reference to Figure 15 A.

At first, on the substrate 1 that has insulation property basically, form a pair of auxiliary electrode (2 and 3) (Figure 15 A).Subsequently, this is connected (Figure 15 B) to auxiliary electrode (2 and 3) with conducting film 4.Japanese Patent Application Publication publication No.H09-330649 discloses the conducting film 4 that comprises Ni and Ni oxide, and wherein, the Ni in the Ni oxide is not less than the 5 atom % of the whole Ni in the conducting film 4, and is not more than 90 atom %.In addition, as the Ni oxide, disclose with NiO and Ni ₂O ₃As the Ni oxide.In addition, also disclose, made conducting film 4 by the particulate film.

In addition, by apply voltage between this is to auxiliary electrode (2 and 3), the operation acceptance of the part of conducting film 4 is called the process of " excitation is shaped ", to form first gap 7 (Figure 15 C).

" excitation is shaped " operation is to make electric current process of flowing in conducting film 4, to form first gap 7 in the part of conducting film 4, wherein owing to electric current has produced Joule heat.Should " excitation shaping " operation make and to form a pair of aspectant electrode (4a and 4b) that first gap 7 was mediate.And under the preferable case, carry out the operation that is called " activation "." activation " operation is usually included in the process that applies voltage in the atmosphere that comprises carbon between this is to auxiliary electrode (2 and 3).This process is forming conductive carbon film (21a and 21b) (Figure 15 D) on the substrate 1 of 7 inside, first gap and near the electrode first gap 7 (4a and 4b).Thereby, in 7 inner second gaps 8 that form by the definition of the gap between the first carbon film 21a and the second carbon film 21b, first gap.Compare with the electron emission device that only forms in " excitation is shaped " operation, " activation " operation sometimes can improve electron emission capability.Process as described above has formed electron emission device.

By making electron source of forming by a plurality of electron emission devices and the substrate surface opposite that constitutes by the luminous component film that comprises fluorophor or the like, and in pressure below atmospheric pressure (being generally vacuum), keep interval between them, can make image display.

Figure 16 A is the plane graph that summary has shown electron emission device after having stood " activation " as described above operation.Figure 16 B summary has shown the sectional view of the line 16B-16B in Figure 16 A, and it is identical with Figure 15 D basically.Under the situation that makes electron emission device emitting electrons as described above, make the electromotive force that puts on auxiliary electrode (2 or 3) be higher than the electromotive force that puts on other auxiliary electrodes (3 or 2).So between auxiliary electrode 2 and auxiliary electrode 3, apply voltage, in second gap 8, produce highfield.So, be appreciated that in a large amount of points (a plurality of electronic launching point) emitting electrons as that part of the terminal periphery (having constituted the neighboring in second gap 8) of the carbon film (21a or 21b) of the auxiliary electrode (3 or 2) that is connected to low potential one side.

Summary of the invention

For example, in a vacuum the conducting film 4 that is made of metal is carried out the excitation method of operating and in comprising the atmosphere of reducible gas the conducting film of being made by metal oxide 4 carried out the excitation method of operating, being named as is routine as described above " excitation is shaped " method of operating.

Yet, though the method for the conducting film 4 that excitation is made of metal is easy,, the required electric energy of " excitation is shaped " operation will become bigger.Therefore, " excitation is shaped " operation has produced the problem such as required equipment performance will reach high level.In addition, be not less than under 30 inches the situation in the hypothesis size of display, attempted standing simultaneously " excitation shaping operation " so that when shortening manufacturing time when many conducting films that are made of metal, in wiring, current amount flowing will be increased widely common the connection for conducting film is set up.Therefore, the wiring that needs is allowed big electric current flow.In addition, produced the voltage drop that causes owing to wiring impedance, sometimes dissimilated so that put on the voltage of corresponding conducting film, this causes the shape generation deviation in the gap of formation continually.

On the other hand, for making the conducting film of making by metal oxide (as PdO) in the atmosphere that comprises reducible gas (for example hydrogen), stand " excitation is shaped " method of operating, compare with the conducting film that is made of metal being carried out " excitation is shaped " operation, the required electric energy of " excitation is shaped " operation can be inhibited.Yet, need control the atmosphere that comprises reducible gas, and the reducible rank of conducting film will be controlled, therefore, compare with the situation that makes the conducting film that is made of metal stand " excitation is shaped " operation in a vacuum, it is complicated to become.In addition, operate in the impedance that the heat that produces in the conductive film 4 little by little changes conducting film owing to need to utilize by " excitation is shaped ", therefore, " excitation is shaped " the required time of operation will become longer.In addition, for the situation of in reducible atmosphere, many conducting films being carried out " excitation is shaped " operation, can not be all in these conducting films all accept this operation simultaneously, therefore, deviation sometimes can take place in the variation of the resistance value of conducting film in operation, and this causes the shape generation deviation in the gap of formation continually.

Therefore, the purpose of this invention is to provide the method for making shapable gap, can obtain the good electron emitting performance, simple equally with the situation of the conducting film 4 that is made of metal, need lower electric energy equally with the situation of the conducting film of making by metal oxide 4, and make at short notice.

Promptly, first aspect of the present invention is to make the method for electron emission device, comprise the process that makes electric current flow through film, this film comprises many first particles of being made by first kind of material, manyly be lower than the impedance of first particle and second particle of making by the second kind of material that is different from first kind of above-mentioned material by its impedance, wherein, above-mentioned film satisfies following any one condition:

(i) ratio of the first above-mentioned particle that comprises in the above-mentioned film is not less than 2% and be not more than 30%, and the ratio of the impedance of the impedance of the first above-mentioned particle and the second above-mentioned particle is not less than 5 and be not more than 1000;

The ratio of the first above-mentioned particle that comprises in the (ii) above-mentioned film is not less than 2% and be not more than 40%, and the ratio of the impedance of the impedance of the first above-mentioned particle and the second above-mentioned particle is not less than 5 and be not more than 800; And

The ratio of the first above-mentioned particle that comprises in the (iii) above-mentioned film is not less than 2% and be not more than 60%, and the ratio of the impedance of the impedance of the first above-mentioned particle and the second above-mentioned particle is not less than 5 and be not more than 400.

Second aspect of the present invention provides a kind of method of making electron emission device, comprise the process that makes electric current flow through film, this film comprises: many first particles of being made by first kind of material, and, many its impedances are lower than the impedance of first particle and second particle of being made by the second kind of material that is different from above-mentioned first kind of material, wherein, described first proportion of particles that comprises in the described film is not less than 2% and be not more than 50%; The ratio of the impedance of the impedance of described first particle and described second particle is not less than 50 and be not more than 400; And the standard deviation of described first particle and described second particle is not more than 33.3% of particle mean size.

In addition, above-mentioned of the present invention being further characterized in that: above-mentioned electric current is being no more than 1 * 10 ^-5In above-mentioned film, flow under the pressure of Pa; Above-mentioned film is placed like this, so that first auxiliary electrode is connected with second auxiliary electrode, applies potential pulse between first auxiliary electrode and second auxiliary electrode, thereby above-mentioned electric current flows in above-mentioned film; Above-mentioned film is to comprise unevenly the first above-mentioned particle under the state that mixes and the film of above-mentioned second particle; And the particle mean size of the first above-mentioned particle and second particle is not less than 5 nanometers and is not more than 20 nanometers.

In addition, the present invention also provides a kind of method of making electron source, and this electron source comprises by a plurality of electron emission devices that utilize above-mentioned manufacture method to make.

In addition, the present invention also provides a kind of method of making image display, and this equipment comprises the electron source and the luminous component of utilization from this electron source electrons emitted irradiation that utilizes above-mentioned manufacture method to make.

Method for manufacturing electron emission device of the present invention, as described above, disposed the conducting film that comprises the particle of making by at least two kinds of materials (first particle and second particle), and first particle and the impedance ratio of second particle and the content ratio of first particle have been set.Therefore, a large amount of points (part) that cause electric field to be concentrated effectively in the time of can being created in execution " excitation is shaped " operation in advance.Therefore, can utilize little electric energy, form the gap at short notice easily, and have good reproducibility, can produce the good electron emission characteristics by this gap.

With reference to the accompanying drawings to the description of one exemplary embodiment, other features of the present invention will become apparent by following.

Description of drawings

Figure 1A, Figure 1B and Fig. 1 C summary have shown the example of manufacture method of the present invention.

Fig. 2 A, Fig. 2 B and Fig. 2 C have shown the floor map of the example of manufacture method of the present invention.

Fig. 3 A and Fig. 3 B have shown the example for the useful potential pulse of excitation shaping.

Fig. 4 be shown conducting film the configuration material content than and auxiliary electrode between resistance value between the schematic diagram of association.

Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D summary have shown the conducting film corresponding to the variation of the content ratio of the configuration material of conducting film.

Fig. 6 A, Fig. 6 B and Fig. 6 C summary description corresponding to the variation of the content ratio of the configuration material of conducting film and the outward appearance in the gap that forms.

Fig. 7 be shown corresponding to the content of the configuration material of conducting film than and the table of the pattern in the variation of configuration material resistance and the gap that forms.

Fig. 8 summary has shown the configuration of the equipment that is used to measure electron emission characteristic.

Fig. 9 summary has shown electron emission characteristic.

Figure 10 summary has shown the example of the configuration of electron source.

Figure 11 is the fragmentary perspective view of image display.

Figure 12 A and Figure 12 B summary have shown the example of the configuration of fluorescent membrane.

Figure 13 is that the information signal of reception such as television broadcasting is to show or to reproduce the block diagram of their equipment.

Figure 14 A, Figure 14 B and Figure 14 C summary have shown the example of the method for making electron emission device of the present invention.

Figure 15 A, Figure 15 B, Figure 15 C and Figure 15 D summary have shown the example of making the method for conventional electrical ballistic device.

Figure 16 A and Figure 16 B summary have shown the plane graph and the sectional view of conventional electrical ballistic device.

Figure 17 A, Figure 17 B, Figure 17 C, Figure 17 D, Figure 17 E and Figure 17 F summary have shown the example of the method for making electron source of the present invention.

Figure 18 summary has shown the example of the excitation manufacturing process of electron source of the present invention.

Embodiment

To Fig. 1 C and Fig. 2 A the method for making electron emission device of the present invention is described to Fig. 2 C below with reference to Figure 1A.Fig. 2 A is a floor map to Fig. 2 C, and Figure 1A is respectively dotted line 1A-1A, 1B-1B in along Fig. 2 A to Fig. 2 C and the schematic cross-section of 1C-1C to Fig. 1 C.

Basically as following (process 1) and (process 2) is described, set up the method for making electron emission device of the present invention.

(process 1)

Prepare a substrate 1, place conducting film 4 (below will describe in detail) above the substrate at this, it comprises first particle (Figure 1A and Fig. 2 A) that has low-impedance second particle and have high impedance.Here, Figure 1A summary has shown the sectional view of the dotted line 1A-1A in Fig. 2 A.Under the preferable case, be based upon resistance value and size (below will describe) that conducting film 4 grades obtain, the particle mean size of the reality of first particle and second particle is not less than 5 nanometers (being equal to or greater than 5 nanometers), and is not more than 20 nanometers (being equal to or less than 20 nanometers).In addition, in practice, except the particle mean size of first particle and second particle is not less than 5 nanometers and is not more than 20 nanometers, the standard deviation of granularity (σ) is not more than 33.3% of particle mean size, make and especially to carry out " the excitation shaping " that below will describe, and be desirable especially for the extraordinary electron emission characteristics of acquisition with good reproducibility.Suppose that particle size distribution is that similar normal state distributes, the value here 33.3% is the value that derives according to particle mean size by 99.9% (≈ 100%) in the scope of ± 3 σ.In addition, in practice, under the preferable case, the difference between the particle mean size of the particle mean size of first particle and second particle is not more than 5 nanometers.In addition, if the morphology difference between first particle and second particle (particle mean size and/or standard deviation) is little, so, first particle that has low-impedance second particle and have a high impedance also can be called " particle of being made by low resistivity materials " and " particle of being made by highly-resistant material " respectively.In addition, under the preferable case, the average film thickness of the conducting film 4 among the present invention is identical or roughly the same with the particle mean size of particle, so that carry out " excitation is shaped " with good reproducibility.In practice, under the preferable case, the average film thickness of conducting film 4 is not less than the particle mean size of particle, and less than one and 1/2nd of the particle mean size of particle, so that carry out " excitation is shaped " with good reproducibility.

(process 2)

Subsequently, make conducting film 4 accept " excitation is shaped " operation, form first gap 7 (Figure 1B and Fig. 2 B).Here, Figure 1B summary has shown the sectional view of the dotted line 1B-1B in Fig. 2 B.

In addition, can also be before respective process as described above and/or add another process afterwards.For example, under the preferable case, " activation " operation that will describe below will be carried out (Fig. 1 C and Fig. 2 C) as (process 2) (process 3) afterwards.

In addition, Figure 1A has shown the example with first auxiliary electrode 2 and second auxiliary electrode 3 to Fig. 1 C and Fig. 2 A to Fig. 2 C, but auxiliary electrode (2 and 3) is not necessarily essential, because only the electric current that flows in conducting film 4 just is absolutely necessary.

Here, is roughly extending perpendicular to direction of current flow (auxiliary electrode 2 is towards the direction of auxiliary electrode 3) in first gap 7 that forms in " excitation is shaped " operation.First gap 7 is rectilinear form always not, sometimes can be crooked shape.In most of the cases all adopt crooked shape.This process will produce the first electrode 4a and the second electrode 4b, and they clip gap 7, and face-to-face basically.That is, in the ideal case, conducting film 4 is divided into two parts by gap 7 fully.Here, conducting film 4 can be divided into two parts (the first electrode 4a can be connected to the second electrode 4b in extremely small zone) fully.However, if in sufficiently high impedance state, only formed gap 7 (space between the first electrode 4a and the second electrode 4b), then do not have actual problem.

Therefore, when being created on of first gap 7 provided sufficiently high impedance between the first electrode 4a and the second electrode 4b, " excitation is shaped " operation was finished.In other words, in that moment when providing sufficiently high impedance between first auxiliary electrode 2 and second auxiliary electrode 3, " excitation is shaped " operation is finished.

For example, can derive the resistance value between the first electrode 4a and the second electrode 4b according to the electric current that flows between auxiliary electrode 2 and the auxiliary electrode 3 by between auxiliary electrode 2 and auxiliary electrode 3, applying voltage (for example, the voltage of about 0.1V).In practice, when the resistance value between auxiliary electrode 2 and the auxiliary electrode 3 reaches with pre-" excitation is shaped " " excitation is shaped " operation is finished.So, if before " excitation be shaped " process and afterwards resistance value can increase and is not less than binary digit, so, (when electronics is launched) diminishes reactive current when driving, thus can realize the having high electronic transmitting efficiency electron emission device of (electric current of emission (Ie)/device current (If)).Yet, self-evident, suppose in " excitation is shaped " process, to have formed gap 7.That is, be not less than binary digit, do not form the operation rather than " excitation is shaped " the of the present invention operation in gap 7 even resistance value increases.

Here, according to the size that electron emission device allows, resistance value of the distance L between the resistance value of wiring, auxiliary electrode 2 and the auxiliary electrode 3, derivation when driving or the like is suitably selected the resistance value of conducting film 4 before " excitation is shaped " operation.Yet, for example suppose that size is not less than 30 inches display and comprises and be no less than 1920 * 1080 electron emission device altogether.Under the preferable case, the real impedance values of conducting film 4 before " excitation is shaped " operation is between being not less than 100 Ω and being not more than in the scope of 100k Ω.In addition,, sometimes connect up so that many conducting films 4 are accepted " excitation is shaped " operation basically simultaneously by many conducting films 4 being connected to one as below will be described with reference to Figure 18, thus the shortening manufacturing time.Consider such situation, under the preferable case, the scope of the resistance value of conducting film 4 is in practice between being not less than 8k Ω and being not more than in the scope of 50k Ω.In addition, the film thickness of conducting film 4 (replaceable under many circumstances is granularity) is set to be not less than 5 nanometers in practice and is not more than 40 nanometers, in view of reproducibility, and because the availability of resistance value as described above is not less than 5 nanometers and is not more than 20 nanometers better.Utilize first a large amount of particles and the second a large amount of particles to form conducting film 4, so that conducting film 4 has such resistance value scope and film thickness scope.

" excitation be shaped " operation in utilizing the present invention successfully increases the resistance value of conducting film 4 and is not less than after the binary digit, end to end from conducting film 4, be substantially perpendicular on the direction of wherein auxiliary electrode 2 and auxiliary electrode 3 aspectant directions, (effectively) forms gap 7.And, in view of the electric current I f that flows between auxiliary electrode 2 and the auxiliary electrode 3 and be applied to auxiliary electrode 2 and auxiliary electrode 3 between voltage Vf, obtained nonlinear characteristic as shown in Figure 9.Here, (can be set fourth as " do not have to increase at resistance value and be not less than under the situation of binary digit " again) under the situation that does not form good gap 7, between auxiliary electrode 2 and auxiliary electrode 3, keeping the ohms current component, therefore, do not occurring enough non-linear.

Under the preferable case, carry out " excitation is shaped " operation by apply potential pulse to conducting film 4.Under the preferable case, be no more than 1 * 10 ^-5The pressure of Pa is carried out " excitation is shaped " operation down.Fig. 3 A and Fig. 3 B have described the situation that applies potential pulse repeatedly, if but use the present invention, in the ideal case, only apply single potential pulse and can in conducting film 4, form gap 7.Yet,, under the preferable case, repeatedly apply potential pulse to conducting film 4 if carry out " excitation is shaped " operation with stable manner.Under the low situation of the reproducibility that forms conducting film 4 and a large amount of conducting film 4 is being connected to same wiring and simultaneously a large amount of conducting film 4 is carried out by relevant wiring under the situation that " excitation is shaped " operate, it is desirable especially repeatedly to apply potential pulse.

Under the situation that applies potential pulse repeatedly, Fig. 3 A shows a kind of technology, this technology makes peak value (magnitude of voltage) substantial constant of pulse, and Fig. 3 B shows a kind of technology, and wherein the peak value of pulse (magnitude of voltage) changes (voltage increases or voltage increases repeatedly/reduces) with respect to the time.

Time T 1 among Fig. 3 A and Fig. 3 B and T2 are respectively the pulse duration and the pulse spacings (rest period) of potential pulse.Under the preferable case, time T 1 is set between being not less than 1 microsecond and being not more than in the scope between 10 milliseconds, and time T 2 is set between being not less than 10 microseconds and being not more than in the scope between 10 milliseconds.According to the pattern and the resistance value of conducting film 4, suitably select the peak value (crest voltage) of potential pulse.

The waveform of the pulse of using is not only limited to triangular wave, but can adopt the needed waveform such as square wave or the like.For example, the triangular wave among Fig. 3 B can increase about 0.1V with step-by-step system.

Under the preferable case, use substrate insulation or insulation basically as substrate 1.For example, can use glass substrate, silica substrate, soda-lime glass substrate, ceramic substrate (such as alumina) and the silicon substrate that is laminated with silicon dioxide layer (being generally silica layer) on it.In order to obtain the good electron emission characteristics, under the preferable case, use so-called " glass with lower alkali content " and " alkali-free glass ", it is compared with soda-lime glass, and the alkali content such as Na reduces." activation " as described below in order to carry out preferably uses the substrate that is coated with silicon dioxide layer (normally silica layer) on glass with lower alkali content substrate or alkali-free glass substrate.

In addition, substrate 1 not only can have by the structure by substrate configuration itself as described above, and can be the substrate that is positioned at the insulation of support component or insulate basically.That is, following pattern also is preferred: utilize the known technology such as photoetching method, form polygon (normally rectangular structure or approach the structure of cuboid) on glass substrate, and conducting film 4 is positioned on its surface.Under these circumstances, such structure is preferred: the surface of the substrate at conducting film 4 places tilts with the plane surface (having applied below with the anode potential of describing to it) of predetermined angle (normally 90 degree or 90 degree basically) with conducting film (metal-back or anode electrode).The surface at conducting film 4 places is configured to the angle that becomes to be scheduled to metal-back or anode electrode, thereby the amount of electrons that arrives anode can increase.

Under the situation of using auxiliary electrode (2 and 3), after being placed on auxiliary electrode (2 and 3) on the substrate 1, under the preferable case, so place conducting film 4, so that first auxiliary electrode 2 is connected with second auxiliary electrode 3.Under these circumstances, conducting film 4 is preferred, because the covering of the corresponding at least part of first auxiliary electrode 2 and second auxiliary electrode 3 can stable electrical be connected.Can use the material of general electric conducting material as auxiliary electrode (2 and 3).For example, can use the metal of from the group that constitutes by Ag, Ni, Cr, Mo, W, Pt, Ti, Al, Cu etc. or its alloy etc., selecting.

Under the situation of pattern of considering the applying electronic ballistic device or the like, suitably select the distance L between first auxiliary electrode 2 and second auxiliary electrode 3 and the width W of auxiliary electrode (2 and 3).Under the preferable case, distance L is set between being not less than 1 μ m and being not more than in the scope of 500 μ m, is set between being not less than 1 μ m and being not more than in the scope between the 20 μ m better.Under the preferable case, consider electronics emission (Ie), width (W) is set between being not less than 5 μ m and being not more than in the scope between the 200 μ m.Under the preferable case, the thickness d of auxiliary electrode (2 and 3) is set between being not less than 10nm and being not more than in the scope between the 10 μ m.In addition, from providing electric current and the viewpoint of the stability of electronics emission when driving to conducting film 4 is stable, preferably the width W of auxiliary electrode (2 and 3) be set to greater than conducting film 4 width W '.

Conducting film 4 of the present invention comprises at least two kinds of particles (high impedance particle and Low ESR particle) that impedance is different.Therefore, we can say first particle of making by high impedance particle 71 and constituted conducting film 4 by second particle that Low ESR particle 70 is made.Correspondingly, the impedance of first particle will be higher than the impedance of second particle.In addition, a large amount of first particle and second particles lay respectively in the conducting film 4.That is, conducting film 4 comprises many first particles and many second particles.In the present invention, as described above, if the morphology difference (standard deviation of particle mean size and/or granularity) in two kinds of particles as described above is not so big, then the expression of " impedance " is equivalent to or is equivalent to basically express " resistivity ".Therefore, first particle is described to " with compared the particle that material with high resistivity is made by the material that constitutes second particle " and " by compare the particle that material with low-resistivity is made with the material that constitutes first particle " respectively with second particle.

Select first particle 71 as described above and second particle 70 so that satisfy below relation with the impedance ratio of detailed description.Here, the ratio of the impedance of the impedance of " impedance ratio " expression first particle and second particle.In other words, " impedance ratio " is the value that is expressed as (impedance of first particle 71)/(impedance of second particle 70).In addition, if the morphology difference between first particle and second particle (particle mean size and/or standard deviation) is not so big, then " impedance ratio " can be expressed as " (constituting the resistivity of the material of first particle)/(constituting the resistivity of the material of second particle) ".Under the preferable case, from the group that constitutes by cobalt oxide, nickel oxide, palladium oxide, bismuth oxide, yttrium oxide, ruthenium-oxide, amorphous carbon or the like, select to constitute the material of first particle.On the other hand, under the preferable case, from the group that constitutes by palladium, cobalt, platinum, bismuth, iridium, ruthenium or the like, select to constitute the material of second particle.In addition, first particle and/or second particle can be made of multiple element respectively, as in the alloy.As an example of such pattern, have such situation: second particle is made of the alloy of palladium and cobalt, and first particle is made of amorphous carbon, and their combination is preferred especially.Here, the resistivity of block (bulk) material certainty is proportional with the resistivity of the material of the particle of nanometer scale, as in the present invention.

In addition, the content of first particle that contains in the conducting film 4 is set to satisfy the relation that below will describe than (ratio of first particle that comprises in the conducting film 4).Here, conducting film 4 is extremely thin films.Therefore, the content ratio of first particle in the conducting film 4 (or second particle) can be expressed as " area ratio/occupancy ratio of first particle in the conducting film 4 (or second particle) " again.Under the situation that the equipment of selecting in by the group that constitutes from below with the FE-AES, the ESCA that describe, XPS, EPMA or the like is measured above the conducting film 4, can be according to the content of first particle than (area ratio/occupancy ratio of first area) calculating content as described above than (area ratio/occupancy ratio).Certainly, also can calculate than (area ratio/occupancy ratio of second area) according to the content of second particle.

Here, conducting film 4 of the present invention also is applicable to by three kinds or more kinds of impedance different particles situation about constituting mutually.

Conducting film 4 is made of a large amount of particles, because can utilize low electric energy, forms the gap 7 that is formed by " excitation is shaped " operation that below will describe with good reproducibility.Its reason is to have formed a large amount of electric field concentrated area (current concentration zone) that below will describe in conducting film 4.

Here, part or all of a large amount of particles that comprise in the conducting film 4 can be that particle wherein adjacent one another are is sintered or the pattern of partial melting (for example, present from by the shape of selecting cucurbit shape or the peanut-shaped group that constitutes).The granularity of particle (can stipulate with the granularity (diameter) of maximum usually) needs not to be uniformly, but as described above, under the preferable case, particle surface geometrical shape difference (particle mean size and/or standard deviation) is preferably less.

Conducting film 4 of the present invention can form with various known manufacture methods, and these methods are selected from the group that is made of sputtering method, evaporation, ink-jet method or the like.For example, utilizing ink-jet method to form under the situation of the conducting film of being made by a large amount of nickel oxide particles and a large amount of platinum (Pt) particle 4, nickel complex and platinum complex are dissolved in a kind of solvent to prepare China ink.With ink-jet apparatus China ink is applied on the substrate 1 as described above.After this, in oxygen-containing atmosphere, carry out roasted processing, can form the conducting film that contains nickel oxide particle and platinum grain.The complex compound that can specify the element of selecting from the group that is made of palladium, cobalt or the like element is as metal complex.In addition, preparation contains the nickel oxide particle that is dispersed in the solvent (decentralized medium) and the China ink of platinum grain, with ink-jet method, spin-coating method or the like China ink is applied to substrate 1, and by roasted substrate 1 removal solvent, the result can form conducting film 4.

Be suitable for conducting film 4 of the present invention and include a large amount of concentrated zones of electric field (or electric current) when carrying out " excitation is shaped " operation.Therefore, along with conducting film 4 becomes the film (film that lacks specific period and systematicness basically) of more non-homogeneous (isomery), it is more remarkable that effect of the present invention will become.In order to obtain so non-homogeneous film, conducting film 4 of the present invention is made of the film that comprises the first a large amount of particle that is in admixture and a large amount of second particle.

In addition, can adopt various technology as the method that forms non-homogeneous film as described above.For example, can use the method that forms film by sputtering method and evaporation, so that, make corresponding film formation time different mutually with the film formation condition for forming first particle and second particle.In addition, also can use such method: provide first particle and second particle to be dispersed in China ink in the solvent, so that this China ink is applied on the substrate 1 with ink-jet method.So, considered the whole bag of tricks, still, the present invention will not be only limited to such method.

Fig. 4 has shown the content ratio of first particle 71 that comprises in the conducting film 4 and the relation between the resistance value (resistance value of conducting film 4) between first auxiliary electrode 2 and second auxiliary electrode 3.That is, (A) among Fig. 4 shown the situation that conducting film 4 only is made of second particle 70, and (D) among Fig. 4 shown the situation that conducting film 4 only is made of first particle 71.In addition, Fig. 5 A has shown the conducting film 4 of first particle 71 of percentage shown in the table that contains among Fig. 4 respectively with the top view summary to Fig. 5 D.

Under the situation that first particle 71 and second particle 70 are mixed equably, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 is corresponding to the variation of the percentage of first particle 71 that comprises in the conducting film 4 and substantial linear ground changes (referring to the dotted line among Fig. 4 60).On the other hand, under the situation that first particle 71 and second particle 70 are anisotropically mixed, as as shown in Fig. 5 B and Fig. 5 C, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 non-linearly changes (referring to the solid line among Fig. 4 61) corresponding to the variation of the content ratio of first particle 71.That is, exist conducting film 4, the first auxiliary electrodes 2 of first particle of (anisotropically mix) and second particle and the resistance value between second auxiliary electrode 3 non-linearly to change according to the variation of the area ratio/occupancy ratio of first particle for having anisotropically.

Subsequently, will be described in the central zone of having concentrated electric field (electric current) in conducting film 4 inside of " excitation is shaped " operation to Fig. 5 D with reference to figure 5A.Here, in Fig. 5 D, Reference numeral 1 is represented substrate at Fig. 5 A; Reference numeral 2 expressions first auxiliary electrode; Reference numeral 3 expressions second auxiliary electrode; Reference numeral 4 expression conducting films; Reference numeral 70 expressions second particle; And Reference numeral 71 expressions first particle.

Pattern among Fig. 5 A is that the percentage (area ratio/occupancy ratio of first particle 71) of first particle 71 that comprises in the conducting film 4 is 0% situation.That is, in the case, conducting film 4 only is made of second particle 70 all over.Therefore, compare with the situation that contains first particle 71, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 will become lower.In addition, the impedance of conducting film 4 does not change basically anywhere, therefore, from the quality aspect, can not produce the specific region that electric field is concentrated (current concentration specifically).

Pattern among Fig. 5 B is that second particle 70 and first particle, 71 boths are present in the situation in the conducting film 4.That is, second particle 70 and first particle 71 anisotropically are present in the conducting film 4.Compare with the situation of Fig. 5 A, the impedance between first auxiliary electrode 2 and second auxiliary electrode 3 will become bigger.In addition, when the conducting film 4 of this pattern was accepted " excitation is shaped " operation, the path of current that flows between first auxiliary electrode 2 and second auxiliary electrode 3 was limited to the part, therefore, produced the zone 72 of electric field concentration of local in the part of conducting film 4.

Pattern among Fig. 5 C is to compare the bigger situation of percentage that makes first particle 71 that comprises in the conducting film 4 with the pattern of Fig. 5 B.In the case, the resistance value itself between first auxiliary electrode 2 and second auxiliary electrode 3 will be greater than the situation of Fig. 5 B.In addition, the conducting film of this pattern 4 is accepted " excitation is shaped " operation, then, current path is limited, and is identical with the situation of Fig. 5 B, and produced the electric field concentration of local in zone 72.

Pattern among Fig. 5 D is that the percentage of first particle 71 that comprises in the conducting film 4 is situations of 100%.That is, in the case, conducting film 4 only is made of first particle 71 all over.Therefore, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 will become and be higher than any pattern of Fig. 5 A in Fig. 5 C.And, identical with the situation of Fig. 5 A in the case, when carrying out " excitation is shaped " operation, the specific region that can not produce the electric field concentration of local.

That is, identical with situation among Fig. 5 B and Fig. 5 C, if provide by first particle 71 and second particle 70 are anisotropically mixed the conducting film 4 that constitutes, the zone 72 that electric field is concentrated in the time of then can being provided at execution " excitation is shaped " operation in advance.Therefore, can utilize low electric energy, form first gap 7 with good reproducibility.Even the conducting film 4 of the pattern among Fig. 5 A and Fig. 5 D is carried out " excitation is shaped " operation, also can form gap 7, and unfavorable basically concentrated with electric field.Therefore, compare with the electric energy that " excitation is shaped " of the present invention operation is required, the conducting film 4 of the pattern among Fig. 5 A and Fig. 5 D will need much more electric energy.Correspondingly, in order to utilize low electric energy the conducting film 4 of the pattern among Fig. 5 A and Fig. 5 D is carried out " excitation is shaped " operation, traditionally, conducting film 4 must form by metal oxide, and accepts " excitation is shaped " operation in containing the atmosphere of reducible gas.Here, utilize metal film to constitute conducting film 4 and need flow through huge electric current, therefore also need a large amount of electric energy.

So, has the conducting film 4 of first particle 71 and second particle 70, the concentrated zone of electric field in the time of being provided at executions " excitation is shaped " operation can in advance conducting film 4 by use.Yet, under the situation of producing electron emission device, only utilize the small gap 7 that in the part of conducting film 4, forms, can not obtain enough electron emission characteristics.In order to obtain enough electron emission characteristics, importantly, extend to the gap 7 of the other end from an end of conducting film 4 in width (W ') direction (being substantially perpendicular to the direction of the auxiliary electrode 2) formation of conducting film 4 towards the direction of auxiliary electrode 3.In order to form the gap 7 that can obtain this enough electron emission characteristic, must produce a large amount of zones 72 of when carrying out " excitation is shaped ", concentrating electric field.The gap 7 of guaranteeing to obtain enough electron emission characteristics as described above can be expressed as such pattern: in practice, compare before with carrying out " excitation is shaped ", the resistance value between the first electrode 4a and the second electrode 4b (resistance value between auxiliary electrode 2 and the auxiliary electrode 3) has increased two digits or bigger.

Therefore, will the conducting film 4 that can produce a large amount of electric field concentrated parts when carrying out " excitation is shaped " operation be described to Fig. 6 C with reference to figure 6A.

In Fig. 6 C, the percentage of first particle 71 in the conducting film 4 (area ratio/occupancy ratio of first area) is fixed as 30% (percentage of second particle 70 (area ratio/occupancy ratio of second area) is 70%) at Fig. 6 A.And summary has shown when making the rate of change of first particle 71 and second particle 72 the morphology difference in the gap 7 that forms in " excitation is shaped " operation.

Under the constant situation of the electric energy (at the electric energy of input between auxiliary electrode 2 and the auxiliary electrode 3) of input when make carrying out " excitation is shaped " operation, the morphology that forms gap 7 can roughly be divided into three types among Fig. 6 A, Fig. 6 B and Fig. 6 C.

Fig. 6 A has shown the situation of impedance ratio ((impedance of first particle 71)/(impedance of second particle 70)) less than 5.That is,, the many gaps 7 that are separated from each other (intermittently) have been formed continually in such cases.Also will can not stride whole zone in width (W ') direction of conducting film 4 and form gap 7, still, first auxiliary electrode 2 continues to keep ohm substantially to be connected by conducting film 4 with second auxiliary electrode 3 continually.Its reason is, the impedance ratio between first particle 71 and second particle 70 is little, so that the quantity of the electric field concentrated area that produces when carrying out " excitation is shaped " operation is little, perhaps, the intensity of the electric field of generation is little.In addition, under the situation of this pattern,, can not obtain big electron emission amount even carry out " activation " operation.In addition, when electronics is launched, the reactive current (device current If) that flows between first auxiliary electrode 2 and second auxiliary electrode 3 will become big.

Fig. 6 B has described impedance ratio and has been set to be not less than 5 and be not more than 1000 situation.In the case, unlike pattern as shown in Figure 6A, conducting film 4 is divided into two parts substantially or fully, and one of them gap 7 is together in series them.And in the case, before carrying out " excitation is shaped " operation and afterwards, the resistance value of conducting film 4 has increased and has been not less than two digits.In addition, in this case,, can obtain big electron emission amount by carrying out " activation " operation.And, in such cases, compare with the situation among Fig. 6 A, can make the reactive current that when electronics is launched, produces less, therefore, can obtain high electronic transmitting efficiency (electron emission current/device current).

Fig. 6 C has described to make impedance ratio greater than 1000 situation.Utilize this situation, identical with as shown in Figure 6A situation, will can not stride whole zone and form gap 7 in width (W ') direction of conducting film 4.Infer that its reason is, identical with the situation of Fig. 6 A, the electric field concentrated area that produces when carrying out " excitation is shaped " is little, and perhaps, the intensity of the electric field that is produced is little.

So, the percentage of first particle 71 that comprises in conducting film 4 is set under the situation of 30% (percentage of second particle 70 is 70%), and impedance ratio is set to be not less than 5 and be not more than 1000.By such setting, can stride whole zone substantially in width (W ') direction of conducting film 4 and form gap 7.In addition, before carrying out " excitation is shaped " operation and afterwards, the resistance value of conducting film 4 can increase and is not less than two digits.

Next, be that the percentage of first particle 71 that comprises in the conducting film 4 has been set to 30% example to the example shown in Fig. 6 C as Fig. 6 A.Therefore, the table among Fig. 7 shown, except making impedance ratio changes, and the gap 7 that forms under the situation that the percentage (area ratio/occupancy ratio of first area) of first particle 71 that comprises in the conducting film 4 is changed.In the table in Fig. 7, horizontal line is represented the percentage (area ratio/occupancy ratio of first area) of first particle 71 that comprises in the conducting film 4, and vertical row is represented impedance ratio.Here, table has as shown in Figure 7 been described such situation: when carrying out " excitation is shaped " in each case, make the voltage (voltage that applies between first auxiliary electrode 2 and second auxiliary electrode 3) to conducting film 4 applies identical.

Here, will not be only limited to the material that will use with to composition the control of particle impedance and to control, but also can for example carry out by the oxidation rank of controlling first particle.In addition, also can control like this: constitute first particle or second particle respectively than (composition ratio) by the content that utilizes two types identical unit usually to change two types element.

The situation that symbol in the table of Fig. 7 " zero " sign is such: situation about describing with Fig. 6 B is identical, utilizes " excitation is shaped " operation to form a continuous gap 7.That is, shown such situation: utilize " excitation is shaped " operation to form gap 7, and before carrying out " excitation is shaped " operation and afterwards, the resistance value of conducting film 4 has successfully increased and has been not less than two digits.

On the other hand, the situation that the symbol in the table of Fig. 7 " x " sign is such: identical with Fig. 6 A with the described situation of Fig. 6 C, do not form good gap 7.

Based on the table among Fig. 7, obviously, adopt following setting (1) to any setting that is provided with in (3), reproducibility that can be good forms the gap that divides (electronics division) conducting film 4 fully in the electronics mode.In other words, adopt and (1) is set to any setting that is provided with in (3), utilize " excitation is shaped " operation to form gap 7, and be not less than two digits than increasing before carrying out " excitation is shaped " operation at the resistance value of carrying out conducting film 4 after " excitation is shaped " operation.Therefore, good gap 7 can be formed, and the good electron emission characteristics can be obtained.

(1): impedance ratio is set to be not less than 5 and be not more than 1000, and the percentage of first particle that comprises in the conducting film is set to be not less than 2% (being equal to or greater than 2%) and is not more than 30% (being equal to or less than 30%).

(2): impedance ratio is set to be not less than 5 and be not more than 800, and the percentage of first particle that comprises in the conducting film is set to be not less than 2% and be not more than 40%.

(3): impedance ratio is set to be not less than 5 and be not more than 400, and the percentage of first particle that comprises in the conducting film is set to be not less than 2% and be not more than 60%.

Satisfy the conducting film 4 that above-described condition (1) arrives any one condition in (3) by use, utilization is equivalent to use the little electric energy of the electric energy in the situation of reducible gas can obtain good gap 7, and need not to use traditionally reducible gas required when " excitation is shaped " of the conducting film of being made by metal oxide.

In other words, for conducting film 4 of the present invention, (A) for the percentage that is included in first particle in the conducting film between being not less than 2% and be not more than situation in 30% the scope, impedance ratio is set to be not less than 5 and be not more than 1000; (B) for the percentage that is included in first particle in the conducting film between greater than 30% and be not more than situation in 40% the scope, impedance ratio is set to be not less than 5 and be not more than 800; (c) for the percentage that is included in first particle in the conducting film between greater than 40% and be not more than situation in 60% the scope, impedance ratio is set to be not less than 5 and be not more than 400.

By such setting, do not need the reducible state (variation of impedance) of conducting film 4 in control " excitation is shaped " operation basically.And such setting can be so that " excitation shaping " required electric energy reduces, thereby can simplify manufacturing equipment." excitation is shaped " the required time of operation can shorten in addition, simultaneously.

In addition, the impedance ratio of the impedance of the impedance of first particle as described above and second particle is set to be not less than 50 and be not more than 400, even reach at the standard deviation that allows granularity as described above under 33.3% the situation, also can obtain the good electron emission characteristics.In addition, at this moment, in practice, the ratio of first particle as described above is set between being not less than 2% and be not more than in 50% the scope under the preferable case.In addition, under the preferable case, the particle mean size of first particle and second particle is set to especially between being not less than 5 nanometers and being not more than in the scope of 20 nanometers.

Here, be used for conducting film 4 of the present invention and will be only limited to those conducting films that only constitute by two kinds of different particles of impedance.That is, the present invention is applicable to that also conducting film 4 is by three kinds or more kinds of impedance different particles situation about constituting mutually.In this case, in practice, by selecting the combination of two kinds of particles, so that total content is than being not less than 70% of conducting film 4, so that, thereby can produce effect of the present invention in the relation as described above that satisfies between two kinds of relevant particles between impedance and the content ratio.

Satisfy the conducting film of the present invention 4 of condition as described above by use, the resistance value after carrying out " excitation is shaped " operation between the first electrode 4a and the second electrode 4b can be not less than two digits than increase before carrying out " excitation is shaped " operation.In addition, can make the form variations in gap 7 become less.In addition, after carrying out " excitation is shaped " operation, can make the reactive current that between the first electrode 4a and the second electrode 4b, flows less.

Correspondingly, be connected to jointly under the situation of " activation " operation of connecting up and below will describe a large amount of conducting film execution simultaneously at a large amount of conducting film (conducting film after carrying out " encourage and be shaped " operation), the reactive current that flows in wiring can reduce.Therefore, can make the voltage drop step-down in the wiring when carrying out " activation " operation.Therefore, can simply and easily carry out strong " activation " operation of uniformity by the public wiring on the corresponding conducting film (electron emission device).

Under the preferable case, " activation " operates in (process 2) as described above and carries out as (process 3) afterwards.Yet, depend on the morphology in first gap 7, the material of the width in gap 7 (distance between the first electrode 4a and the second electrode 4b), conducting film 4, " activation " operation can improve electron emission current (Ie) and electronic transmitting efficiency (Ie/If).Here, the width in the gap 7 that forms in process 2 is not less than 1 nanometer and is not more than 10 nanometers, and (when electronics is launched) can keep under the situation of stable electron emission characteristic in long-time when driving, and not necessarily must carry out " activation " operation.For example, if the width that utilizes the gap 7 that " excitation is shaped " operation forms is usually between being not less than 1 nanometer and being not more than within the scope of 10 nanometers (under the preferable case, be not less than 3 nanometers and be not more than 10 nanometers), sometimes needn't carry out " activation " operation.

By carrying out " activations " operation, on the surface of the substrate 1 of 7 inside, first gap that can in being located at " excitation is shaped ", form and the last placement conductive carbon film (21a and 21b) (referring to (Fig. 1 C and Fig. 2 C)) of electrode (4a and 4b) in its vicinity.Therefore, in first gap 7, form second gap 8.Second gap 8 is corresponding to the gap between the first carbon film 21a and the second carbon film 21b.The width in second gap 8 (distance between the first carbon film 21a and the second carbon film 21b) is set to usually between being not less than 1 nanometer and being not more than within the scope of 10 nanometers (under the preferable case, be not less than 3 nanometers and be not more than 10 nanometers).Under the situation that is not less than 3 nanometers,, also can in long-time, keep stable electronics emission even apply voltage less than 30V to second gap 8.Surpassing under the situation of 10 nanometers, voltage (causing the required voltage of electronics emission) required during driving will increase, and the cost of the drive circuit that will use will uprise simultaneously.

By (for example, organic gas in) the atmosphere, (between auxiliary electrode 2 and auxiliary electrode 3) applies potential pulse repeatedly between the first electrode 4a and the second electrode 4b, can carry out " activation " operation comprising carbonaceous gas.Here, under the preferable case, apply potential pulse repeatedly, wherein periodically put upside down the relation (relation of the electromotive force between auxiliary electrode 2 and the auxiliary electrode 3) of the electromotive force between the first electrode 4a and the second electrode 4b.Periodically put upside down by the relation (relation of the electromotive force between auxiliary electrode 2 and the auxiliary electrode 3) that makes the electromotive force between the first electrode 4a and the second electrode 4b and to apply potential pulse, can be effectively on the first electrode 4a side and the second electrode 4b side depositing carbon films all.

Organic substance is the typical case of carbonaceous gas as described above.Organic substance can be selected from the group that for example is made of the aliphatic hydrocarbon of alkane, alkene, alkynes, aromatic hydrocarbon, alcohol, aldehyde, ketone, amine, carbolic acid, carvol, organic acid or the like such as sulfone acid.In addition, specifically, can use from the group that constitutes by methane, ethane, propane or the like, select, be expressed as C _nH _2n+2Saturated hydrocarbons and from the group that constitutes by ethene, propylene or the like, select, be expressed as such as C _nH _2nThe unsaturated hydrocarbons of molecular formula.In addition, also can use the material of from the group that constitutes by benzene, toluene, methyl alcohol, ethanol, formaldehyde, acetaldehyde, acetone, methylethylketone, methylamine, ethamine, carbolic acid, carbamic acid, acetate, propionic acid or the like, selecting.

" activation " operation can form by carbon or by with atmosphere in the film (

carbon film

21a and 21b) made of the synthetic carbon compound of the organic substance that exists.Therefore, generally speaking, emission current Ie can improve significantly.

Carbon or carbon compound are from for example electing the group by graphite (comprising so-called HOPG, PG and GC) and amorphous carbon (mixture of the microcrystal of amorphous carbon or amorphous carbon and graphite as described above) formation.Here, HOPG represents almost complete crystal structure of graphite; PG represents to comprise the crystal structure of graphite of the particle of about 20 nanometers, and wherein crystal structure is a little somewhat unordered; And GC represents to comprise the crystal structure of graphite of the particle of about 2 nanometers, and wherein crystal structure is further unordered.

In order to keep the good electron emission characteristics in long-time, under the preferable case, the film thickness of carbon film (21a and 21b) is set between being not less than 10 nanometers and being not more than in the scope of 100 nanometers.

" activation " for example makes can measure the device current (If) that flows at (between first auxiliary electrode 2 and second auxiliary electrode 3) between the first electrode 4a and the second electrode 4b, finishes measurement when the device current value has reached desired value.Here, the pulse duration of employed potential pulse, pulse spacing, peak value of pulse or the like suitably are set to desired value in " activation " operation.

Utilize and " activation " to operate the feasible width that can dwindle first gap 7 effectively of conductive carbon film (21a and 21b) of deposition, therefore, can dwindle the required driving voltage of electronics emission, and improve electronic transmitting efficiency (Ie/If).

In addition, under the preferable case, in (process 3) as described above afterwards, as (process 4), the substrate 1 that has formed carbon film (21a and 21b) is in the above accepted bake operation.This process makes the electron emission device that forms of " activation " as described above by carrying out operation remain in the subatmospheric atmosphere (decompression atmosphere) at pressure and accepts heat treated, thereby removal is attached to the extra impurity on the surface of the surface of substrate 1 and electron emission device.

When curing processing, the dividing potential drop of the organic component in the subatmospheric atmosphere of pressure is the dividing potential drop that roughly no longer has carbon or carbon compound deposition at it down.Usually, the dividing potential drop of carbon or carbon compound is set to be no more than 10 ^-6Pa is no more than 10 under the preferable case ^-8Pa.

In addition, the condition of curing is set in 80 ℃ to 250 ℃ scope, is not less than 150 ℃ under the preferable case.Must reduce the pressure in the vacuum tank as much as possible, be no more than 10 under the preferable case ^-5Pa is no more than 10 ^-6Pa is then more excellent.

Atmosphere during electron emission device of the present invention that the process by as described above of driving forms, under the preferable case, the state of the atmosphere when keeping bake operation as described above to finish, but be not only limited to this.For example, if remove organic substance fully,, also can keep sufficiently stable characteristic even then vacuum degree itself increases or dwindles.Adopt such vacuum atmosphere can suppress extra carbon or carbon compound deposition, can remove the H that adheres in vacuum tank or substrate or the like ₂O, O ₂Or the like, therefore stablized device current And if emission current Ie.

In addition, be preferably in before " excitation is shaped " as described above process, based on conducting film 4, checking constitutes first particle of conducting film 4 as described above of the present invention and the impedance ratio of second particle, and the content ratio of first particle that comprises in the conducting film 4.Yet, for example with near the gap 7 compare, as the part of conducting film 4 and be positioned at the influence that part on the auxiliary electrode (2 and 3) almost is difficult to be subjected to easily make the process of electron emission device or image display.Correspondingly, to the content of first particle in impedance ratio as described above and the conducting film 4 than and composition than situation about analyzing under, for example that part as described above is analyzed, thereby can be measured " excitation is shaped " state of conducting film 4 before effectively.

As the method for the content of measuring first particle in the conducting film 4 than (" area ratio/occupancy ratio "), example can comprise the method for selecting from the group by FE-AES (field emission Auger electron spectroscopy determination method), ESCA (chemical analysis electronics Spectrum Method) and XPS (x-ray photoelectron spectroscopy) formation for example.That is,, can measure composition by on the surface of conducting film 4, carrying out the two-dimensional surface analysis.ESCA and XPS can measure based on the state of the chemical bond of conducting film 4 lip-deep unit ares (can be defined as having 1 μ m usually * 1 μ m size just put the shape zone) by mapping.

Under the situation that conducting film 4 is made of a large amount of particles, can also use field emission Auger electron spectrometer (FE-AES) to come the composition of corresponding particle is analyzed.Compare with distance and width thereof between auxiliary electrode 2 and the auxiliary electrode 3, the film thickness of conducting film 4 has very little value.Therefore, will only the surface state of conducting film 4 be measured.Can utilize the top of method as described above from conducting film 4, the content that calculates first particle (first area) and second particle (second area) effectively is than (area ratio), and the area ratio/occupancy ratio of first particle (first area) and/or second particle (second area).Here, can be used for conducting film of the present invention and do not get rid of these: in its surface geometry table shape, in its part, have multiple (normally two kinds) particle stacked in its film thickness direction.

In addition, can also utilize various method of measurement that the impedance of first particle as described above and/or second particle is measured, for example a part of conducting film that is positioned on the auxiliary electrode (2 and 3) by cut-out is measured.

In addition, the particle composition is analyzed, can be contacted with particle, utilize the contact mode of AFM (atomic force microscope), measure the impedance of relevant particle by analysis by the probe that makes AFM by utilizing FE-AES as described above.Under the situation that adopts the method, the preferably special conducting film (particle) that is positioned on the auxiliary electrode (2 and 3) of measuring.According to the method, can measure the impedance of particle based on the electric current that between the probe of AFM and auxiliary electrode, flows.

Below with reference to Fig. 8 and Fig. 9 fundamental characteristics by the electron emission device of the present invention of process acquisition as described above is described.Here, the electron emission device of having accepted " activation " as described above operation will be described.In addition, in order to simplify description, omitted auxiliary electrode (2 and 3) in the figure.

Fig. 8 summary has shown the example of vacuumizing equipment, and this vacuumizing equipment also has as the function of measuring assessment apparatus.Still for the particle among Fig. 8, identical reference character is represented as Figure 1A to the identical particle shown in Fig. 1 C.

In Fig. 8, Reference numeral 55 expression vacuum tanks, Reference numeral 56 expression exhaust pumps.In vacuum tank 55, placed electron emission device.Reference numeral 51 expressions are used at the power supply that applies device voltage Vf between the first electrode 4a and the second electrode 4b between (at first auxiliary electrode 2 and second auxiliary electrode 3).Reference numeral 50 expressions are used for measuring the ammeter at the device current If that flows between (at first auxiliary electrode 2 and second auxiliary electrode 3) between the first electrode 4a and the second electrode 4b.Reference numeral 54 expressions are used to catch the anode electrode from the emission current Ie of electron emission device emission.Reference numeral 53 expressions are used for the high voltage source that anode electrode 54 applies voltage.Reference numeral 52 expressions are used to measure the ammeter from the emission current Ie of electron emission device emission.The voltage of anode electrode 54 and can be measured from 1kv to 100kV, sets distance H between anode electrode and the electron emission device between within 1 millimeter to 8 millimeters scope.In vacuum tank 55, be provided at and measure required instrument under the vacuum atmosphere,, make and under desirable vacuum atmosphere, to measure and to assess as vacuum gauge or the like (not showing in the drawings).

Exhaust pump 56 can be made of the high-vacuum apparatus system, comprises turbine pump, rotary pump or the like, also the ultra high vacuum device systems can be arranged, and comprises ionic pump or the like.Here shown vacuum equipment can be heated by heater, and heater does not show in the drawings.Correspondingly, utilize this vacuum equipment, can carry out above-described " excitation is shaped " process.

Fig. 9 summary has shown emission current Ie and device current And if has utilized relation between the device voltage Vf that vacuum equipment as shown in Figure 8 measures.In Fig. 9, If compares with device current, and Ie is significantly little for emission current, therefore, shows with the unit of selecting alternatively.Here, vertical axis and trunnion axis both are calibrated linearly.Successfully formed under the situation of gap 7 with satisfied condition such as width as described above utilizing " excitation is shaped " operate, even do not carry out " activation " operation, also can obtain to be similar to the characteristic as shown in Figure 9 of back " activation " operating characteristic.

Can find out obviously that from Fig. 9 for emission current Ie, electron emission device of the present invention has following three features.

That is, at first, be not less than a certain voltage and (be called " threshold voltage " by applying; Vth among Fig. 9) device voltage, emission current Ie increases apace, on the other hand, when being no more than threshold voltage vt h, almost detects less than emission current Ie.That is, it is the nonlinear device that has different threshold voltage vt h for emission current Ie.

Secondly, because emission current Ie depends on device voltage Vf in the mode that dullness increases, so can control the former by the latter.

The 3rd, the emission electric charge (referring to Fig. 8) of being caught by anode electrode 54 depends on the time that applies device voltage Vf.That is, can the time when applying device voltage Vf control the quantity of electric charge of catching by anode 54.

From above description as can be seen, electron emission device of the present invention will become and can control electron emission characteristic like a cork according to input signal.By utilizing this characteristic, be feasible to the application in various fields, in the situation of the electron source that constitutes as lining up, imaging device or the like by many electron emission devices.

Next, will the application example of electron emission device of the present invention be described.For example, can be placed in a plurality of electron emission devices of the present invention on the substrate, in electron source and the image display.

For electron emission device, can adopt various schemes.As example, the first conducting film 4a and the second conducting film 4b are connected to first wiring and second wiring respectively jointly, so that many electron emission devices of arranging in a direction (direction of row) are connected in parallel.On same substrate, arranged the electron emission device that many row so constitute.So place control electrode (also being called " grid "), being located at directions (directions of row), and be positioned at the top of corresponding electron emission device perpendicular to first and second wirings of extending in same direction (direction of row).By adopting such configuration, can control from corresponding electron emission device electrons emitted.

On the other hand, have such situation: a plurality of electron emission devices are the arrangement of matrix state in X-direction and Y direction, be arranged in the wiring that is connected to directions X with the first conducting film 4a of a plurality of electron emission devices of delegation jointly, the second conducting film 4b that is arranged in a plurality of electron emission devices of same row is connected to the wiring of Y direction jointly.Such pattern is so-called " simple matrix " layout.To describe the simple matrix layout in detail below.

Electron emission device of the present invention has three characteristics as described above.That is, can utilize the peak value and the width of the pulse voltage that exceeds threshold voltage that between the first conducting film 4a and the second conducting film 4b, applies to control from the electron emission device electrons emitted.On the other hand, under threshold value or lower voltage condition, little radiation will take place.According to this characteristic, also be to exist under the situation of a large amount of electron emission devices, if suitably apply the voltage of pulse type, then can select electron emission device, with the control electron emission amount according to input signal to each electron emission device.

Comprise based on this principle below with reference to Figure 10 description, by electron emission device of the present invention being arranged in the substrate (back plate) 71 of the electron source that obtains in " simple matrix " layout.In Figure 10, Reference numeral 71 expression substrates (back plate); The wiring (Dx1 is to Dxm) of Reference numeral 72 expression directions Xs; And the wiring (Dy1 is to Dyn) of Reference numeral 73 expression Y directions.Reference numeral 74 expressions electron emission device of the present invention.

Up to the directions X wiring 72 that Dxm constitutes m unit, can utilize the method for from the group that constitutes by vacuum vapor deposition method, impact system, sputtering method or the like, selecting to form this directions X wiring 72 by wiring Dx1, Dx2.The suitably material of designing wiring, film thickness and width.By wiring Dy1, Dy2 constitutes the Y direction wiring 73 of n unit up to Dyn, and can adopt and form the Y direction with the directions X 72 identical modes that connect up and connect up 73.Between the Y direction wiring 73 of wiring 72 of the directions X of these m unit and n unit, provide the interlayer insulating film that does not have demonstration in the figure, separated (m and n both are positive integers) so that both are electric.

The method that the interlayer insulating film utilization that does not have among the figure to show is selected from the group that is made of vacuum vapor deposition method, impact system, sputtering method or the like is by silicon dioxide (SiO normally ₂) or the like constitute.Suitably select film thickness, material and the manufacture method of interlayer insulating film, so that can tolerate electrical potential difference by directions X wiring 72 and the Y direction wiring 73 intersection point places that form.Pull out to space outerpace inside in directions X wiring 72 and Y direction wiring 73 image display from remain below atmospheric pressure or the like.

In the first conducting film 4a (first auxiliary electrode 2) that constitutes each electron emission device 74 and the directions X of m the unit wiring 72 any one is electrically connected, the Y direction of the second conducting film 4b (second auxiliary electrode 3) and n unit connect up in 73 any one be electrically connected.

The material that constitutes wiring 72 and wiring 73 and the material of formation first and second conducting films (first and second auxiliary electrodes) can be that the part of component is identical, also can be identical, also can differ from one another.

Here, will utilize Figure 17 to describe to make the example comprise with the method for the substrate (back plate) of the electron source of such " simple matrix " layout arrangement below.

At first, on substrate (back plate) 71, provide the electrode unit (2 and 3) (Figure 17 A) that comprises first auxiliary electrode 2 and second auxiliary electrode 3 by the matrix state with desired quantity (for example, 1920 (row) * 1080 (OK)).

Then, with the quantity identical (or greater than this equal number), provide directions X wiring 72 (Figure 17 B) that make auxiliary electrode 3 carry out common connection in vertical direction with the quantity of the row that are equivalent to electrode unit.

Each place, crosspoint that Y direction wiring 73 that will form in next process subsequently, and directions X wiring 72 intersect forms insulating barrier 44 (Figure 17 C).

Then, with the quantity identical (or greater than this equal number), provide the Y direction wiring that makes auxiliary electrode 2 carry out common connection in the horizontal direction 73 (Figure 17 D) with the quantity of the row that is equivalent to electrode unit.

Next, form conducting film of the present invention 4 as described above, so that each film makes first auxiliary electrode 2 of each electrode unit be connected (Figure 17 E) with second auxiliary electrode 3 with the quantity identical with electrode unit quantity.

Subsequently, in each conducting film 4, provide gap 7 (Figure 17 F).Under the preferable case, simultaneously in being connected to the unit of a Y direction wiring 73 jointly, all form gap 7 basically.

Referring now to Figure 18 describe ad hoc approach (here, for the particle among Figure 18, used with other figures in identical Reference numeral represent identical particle).For example, utilize switching circuit 1403 to select the directions X wiring 72 of all unit, synchronously select with a Y direction wiring in the Y direction wiring of selecting a large amount of unit.As the technology of selecting all directions X wirings 72, for example, under the preferable case, all directions X wirings all are connected to common electrode 1401.In addition, under the preferable case, utilize pulse generation source 1402, between a Y direction wiring that utilizes switching circuit 1403 to select and all directions Xs wiring 72, apply potential pulse as shown in Figure 3, " excitation is shaped " as described above to carry out process.So, the difference of time of origin order more or less on all unit that are connected to selected Y direction wiring 73 jointly (being connected to the conducting film 4 of selected Y direction wiring jointly), but can form gap 7 simultaneously basically.In addition, sequentially select the switching Y direction wiring of such operation, can form gap 7 all unit by utilizing switching circuit 1403.

Here, shown the example of each Y direction wiring being carried out " excitation is shaped " process, but, if selected the Y direction wiring of a plurality of unit simultaneously, also the conducting film 4 that can side by side connect up to the Y direction that is connected to a plurality of unit of selecting is simultaneously jointly basically carried out " excitation is shaped " operation.

In addition, in conducting film 4 of the present invention, in the ideal case, can form gap 7 by applying a potential pulse.Therefore, in the ideal case, only for the quantity of the unit of Y direction wiring, the just pulse that need in " excitation is shaped " process, apply (for example, the Y direction wiring 73 for 1080 unit provides 1080 subpulses).Yet, depend on the deviation of the impedance of wiring, the impedance of electrode unit, impedance of conducting film 4 or the like, always the primary voltage pulse do not form by applying in gap 7.Correspondingly, for " excitation is shaped ", under the preferable case, the potential pulse that applies to the wiring of the Y of each unit direction is applied in repeatedly, so that stably form good gap 7 with good reproducibility.

In addition, the quantity of the unit of the potential pulse that applies to the wiring of each unit Y direction greater than 1 situation under, under the preferable case, apply potential pulse to the unit that is connected to other Y direction wirings between the interval between the unit of the potential pulse series (interval between pulse and the pulse) jointly.Promptly, in the description that utilizes Figure 18 to carry out, for example, from when select Y direction wiring Dy1 begin with the time that applies potential pulse up to select Y direction wiring Dy1 with time period with after-applied potential pulse in, apply potential pulse from Y direction wiring Dy2 to Dy1080 continuously.So, can shorten " excitation is shaped " required time span of process.In addition, by selecting the Y direction wiring of a plurality of unit, can shorten the required time span of " excitation is shaped " operation corresponding to this element number further.For example, by Y direction wiring (Dy1 is to Dy1080) is divided into 10 unit, be provided with 108 groups.Select a Y direction wiring simultaneously in from 108 groups each group, apply potential pulse once.Subsequently, select another Y direction wiring simultaneously in the group of each from 108 groups, apply potential pulse once.Repeat this process continuously, the wiring of the Y direction of 10 unit can be accepted " excitation is shaped " operation simultaneously basically.So, can on a large amount of conducting film 4, form gap 7 at short notice.

What not do not show among this figure in addition, is used to apply sweep signal so that be chosen in the directions X wiring 72 that the sweep signal bringing device of the row of the electron emission device 74 that directions X arranges is connected to the electron source of " simple matrix " as described above type.On the other hand, being used for of not showing among this figure is modulated at each row of the electron emission device 74 that the Y direction arranges corresponding to input signal modulation signal generating apparatus is connected to Y direction wiring 73.The balanced voltage that is used as between sweep signal and the modulation signal to the driving voltage that each electron emission device applies provides.

Next, will the image display that utilize such matrix-type electron source to constitute be described with reference to Figure 11, Figure 12 A and Figure 12 B.Figure 11 summary has shown the example of the display floater 88 of image display; And Figure 12 A and Figure 12 B summary have shown the example of the fluorescent membrane 84 that uses in the display floater 88 in Figure 11.

In Figure 11, Reference numeral 71 expressions are equipped with the substrate (back plate) of a plurality of electron emission devices 74; And

Reference numeral

72 and 73 expressions are connected to the directions X wiring and the wiring of Y direction of a pair of auxiliary electrode (2,3) of electron emission device.Reference numeral 86 expressions comprise the panel of fluorescent membrane 84, conducting film (metal-back) the 85th, anode electrode that forms or the like on the inner surface of glass substrate 83.Reference numeral 82 expression scaffolds, back plate 71 and panel 86 are connected to scaffold 82.Reference numeral 88 expression display floaters, and comprise panel 86, scaffold 82 and back plate 71.

Here, the supporting member that is called " packing ring " that does not show among the figure can be installed between panel 86 and the back plate 71, the display floater 88 that has the enough atmospheric intensity of antagonism with formation.

Figure 12 summary has shown the example of fluorescent membrane 84.Under monochromatic situation, fluorescent membrane 84 can only be made of fluorophor.The colour phosphor film can be made of extinction parts (dark features) 91 that is called " secret note " (Figure 17 A) or black matrix" (Figure 17 B) or the like and fluorophor 92.Under the situation of color monitor, provide the purpose of extinction parts 91 to be: by the border blackening between the fluorophor 92 that makes the emission different color light, make color mix or the like become so not remarkable, and suppress the contrast decline that outside reflection of light produced in the fluorescent membrane 84.As the material of extinction parts 91,, can also use material conduction, not too transparent and that reflectivity is weak except containing the material of graphite as main component.

Usually, provide anode electrode (conducting film) 85 in the inboard of fluorescent membrane 85 (back plate one side).This utilizes the film formed anode electrode of metal such as aluminium film or the like to be called " metal-back ".Provide the purpose of metal-back to be: to make the light that is drawn towards inboard (back plate one side) from the light of fluorophor emission reflex to a side of panel 86, thereby improve the luminous brightness of display.In addition, as anode electrode activator metal shell,, prevent that fluorophor from suffering because the damage that anionic impacts that produce in display floater 88 inside or the like cause so that apply beam voltage.Carry out smoothing operation (being called " plated film " usually) by surface after producing fluorescent membrane, after this, and utilize vacuum evaporation or the like method depositing Al then, thereby produce metal-back the fluorescent membrane inboard.

In order to strengthen the conductive characteristic of fluorescent membrane 84 further, can transparency electrode (not showing in the drawings) be provided for panel 86 in outer surface one side (between fluorescent membrane 84 and glass substrate 83) of fluorescent membrane 84.

As described below, under the preferable case, form such display floater 88.That is, utilize manufacture method as described above of the present invention, on the plate 71 of back, form a large amount of electron emission devices (substrate that comprises electron source is provided) in advance.On the other hand, utilize method as described above or the like on panel 86, to form fluorescent membrane 84 and metal-back 85.And, between back plate 71 and panel 86, place scaffold 82, the bonding part that utilizes the bonding and sealing of the adhesive of from the group that constitutes by indium, frit (flit glass) or the like and so on, selecting to form by scaffold 82 and panel and back plate.Here, if at the joint of carrying out under the subatmospheric predetermined pressure between scaffold 82 and panel and the back plate, can obtain such display floater 88, wherein the space between panel and the back plate remains under the predetermined pressure.

Apply voltage to Dxm and Dy1 to Dyn each electron emission device 74 by terminal Dx1, thereby so that make desired electron emission device emitting electrons to display floater as described above 88 inside.At this moment, apply the voltage that is not less than 5kV and is not more than 30kV to conducting film 85, under the preferable case, apply the voltage that is not less than 10kV and is not more than 25kV by high voltage terminal 87.Here, the distance between panel 86 and the substrate 71 is set to be not less than 1 millimeter and be not more than 5 millimeters, under the preferable case, is not less than 1 millimeter and be not more than 3 millimeters.So, penetrate conducting film 85, impact fluroescence body film 84 from selected electron emission device electrons emitted.After this, activating fluorescent body 92 also makes it luminous, with display image.

Here, in configuration as described above, such as material of corresponding particle or the like in detail part be not only limited to content as described above, but can suitably make amendment according to purpose.

In addition, utilize the display floater of describing with reference to Figure 11 of the present invention 88, can constitute the image demonstration/reproducer such as TV or the like of demonstration or information reproduction.

Specifically, receive the receiver of the broadcast singal such as television broadcasting and selective reception to the tuner of signal make through showing one of at least in the video information, text message and the audio-frequency information that comprise in the tuning signal and/or being reproduced on the screen of display floater 88.Here, " screen " can be expressed as the fluorescent membrane 84 corresponding to as shown in figure 11 display floater 88.This configuration can constitute the information display reproduction equipment such as TV.Certainly, under the situation of broadcast singal through coding, information display reproduction equipment of the present invention also can comprise decoder.In addition, audio signal output and synchronously reveals with the video information and the text message that are presented on the display floater 88 in the audio reproducing apparatus such as loud speaker that provides separately or the like again.

In addition, for example, can carry out as follows that video information or text message are outputed in the display floater 88 to show and/or to reproduce their method.At first, based on video information that receives and text message, produce picture signal corresponding to the respective pixel of display floater 88.The picture signal that produces is input to the drive circuit of display floater 88.And, based on the picture signal that is input to drive circuit, control the voltage that is applied to each electron emission device of display floater 88 inside from drive circuit, thus display image.

Figure 13 relates to the block diagram of television equipment of the present invention.Receiving circuit is made of tuner, decoder or the like; TV signal by network reception such as satellite broadcasting, terrestrial broadcast or the like and data broadcasting or the like; And with the decoding video data output to I/F unit (interface unit).The I/F unit is converted to the display format of display device with video data, view data is outputed to display floater 88 as described above.Image display comprises drive circuit and control circuit.Control circuit is carried out the image processing such as adjusting operation or the like that is suitable for display floater to the view data of input, and the control signal of view data and corresponding kind is outputed to drive circuit.Drive circuit based on the input view data with drive signal output to display floater 88 each the wiring (referring to the wiring Dox1 among Figure 11 to Doxm and the wiring Doy1 to Doyn), and the demonstration television video.Receiving circuit and I/F unit can be used as set-top box (STB) and are encapsulated in the housing that separates with image display, also can be in image display is encapsulated in same housing.

In addition, interface can be configured to be connected to image storage apparatus and image output device, and this image output device is selected from the group that is made of printer, digital video camcorder, digital camera, hard disk drive (HDD), digital video disk (DVD) or the like.So, the image that is stored in the image storage apparatus may be displayed on the display floater 88.In addition, information display reproduction equipment (or TV) can be configured to and can handle the image that is presented on the display floater 88 as required, and they are outputed to image output device.

The configuration of information display reproduction equipment as described herein is an example, and based on technical thought of the present invention, various variations also are feasible.In addition, information display reproduction equipment of the present invention also can be connected to TeleConference Bridge and the system such as computer or the like, thereby constitutes various information display reproduction equipment.

[example]

Specific example below will utilizing is now described the present invention in detail, and still, the present invention is not only limited to these examples, in the scope that realizes target of the present invention, can replace and change in design each element.

[example 1]

The method of the production electron emission device of this example is described to Figure 14 C below with reference to Figure 14 A.

(process a)

Utilize sputtering method deposition of silica layer on soda-lime glass, and used as substrate 1.Subsequently, after this substrate 1 of cleaning, utilize vacuum vapor deposition method continuously deposit thickness be that the Ti and the thickness of 5 nanometers is the Pt of 25 nanometers, after this, the pattern of accepting to utilize photoetching technique to carry out forms (pattern), to form auxiliary electrode (2 and 3) (Figure 14 A).Distance L between the auxiliary electrode is set to 10 μ m.So, on substrate 1, be provided with first auxiliary electrode 2 and second auxiliary electrode 3.And, also formed the conducting film 4 (Figure 14 B) that links first auxiliary electrode 2 and second auxiliary electrode 3.Constitute conducting film 4 by a large amount of CoO particles and a large amount of Pd particles, utilize sputtering method to make this conducting film.A CoO particle and Pd material anisotropically is blended in the conducting film 4.The width W of conducting film 4 ' (referring to Fig. 2 A) correspondingly is set to 60 μ m.

Here, by the sedimentation time of control respective material, the content that changes the CoO particle that comprises in the conducting film 4 and Pd particle is than (composition than), to produce five kinds of conducting films 4 (referring to (table 1) described below).That is, utilize process a as described above to produce five samples (each sample all comprises any in five kinds of shown in following described (table 1) conducting films 4, and first and second auxiliary electrode all is connected to this conducting film).Here, in this example, the impedance of cobalt oxide is 150 (CoO: Pd=150: 1) with the ratio of the impedance of palladium.Can utilize shown sample No.1 of table 1 and No.5 to obtain the impedance of CoO and the impedance of Pd.As described above, the impedance that can utilize the contact mode of AFM to measure corresponding particle (CoO and Pd).In addition, can utilize FE-AES to measure content than (area ratio/occupancy ratio).

[table 1]

No.	CoO content ratio	Pd content ratio	Impedance (conducting film)
No.	CoO content ratio	Pd content ratio	Impedance (conducting film)	1	100％	0％	30kΩ
2	60％	40％	7.5kΩ	1	100％	0％	30kΩ
2	60％	40％	7.5kΩ	3	50％	50％	5kΩ
4	30％	70％	1.2kΩ	3	50％	50％	5kΩ
4	30％	70％	1.2kΩ	5	0％	100％	200

Here, formed the film thickness of five kinds of conducting films 4 (No.1 is to No.5) respectively, so that produce the film thickness of average 15 nanometers.In addition, having constituted first particle of five kinds of conducting films 4 and the particle mean size of second particle all is 15 nanometers, and the standard deviation of granularity is 2 nanometers.That is, the standard deviation of granularity is 13.3%.

Each sample in five samples as described above is all accepted the processing of following process b and process c in vacuum tank 55 as shown in Figure 8.

(process b)

Between first auxiliary electrode 2 and second auxiliary electrode 3, apply potential pulse, to carry out " excitation is shaped " operation.Here, the pressure in the vacuum tank 55 remains on and is no more than 10 ^-5Pa.As for impulse waveform, the triangular wave pulse of having used the peak value shown in Fig. 3 B to increase gradually.Here, adopted the pulse duration of T1=1 millisecond, and pulse spacing T2=10 millisecond.

For the sample of the conducting film 4 that comprises No.1, gap 7 utilizes peak value 50V to form, and first gap 7 that forms is not continuous, but discrete state.

For the sample of the conducting film 4 that comprises No.2, gap 7 utilizes peak value of pulse 20V to form.

For the sample of the conducting film 4 that comprises No.3, gap 7 utilizes peak value of pulse 15V to form.

For the sample of the conducting film 4 that comprises No.4, gap 7 utilizes peak value of pulse 8V to form.

For the sample of the conducting film 4 that comprises No.5, gap 7 utilizes peak value of pulse 5V to form, and first gap 7 that still forms does not have to arrive the other end (referring to Fig. 2 A) in the direction of the width (W ') of conducting film 4 from an end.

Measured and comprised that No.2 is to first auxiliary electrode 2 of the sample of the conducting film 4 of No.4 and the resistance value between second auxiliary electrode 3, discovery is being carried out " excitation is shaped " before and afterwards, and the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 increases and is not less than binary digit (being not less than 100 times).In addition, as the result who utilizes electron microscope that the pattern in gap 7 is observed, comprising that No.2 is under the situation of the sample of the conducting film 4 of No.4, from the end to end of conducting film 4, form gap 7 continuously being substantially perpendicular to the direction of auxiliary electrode 2 towards the direction of auxiliary electrode 3.

On the other hand, for the conducting film 4 of No.1, as shown in Figure 6A, having formed a plurality of (dispersing) gaps that separate, also is macroscopic view, and conducting film 4 divides fully inadequately.In addition, the also non-constant width of the width in the gap 7 of formation (length of auxiliary electrode 2 in the direction of auxiliary electrode 3) even carried out " activation " operation that below will describe, still can not obtain enough electron emission characteristics.And, formed a plurality of (discrete) gaps that separate for the conducting film 4 of No.5, shown in Fig. 6 C.In addition, for the sample of the conducting film 4 that comprises No.1 and No.5, the resistance value after execution " excitation shaping " is operated between auxiliary electrode 2 and the auxiliary electrode 3 is approximately execution and " encourages and be shaped " 10 times that operate resistance value before.

(process c)

After process b as described above, comprise that No.2 as described above accepts " activation " operation to the sample of the conducting film of No.4.Specifically, in vacuum tank 55, introduce three nitriles (trinitrile) gas, between auxiliary electrode 2 and auxiliary electrode 3, apply the square-wave voltage pulse that peak value is 20V repeatedly, simultaneously, periodically put upside down the electromotive force relation between auxiliary electrode 2 and the auxiliary electrode 3.Here, pulse duration and pulse spacing are set to 1 millisecond and 10 milliseconds respectively.Therefore, for any sample, the electric current that flows between auxiliary electrode 2 and auxiliary electrode 3 all can increase along with the time.When the electric current that flows between auxiliary electrode 2 and auxiliary electrode 3 reached about 1mA, " activation " operation was finished.By carrying out " activation " operation, the first carbon film 21a and the second carbon film 21b in any sample, have all been formed, shown in Fig. 1 C.Here, between the first carbon film 21a and the second carbon film 21b, form second gap 8, on the surface of the substrate 1 that is positioned at second gap 8, formed recessed portion 22.

(process d)

After process c, No.2 accepts heating operation to the sample of No.4 with vacuum tank 55.Here, in the heating operation process, continue the exhaust in the vacuum tank 55.This operation is called " activation " operation.Pressure in vacuum tank 55 reaches and is no more than 1.3 * 10 ^-6During Pa, " activation " operation is finished.

Produced by process as described above and to have had the electron emission device of No.2 to the conducting film of No.4.

Subsequently, keeping utilizing " activation " as described above to operate under the state of the vacuum degree that forms, electron emission device as described above is measured electron emission characteristic.Measurement is performed such: utilize power supply 51 to apply potential pulse between auxiliary electrode 2 and auxiliary electrode 3, and anode electrode 54 applies 1KV.Distance H between anode electrode 54 and the device is set to 4 millimeters.Therefore, with Fig. 9 in identical non-linear voltage-device current characteristic together, observed the good electron emission characteristics.

[comparative example 1]

For comparative example 1, used palladium oxide film as conducting film 4.In addition, " excitation is shaped " operation is what to carry out in containing the atmosphere of hydrogen as reducible gas.Otherwise, produced the film identical with example 1.

Here, used three kinds of palladium oxide films conducting film 4 of example 1 as a comparison, as shown in table 2 below.That is, three kinds of samples (all by any formation in three kinds of conducting films 4 shown in following (table 2), first and second auxiliary electrode is connected to this conducting film to each sample) have been produced.Here, the width W of conducting film 4 ', the distance L between the auxiliary electrode or the like (referring to Fig. 2 A) is set to example as described above in identical.In addition, " impedance " in (table 2) is corresponding to the resistance value between the auxiliary electrode.

[table 2]

No.	Average film thickness	Impedance
No.	Average film thickness	Impedance	6	15nm	3kΩ
7	10nm	20kΩ	6	15nm	3kΩ
7	10nm	20kΩ	8	5nm	40kΩ

In " excitation is shaped " operation, the inside of vacuum tank 55 is vented to and is no more than 10 ^-5Pa; After this, introduce reducible gas (N ₂: 98% and H ₂: 2%), the pressure in vacuum tank 55 reaches 1.3 * 10 ^-3Pa; Between auxiliary electrode 2 and auxiliary electrode 3, repeatedly apply potential pulse.The impulse waveform of using in " excitation is shaped " operation is different from the impulse waveform of example as described above, and it has used the triangular wave pulse with constant peak value as shown in Figure 3A.Adopted the pulse duration of T1=1 millisecond, and the pulse spacing of T2=10 millisecond.

Shown result in the below described table 3 to " excitation is shaped " operation of each sample of this comparative example.Five identical conducting films 4 (No.6-1 is to No.6-5) of No.6 are provided here.In addition, No.6-1 accepts to utilize respectively " excitation is shaped " operation of different magnitudes of voltage (2V, 10V, 8V, 25V and 30V) execution to five conducting films 4 of No.6-5.

Here, when carrying out " excitation is shaped " operation, the maximum current that flows between auxiliary electrode 2 and auxiliary electrode 3 is defined as the electric current that is shaped: I _Form, and the voltage that applies between auxiliary electrode 2 and auxiliary electrode 3 is defined as the voltage that is shaped: V _FormThe summation of shaping electric current as described above and shaping voltage is defined as the power that is shaped: P _FormIn addition, be defined as curring time from " excitation be shaped " operation beginning reaches the resistance value of the conducting film 4 before " excitation is shaped " operation up to the resistance value (resistance value between auxiliary electrode 2 and the auxiliary electrode 3) of conducting film 4 1000 times the required time of resistance value: T _Form

[table 3]

No.	I _form [mA]	V _form [V]	P _form [mW]	T _form (sec]
No.	I _form [mA]	V _form [V]	P _form [mW]	T _form (sec]	6-1	30	30	900	0.01
6-2	20	25	500	0.1	6-1	30	30	900	0.01
6-2	20	25	500	0.1	6-3	10	18	180	500
6-4	5	10	50	1600	6-3	10	18	180	500
6-4	5	10	50	1600	6-5	100	2	200	3500
7	2	20	40	1500	6-5	100	2	200	3500
7	2	20	40	1500	8	2	25	50	1300

The result of the conducting film 4 of No.6 (No.6-1 is to No.6-5) at first, will be described.

At V _FormBe under the situation of No.6-4 of 10V, find P _FormPresent minimum value.So, using under the situation of palladium oxide as the metal oxide of conducting film 4, finding in reducible (or polymerization) gas, to carry out " excitation is shaped " operation and can make V _FormDescend, therefore also make P _FormDescend.

Next, the conducting film 4 (No.7 and No.8) that description is had the impedance of the conducting film that is higher than No.6.Here, in table 3, only shown to make P _FormMinimum condition.Shown the situation that applies different mutually voltage (20V and 25V) to conducting film 4.

For the sample of conducting film 4, find that any situation all needs about 1000 to 2000 seconds T with No.7 and No.8 _Form, but can make P _FormDescend.

Here, for the sample of No.6, when attempting not using reducible gas to carry out " excitation is shaped " operation, under the shaping voltage of 25V, can not in one hour, finish shaping operation at 2V to No.8.That is power is indispensable with shortening the operating time in " excitation shaping operation " to reducing, to find to utilize reducible gas.

Next, shown result below in the described table 4 to comprising that No.1 shown in the example carries out same inspection to the sample of the conducting film 4 of No.5.Here, the impulse waveform of using in " excitation is shaped " operation is different from the impulse waveform of example as described above, and it has used the triangular wave pulse with constant peak value shown in Fig. 5 A.Adopted the pulse duration of T1=1 millisecond, and the pulse spacing of T2=10 millisecond.In addition, different with comparative example as described above, when carrying out " excitation is shaped " operation, do not use reducible gas.

[table 4]

No.	I _form[mA]	V _form[V]	P _form[mW]	T _form[sec]
No.	I _form[mA]	V _form[V]	P _form[mW]	T _form[sec]	1	2.6	50	130	0.01
2	2.6	20	52	0.01	1	2.6	50	130	0.01
2	2.6	20	52	0.01	3	3	15	45	0.01
4	7	8	56	0.01	3	3	15	45	0.01
4	7	8	56	0.01	5	25	5	125	0.01

Along with the content ratio of the Pd in the conducting film 4 becomes higher, can make V _FormBecome lower.Yet, described as top example under the situation of the sample of conducting film with No.1 and No.5, even carried out " activation " operation, can not obtain enough electron emission amounts.

Here, particular importance a bit be, for having the sample of No.2 to the conducting film of No.4, P _FormSmaller, be approximately the level of 50mW, T _FormVery short, be 0.01 second level.Because T _FormIt is 0.01 second; Pulse duration is the T1=1 millisecond; Pulse spacing is the T2=10 millisecond, finds that only applying the primary voltage pulse basically can form good gap 7.

As described at comparative example, under the situation that conducting film 4 execution " excitation is shaped " of adopting the common metal oxide are operated, subsidiary introducing promotes the gas of conducting film reduction (or polymerization), finally can realize the low P of about 50mW _FormYet,, need not to use reducible gas just can realize low P for conducting film of the present invention (for example, No.2 is to the conducting film of No.4) _FormIn addition, also there is no need to go back the conducting film that the reason metal oxide is made, and can obtain short T _Form

Here, when manipulating reducible gas, it is bigger that shaping power sometimes becomes for " excitation is shaped " of carrying out to the conducting film 4 of No.4 with No.2, and this does not meet wish.Its reason is that the conductive mechanism of conducting film 4 changes.Therefore, in the present invention, in practice, the atmosphere in " excitation is shaped " operation remains on and is no more than 10 ^-5Help to form stable gap 7 under the pressure of Pa, therefore more preferably.

In addition, No.2 to the electron emission characteristic of the sample of No.4 with the sample of No.6-3 have been carried out " activation " operation identical with example 1 roughly suitable with the electron emission characteristic after " stabilisation " operation.And the fluctuation ratio No.2 of electron emission amount is low to the sample of No.4.Infer that its reason is: when carrying out " excitation is shaped " operation, the conducting film of the sample of No.6-3 is reduced, and by contrast, No.2 does not have reduction to the conducting film of the sample of No.4, and still keeps high impedance status.

So, according to the present invention, in " excitation is shaped " operation, can balance low-power (P _Form) and short operation time (T _Form), and can obtain the good electron emission characteristics.

[example 2]

The standard deviation of the granularity in this example is greater than the standard deviation in the example 1.

(process a)

Owing to identical in example 1, on soda-lime glass, form silicon dioxide layer, auxiliary electrode (2 and 3) and conducting film 4, therefore will omit its explanation here.In addition, identical in the width W of thickness of electrode, electrode distance L, conducting film 4 ' also and the example 1.

Here, by the corresponding sputtering power generation sample of control CoO and Pd, to comprise CoO and the Pd that comprises in the conducting film 4, its granularity is different from the granularity (referring to following described (table 5)) in the example 1.The particle mean size both of CoO and Pd is set to 15 nanometers, and standard deviation is 5 nanometers, greater than the standard deviation in the example 1.The average film thickness of conducting film 4 also is 15 nanometers.Here, identical with example 1 in this example, the ratio of the impedance of the impedance of cobalt oxide (CoO) (first particle) and palladium (Pd) (second particle) is CoO: Pd=150: 1.

[table 5]

No.	CoO content is than Pd content ratio	Impedance (conducting film)
No.	CoO content is than Pd content ratio	Impedance (conducting film)	9	100％ 0％	40kΩ
10	60％ 40％	6kΩ	9	100％ 0％	40kΩ
10	60％ 40％	6kΩ	11	50％ 50％	4kΩ
12	30％ 70％	1.5kΩ	11	50％ 50％	4kΩ
12	30％ 70％	1.5kΩ	13	2％ 98％	400Ω
14	0％ 100％	300Ω	13	2％ 98％	400Ω

((process d) operated in process-b), " activations " operation (process c) and " stabilisation " in " excitation be shaped " operation that in six samples as described above (No.9 is to No.14) each has all been accepted below will describe.

(process b)

Between first auxiliary electrode 2 and second auxiliary electrode 3, apply potential pulse, to carry out " excitation is shaped " operation.Pressure in the vacuum tank is identical with example 1 with the pulse that applies to conducting film, will omit its explanation here.

For the sample of the conducting film 4 that comprises No.9, gap 7 utilizes peak value of pulse 100V to form.Yet the gap 7 of formation comprises a plurality of (dispersing) gaps that separate.

For the sample of the conducting film 4 that comprises No.10, gap 7 utilizes peak value of pulse 25V to form.

For the sample of the conducting film 4 that comprises No.11, gap 7 utilizes peak value of pulse 16V to form.

For the sample of the conducting film 4 that comprises No.12, gap 7 utilizes peak value of pulse 10V to form.

For the sample of the conducting film 4 that comprises No.13, gap 7 utilizes peak value of pulse 5V to form.

For the sample of the conducting film 4 that comprises No.14, gap 7 utilizes peak value of pulse 5V to form.

Yet first gap 7 of formation does not have to arrive the other end (referring to Fig. 2 A) in the direction of the width (W ') of conducting film 4 from an end.

Measured and comprised that No.10 is to first auxiliary electrode 2 of the sample of the conducting film 4 of No.13 and the resistance value between second auxiliary electrode 3, discovery before carrying out " excitation is shaped " operation and afterwards, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 has increased and has been not less than binary digit (being not less than 100 times).In addition, as the result who utilizes electron microscope that the pattern in gap 7 is observed, comprising that No.10 is under the situation of the sample of the conducting film 4 of No.13, from the end to end of conducting film 4, in the direction of the direction of auxiliary electrode 3, form gap 7 continuously being substantially perpendicular to auxiliary electrode 2.

On the other hand, for the conducting film 4 of No.9, as shown in Figure 6A, having formed a plurality of (dispersing) gaps that separate, also is from macroscopic view, and conducting film 4 is not separately.In addition, the also non-constant width of the width in the gap 7 of formation (auxiliary electrode 2 is towards the length of the direction of auxiliary electrode 3) even carried out " activation " operation that below will describe, still can not obtain desired electron emission characteristic.And, a plurality of separated gaps have been formed, shown in Fig. 6 C for the conducting film 4 of No.14.In addition, for the sample of the conducting film 4 that comprises No.9 and No.14, the resistance value after execution " excitation shaping " is operated between auxiliary electrode 2 and the auxiliary electrode 3 is approximately execution and " encourages and be shaped " 10 times that operate resistance value before.

(process c)

After process b as described above, comprise that No.10 as described above accepts " activation " operation to the sample of the conducting film of No.13.Pressure in the vacuum tank (having introduced gas) is identical with example 1 with the pulse that applies to conducting film, will omit its explanation here.

For any sample, the electric current that flows between auxiliary electrode 2 and auxiliary electrode 3 all can increase along with the time.When the electric current that flows between auxiliary electrode 2 and auxiliary electrode 3 reached about 1mA, " activation " operation was finished.By carrying out " activation " operation, the first carbon film 21a and the second carbon film 21b in any sample, have all been formed, shown in Fig. 1 C.Here, between the first carbon film 21a and the second carbon film 21b, form second gap 8, on the surface of the substrate 1 that is positioned at second gap 8, formed recessed portion 22.

(process d)

After process c, carry out " stabilisation " identical with example 1 and operate.

Produced by process as described above and to have had the electron emission device of No.10 to the conducting film of No.13.Keeping utilizing " stabilisation " to operate under the state of the vacuum level that forms, measure electron emission characteristic, therefore, observed the nonlinear voltage-device current characteristic identical with Fig. 9.

Yet the electron emission characteristic of the sample of No.10 (particularly electron emission amount) is lower than the electron emission characteristic of the sample of the No.2 in the example 1.Other samples also are lower than those samples in the example 1 aspect electron emission characteristic, still, and as the not appearance of remarkable reduction of the electron emission characteristic in the sample of No.10.This standard deviation of sample that is attributable to example 2 is greater than the standard deviation of the sample of example 1.

As described above, under the significant situation of standard deviation, conducting film 4 desired conditions will be somewhat different than the condition that is used for example 1.

Result as this example, be 150 and allow standard deviation to reach under the situation of 33.3% (≠ 5nm/15nm * 100) of particle mean size at impedance ratio, the ratio of first particle that comprises in the conducting film 4 is set to so just can obtain the good electron emission characteristics between being not less than 2% and be not more than in 50% the scope.

Here, impedance ratio described be 150 situation, still, if impedance ratio is between being not less than 50 and be not more than in 400 the scope; If standard deviation is not more than 33.3%; And if the ratio of first particle is set to then can obtain the good electron emission characteristics between being not less than 2% and be not more than in 50% the scope.

[example 3]

This example is the particle that constituted conducting film 4 is different from the analog value in example 1 and the example 2 aspect impedance ratio and granularity a situation.Production process is almost identical with example 2 with example 1, therefore, will only describe different parts below.

(process a)

Owing to such in example 1, on soda-lime glass, formed silicon dioxide layer, auxiliary electrode (2 and 3) and conducting film 4, will omit its explanation here.In addition, the width W of thickness of electrode, electrode distance L, conducting film 4 ' also and example 1 and 2 is identical.

Here, produce sample by the corresponding sputtering time of controlling corresponding material, to comprise CoO and the Pd that comprises in the conducting film 4, its granularity is different from the granularity (referring to following described (table 6)) in example 1 and the example 2.In addition, for any sample, the content of the CoO that comprises in the conducting film 4 is than all being set to 2%.

Here, in this example, for the sample of No.15, the ratio of the impedance of cobalt oxide and the impedance of palladium was set to 10: 1; For the sample of No.16, it is 50: 1; For the sample of No.17, it is 150: 1; For the sample of No.18, it is 400: 1; For the sample of No.19, it is 1000: 1.In addition, the cobalt oxide in each sample and the particle mean size of palladium (corresponding to the average film thickness of conducting film 4) are set to 5 nanometers for the sample of No.15; Sample for No.16 is set to 7 nanometers; Sample for No.17 is set to 15 nanometers; Sample for No.18 is set to 20 nanometers; Sample for No.19 is set to 50 nanometers.The standard deviation of the granularity in each sample is set to 13.3% of particle mean size.

[table 6]

No.	CoO content ratio	Pd content ratio	Film thickness	Impedance (conducting film)
No.	CoO content ratio	Pd content ratio	Film thickness	Impedance (conducting film)	15	2％	98％	5nm	1200Ω
16	2％	98％	7nm	800Ω	15	2％	98％	5nm	1200Ω
16	2％	98％	7nm	800Ω	17	2％	98％	15nm	300Ω
18	2％	98％	20nm	130Ω	17	2％	98％	15nm	300Ω
18	2％	98％	20nm	130Ω	19	2％	98％	50nm	50Ω

Five samples as described above are accepted " excitation is shaped " operation (process b) respectively in vacuum tank 55 as shown in Figure 8, form good gap 7 in all samples.

In addition, identical with example 1 with example 2, comprise that No.15 accepts " activation " operation and " stabilisation " operation to the sample of the conducting film of No.19.After this, keeping utilizing " stabilisation " to operate measurement electron emission characteristic under the state of the vacuum level that forms, therefore, in the sample of No.18, observed the good electron emission characteristics identical at No.15 with the sample 11 to 13 of the sample 2 to 4 of example 1 and example 2.Yet, the sample of No.19 low than in example 1 and the example 2 aspect electron emission characteristic.Infer that this is attributable to particle mean size and standard deviation.

[example 4]

Identical with example 2, example 4 is to make the example of the standard deviation of granularity greater than the standard deviation of example 3.To describe below for each sample in the example 4, the standard deviation of granularity is set to 33.3% situation of particle mean size.

(process a)

Owing to identical in example 1, on soda-lime glass, formed silicon dioxide layer, auxiliary electrode (2 and 3) and conducting film 4, will omit its explanation here.In addition, identical in the width W of thickness of electrode, electrode distance L, conducting film 4 ' also and example 1 and 2.

Here, the corresponding sputtering time and the sputtering power of the corresponding material by control CoO and Pd, CoO that comprises in the control conducting film 4 and the particle mean size (corresponding to the film thickness in following described [table 7]) of Pd.Here, for any sample, the content of CoO ratio is set to 2%.

Here, in this example, for sample 20, the ratio of the impedance of cobalt oxide and the impedance of palladium was set to 10: 1; Be set to 50: 1 for sample 21; For sample 22 for being set up 150: 1; Be set to 400: 1 for sample 23; Be set to 1000: 1 for sample 24.Impedance ratio is identical with impedance ratio in the example 3, and standard deviation (σ) is set to 33.3%.

[table 7]

No.	CoO content ratio	Pd content ratio	Film thickness	Resistance (conducting film)
No.	CoO content ratio	Pd content ratio	Film thickness	Resistance (conducting film)	20	2％	98％	5nm	1500Ω
21	2％	98％	7nm	1000Ω	20	2％	98％	5nm	1500Ω
21	2％	98％	7nm	1000Ω	22	2％	98％	15nm	400Ω
23	2％	98％	20nm	200Ω	22	2％	98％	15nm	400Ω
23	2％	98％	20nm	200Ω	24	2％	98％	50nm	60Ω

Five samples as described above are accepted excitation shaping operation (process b) respectively in vacuum tank 55 as shown in Figure 8.

(process b)

Between first auxiliary electrode 2 and second auxiliary electrode 3, apply potential pulse, to carry out " excitation is shaped " operation.Identical in pressure in the vacuum tank and the pulse that applies to conducting film 4 and the example 1 will be omitted its explanation here.

For the sample of the conducting film 4 that comprises No.20, gap 7 utilizes peak value of pulse 10V to form, and still, the deviation of the width in first gap 7 of formation is greater than the sample of No.21 to No.23.

For the sample of the conducting film 4 that comprises No.21, gap 7 utilizes peak value of pulse 6V to form.

For the sample of the conducting film 4 that comprises No.22, gap 7 utilizes peak value of pulse 5V to form.

For the sample of the conducting film 4 that comprises No.23, gap 7 utilizes peak value of pulse 5V to form.

For the sample of the conducting film 4 that comprises No.24, gap 7 utilizes peak value of pulse 3V to form, and still, the deviation of the width in first gap 7 of formation is greater than the sample of No.21 to No.23.

Measured and comprised that No.21 is to first auxiliary electrode 2 of the sample of the conducting film 4 of No.23 and the resistance value between second auxiliary electrode 3, discovery before carrying out " excitation is shaped " operation and afterwards, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 has increased and has been not less than binary digit (being not less than 100 times).In addition, as the result who utilizes electron microscope that the pattern in gap 7 is observed, comprising that No.21 is under the situation of the sample of the conducting film 4 of No.23, from the end to end of conducting film 4, in the direction of the direction of auxiliary electrode 3, form gap 7 continuously being substantially perpendicular to auxiliary electrode 2.As for comprising that No.20 is to first auxiliary electrode 2 of the sample of the conducting film 4 of No.24 and the resistance value between second auxiliary electrode 3, with afterwards, the resistance value between first auxiliary electrode 2 and second auxiliary electrode 3 has roughly increased binary digit before execution " excitation is shaped " operation.In addition, the non-constant width of the width in the gap 7 that in the conducting film 4 of No.20, forms (in the length of auxiliary electrode 2 in the direction of auxiliary electrode 3).

After process b as described above, No.20 as described above accepts " activation " as described above operation and " stabilisation " operation to the sample of No.24.After this, keeping utilizing " activation " as described above to operate under the state of the vacuum level that forms, measure corresponding electron emission characteristic.Measurement is performed such: utilize power supply 51 to apply potential pulse between auxiliary electrode 2 and auxiliary electrode 3, and anode electrode 54 applies 1KV.Distance H between anode electrode 54 and the device is set to 4 millimeters.Therefore, though No.21 is lower than No.16 in the example 3 to the sample of No.19 to the sample of No.23 aspect electron emission characteristic,, on the whole, still can obtain the good electron emission characteristics.In addition, the sample of No.20 and No.24 has been accepted " activation " operation, and is still, however, much lower to the sample of No.24 than No.20 aspect electron emission characteristic.

As described above, under the relatively more significant situation of standard deviation, conducting film 4 desired conditions will be different from the condition that is used for example 3.As in this example, than being under 2% the situation, allowing standard deviation to reach under 33.3% the situation at the content of first particle, utilize between being not less than 50 and be not more than impedance ratio within 400 the scope, can obtain the good electron emission characteristics.Here, the content of having described first particle is than the situation that is 2%, but for the content of first particle than between being not less than 2% and be not more than situation in 50% the scope, be not more than at the standard deviation of granularity under 33.3% the situation of particle mean size, utilization can obtain the good electron emission characteristics between being not less than 50 and be not more than impedance ratio within 400 the scope.

As described above, according to the present invention, can in the conducting film of electron emission device, form the electric field concentrated area in advance, therefore, it is little can making the electric current that flows in conducting film when carrying out " excitation is shaped " operation, and has big surplus, can also shorten the operating time simultaneously.That is,, can in the quite short time, utilize the power consumption that is equivalent to use conventional reducible gas to carry out the saving of " excitation is shaped " operation to carry out " excitation is shaped " operation according to the present invention.

Though be to describe of the present inventionly with reference to one exemplary embodiment, should be appreciated that the present invention is not limited only to illustrated one exemplary embodiment.The scope of following claim should have the most widely to be explained, so that comprise all such modifications and equivalent structure and function.

Claims

1. method of making electron emission device,

Comprise the process that makes electric current flow through film, this film comprises: (a) many first particles of being made by first kind of material, and (b) many its impedances are lower than the impedance of first particle and second particle of being made by the second kind of material that is different from described first kind of material, thereby in the part of described film, form the gap

It is characterized in that described film satisfies following condition (i) any one condition in (iii):

(i) ratio of described first particle that comprises in the described film is not less than 2% and be not more than 30%, and the ratio of the impedance of the impedance of described first particle and described second particle is not less than 5 and be not more than 1000;

The ratio of described first particle that comprises in the (ii) described film is not less than 2% and be not more than 40%, and the ratio of the impedance of the impedance of described first particle and described second particle is not less than 5 and be not more than 800; And

The ratio of described first particle that comprises in the (iii) described film is not less than 2% and be not more than 60%, and the ratio of the impedance of the impedance of described first particle and described second particle is not less than 5 and be not more than 400.

2. method of making electron emission device,

Comprise the process that makes electric current flow through film, this film comprises (a) many first particles of being made by first kind of material, and, (b) many its impedances are lower than the impedance of first particle and second particle of being made by the second kind of material that is different from described first kind of material, thereby in the part of described film, form the gap

It is characterized in that described first proportion of particles that comprises in the described film is not less than 2% and be not more than 50%;

The ratio of the impedance of the impedance of described first particle and described second particle is not less than 50 and be not more than 400; And

The standard deviation of described first particle and described second particle is not more than 33.3% of particle mean size.

3. the method for manufacturing electron emission device according to claim 1 and 2, it is characterized in that, described film is placed like this, so that first auxiliary electrode is connected with second auxiliary electrode, between first auxiliary electrode and second auxiliary electrode, apply potential pulse, thereby described electric current flows in described film.

4. the method for manufacturing electron emission device according to claim 1 and 2 is characterized in that, described first particle and described second particle are inhomogeneous mixing.

5. the method for manufacturing electron emission device according to claim 1 and 2 is characterized in that, described electric current is being no more than 1 * 10 ^-5In described film, flow under the pressure of Pa.

6. the method for manufacturing electron emission device according to claim 1 and 2 is characterized in that, the particle mean size of described first particle and second particle is not less than 5 nanometers and is not more than 20 nanometers.

7. a manufacturing comprises the method for the electron source of a plurality of electron emission devices, it is characterized in that, each in described a plurality of electron emission devices all utilizes claim 1 or 2 described manufacture methods to make.

8. method of making image display, this equipment comprise electron source and utilize from the luminous component of this electron source electrons emitted irradiation, it is characterized in that described electron source utilizes manufacture method according to claim 7 manufacturing.