WO2004095494A1 - Electron-emitting material, its producing method, electron-emitting device using same, and image drawing device - Google Patents

Abstract

An electron-emitting material having a field-emission start voltage or work function smaller than conventional ones. The material comprises a substrate (102) and a graphite sheet (101) laminated on the substrate (102). (1) The graphite sheet (101) has a structure in which graphenes each composed of a carbon hexagonal network surface are layered, (2) the graphemes are so stacked that the c-axis direction of each grapheme is substantially perpendicular to the surface of the substrate (102), (3) the graphite sheets (101) is so laminated on the substrate (102) that the c-axis direction of each grapheme is substantially perpendicular to the surface of the substrate (102), and (4) the graphite sheet (101) each contains an element other than carbon as a second element.

Description

 Electron emitting material, its production and its use, electron leakage element and U-shaped device

 The present invention relates to a sculpture-emitting material used for a display, a mf, an emitter, a lamp, an electric device, and the like, and a method for producing the same. Further, the present invention relates to an electron element and a surface image drawing apparatus using a light emitting material.

 Akira Keisuke Seta

 In recent years, there has been an increasing demand for thinner display devices, larger area, lower power consumption, and the like for display devices. In order to respond to such demands, it has been studied that shelves can be provided with cold electron sources with few electron sources.

 In 1991, a carbon nanotube, a cylindrical carbon material with a diameter of just 10 nm and a length of several μm, was developed. Until it was developed, a display using a Spindt-type (for example, Journal of Applied Physics, Vol. 39, No. 7, P3504 (1968)), a cold-type display made of conical metal, was used. Many have been reported. However, carbon nanotubes not only have excellent electrical conductivity, conductivity, and corrosion resistance of carbon materials, but also have a very small curvature. For this reason, carbon nanotubes are expected to be high-efficiency, robust, and stable electronic devices even in power. Therefore, the mainstream of R & D has begun to shift to carbon nanotubes (for example, Applied Physics Letters, Vol. 78, No. 4, P 539 (2001)).

On the other hand, Japanese Patent Application Laid-Open No. 2000-178016 discloses that an artificial graphite sheet can be obtained by increasing a polymer sheet in two stages. This graphite sheet is a carbon material (excellent electrical conductivity, conductivity, corrosion resistance, excellent flexibility, and a polymer sheet can be used to form a large sheet easily. It has 赚. List of other documents related to the present invention

 (1) Japanese Patent Application Laid-Open No. H10-269929: This publication describes that the emitter composition consisting of a photoresist (辦, indicated by reference numeral 21 on the front page of the publication) includes argon, phosphorus, boron, and carbon. There is disclosed a method of manufacturing an electron emission emitter formed by illuminating some of the ions.

 (2) US Patent No. 5863467 (Japanese Unexamined Patent Application Publication No. 11-1621): This gazette will be described later.

 (3) Japanese Patent Laid-Open Publication No. 2003-16908: This publication discloses an electron having an electron-emitting layer made of graphite or the like (indicated by reference numeral 5 in FIGS. 1 and 4 (e) of the publication). An emissive element is disclosed.

 (4) Japanese Patent Application Laid-Open No. H10-188778 (particularly, step No. 0066): This publication discloses a carbon body formed with male fine particles (reference numeral 21 in FIGS. 1 and 2 of the publication) as cores (reference numeral same as above). 22) An electron formed by arranging a plurality of electron emitters (5) terminated by a low work fee (23), such as lithium, on the (3) An emissive element is disclosed. JP-A-11-40044 can be mentioned as a publication related to this publication.

 (5) Japanese Patent Application Laid-Open No. Sho 62-91413: This publication discloses a semi-metal / metal multilayer material structure obtained by ion-implanting carbon in the c-axis direction of lamellar dalafite.

 (6) JP 2001-288625 ^ A: This publication includes a graphene sheet having a truncated ice cream cone shape (reference numeral 12 in FIG. 2 of the publication). ), A graphitic nano-fino material having a circular separation and the like stacked through the layer is disclosed. It is also disclosed that this graphite nanofino material is used as an electron emission source.

(7) Japanese Unexamined Patent Publication No. 2-174059: In this publication, a lithium ion-containing graphite compound thin film was dedoped by this lithium ion force and a defect was left in a portion where the lithium ion was present. Lithium containing graphite thin film crystallized as-is and doped lithium ions A solid-state positive electrode is disclosed.

(8) Japanese Patent Application Laid-Open Publication No. 2000-3-17780669: Date of filing of Japanese patent application (Japanese Patent Application No. 2003-1131641) This publication, which was published after this date, includes a graphite layer (reference numeral 4003 in FIG. 4 of the same publication) that adsorbs impurities such as Cs and Ba with ions ¾λ ^ ¾¾¾¾, It is disclosed that a cooling is obtained by performing a force ration. In addition, the graphite caused by the laser annealing shows that the connection in either direction between the planes and in the plane is not high (4 is also high. In addition, the formation of the ^^ J formed by the intercalation depends on the impurity species and the stage. MC by the order n _{m. n} (m is 6 or 8 ^ T.) and order to be defined, the impurity concentration is made to exceed 3%. disclosure of the invention

 However, a method for producing a large amount of carbon nanotubes having a single structure at low cost is still under development. In addition, the process of forming the discharge portion, which is excellent in uniformity and uniformity over time, has not been performed.

 On the other hand, the graphite sheet has excellent electrical conductivity, conductivity, and corrosion resistance of the carbon material, and can form a large-sized sheet having a uniform thickness, so that an electron-emitting portion such as a large-area display device can be formed. It is a material suitable for. However, since the surface does not have a structure with a curvature as small as a carbon nanotube on the surface, a large field emission start is required.

 The work function is an important value in describing the release characteristics along with the size of m release start £. When the work function is small, the amount can be increased with a small ¾Ε change. However, the magnitude of the work function is determined by the electronic state of the material that contributes to the emission. For this reason, even if a carbon material whose graphite is well defined and a structure having a curvature similar to that of a carbon nanotube is formed, performance exceeding that of a carbon nanotube cannot be obtained.

 The present invention provides an electron emission material that has excellent electric conductivity, conductivity, and corrosion resistance of a carbon material, has a small field emission start and work function, and can display a large-area display device. Its main purpose is to:

That is, the present invention provides the following electron-emitting sheet material, its manufacturing method, and The present invention relates to a used electronic thigh element and an image drawing element.

 1. An electron emission sheet comprising (102) and a graphite sheet (101) drawn on (102),

 (1) tilf self-graphite sheet (101) force It has a structure viewed as a graphenka layer consisting of multiple carbon hexagonal mesh planes.

 (2) the dalaphens are arranged so that the c-axis direction of each dalafen is substantially perpendicular to the substrate (102) plane,

 (3) The graphite sheet (101) is placed on ESt and (102) so that the c-axis direction of each graphene is substantially perpendicular to the IfifSSlg (102) plane.

 (4) tfflB graphite sheet (101) Force S, including elements other than carbon as the second element,

Electron emission sheet material.

2. An electron-emitting sheet material of the 1st fiber, wherein the peak of the (002 ⁿ ) plane (where n is a natural number) is & in the X-ray diffraction pattern of the graphite sheet.

 3. The #f | 5¾l electron-emitting sheet material whose peaks on the (002) and (004) planes in the X-ray diffraction pattern of the terrible graphite sheet.

 4. An electron-emitting sheet material as described in | ίίΐΒ¾1 where the second element of ffrlE is between the layers of dalaphen.

 5. A m ^ 1 f mfe electron emission sheet material in which the concentration of the second element of SfllE is 0.001 to 3 atomic%.

 6. The electron-emitting sheet material according to t1, wherein the concentration of the disgusting second element is 0.005 atomic% or more and 2 atomic% or less.

 7. The concentration of the second element is 0.01 atom. /. The electron-emitting sheet material according to item 1 above, which is not less than 1 atomic%.

 8. The electron-emitting sheet material according to the above item 1, wherein the thickness of the sheet is 10 μm or more and 1000 μm or less.

9. An electron-emitting sheet material of tffil 1 in which part or all of the second element forms a surface layer from the sheet surface to a depth of 10% of the sheet thickness. 10. An electron emission sheet material according to claim 1, wherein the second element is at least one element selected from the group consisting of Al-Li element and Al-earth element ^ S element.

 11. An electron-emitting sheet material having a modest e> 1 in which the second element is at least one of Li, Na, K, Cs, Rb, Ca, 3]: and 8 &.

 12. The electron-emitting sheet material according to | 1¾ ^ 1, wherein the second element is at least one of nitrogen and crane.

 13. The electron emission sheet material according to item 5.1, wherein the second element is at least one of rare gas elements.

 14. The electron emission sheet material of the preceding Kg 1 wherein the second element is at least one of Ne, Ar, Kr and Xe.

 15. The second element is 1) to 3) below;

 1) At least one of the elements and elements

2) at least one of nitrogen and

 3) At least one rare gas element

 The electron emission sheet material according to fiJtS¾1, wherein the two or three yarns are:

 16. Manufacture of electron emission sheet Byeon, including fiber (102) and graphite sheet (101) laminated on SiltfiS ^ (102):

 (1) The terrible graphite sheet (101) has a structure in which graphite composed of a plurality of carbon hexagonal mesh planes is laminated in layers.

 (2) Each dalaphen is stacked so that the c-axis direction of each graphene is substantially perpendicular to the ffffBSK (102) plane.

 (3) The graphite sheet (101) is laminated on the substrate (102) such that the c-axis direction of each graphene is substantially perpendicular to the filtS¾t anti- (102) plane. So,

 A method for producing an electron-emitting sheet material, comprising a second element applying step of applying a second element other than carbon as an atom, molecule or cluster to a disgusting graphite sheet.

 17. After the step of adding 2 mm elements, the key further comprises a step of further heat-treating the key Dalafite sheet.

18. The disgust second element application process a) ion implantation step of implanting at least one kind of atom and cluster ionized as a second element into a graphite sheet;

 Made of «6« electron-emitting sheet material

 1 9.

 b) A radical irradiation step of irradiating at least one of the radicalized atoms, molecules and clusters as a second element on a graphite sheet

 A method for producing an electron emission sheet material of fiitffig l 6 | ¾¾ having the following.

 20. The tooth second element application process

 c) Neutral substance reaching process in which at least one kind of electrically neutral atoms, molecules and clusters as the second element reaches the graphite sheet.

 Made of fijfB¾l 6 電子 electron emission sheet material

 The 21.2 element providing step includes the following steps a) to c);

 a) an ion implantation step of implanting at least one kind of atoms, molecules and clusters ionized as a second element into a dalaphite sheet;

 b) a radical irradiation step of irradiating at least one of the radicalized atoms, molecules and clusters as a second element on a graphite sheet; and

 c) A process for reaching at least one of electrically neutral atoms, molecules and clusters as the second element to the graphite sheet.

The production of the electron-emitting sheet material according to the above item 16 having two or three types of processes at¾¾ ₀

 2 2. A method for producing an electron-emitting sheet material of tiltffiil 6 words obtained by attacking a polymer sheet with a Daraphyte sheet.

 2 3. The polymer sheet is made of polyphenylene oxadiazole, polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazolone, polythiazonole, polyamide, polyimide, polyamide. A method for producing an electron-emitting sheet material according to Item 22 which is at least one of imide and polyacrylonitrile.

 2 4. Self-polymer sheet force Manufacture of the electron emission sheet material described in 22.

2 5. The electrode according to 22, wherein the ttl polymer sheet is an aromatic polyimide. ^ Of child release sheet material

 26. A first heat treatment step in which the temperature is increased from the first tB¾ in the gas at the first temperature and calcined at a temperature of 1000 ° C or more and less than 2500 ° C in the gas; A second heat treatment step of firing at 2500 ° C. or higher at a second rate from the second start in an inert gas after the step, and producing the electron emission sheet material according to item 22.

27. The production of the electron-emitting sheet material according to the above item 16, wherein in the X-ray diffraction pattern of the graphite sheet, the peak of the (002 ⁿ ) plane (where n represents an axis) is infinite. Wind

 28. In the X-ray diffraction pattern of the graphite sheet, the peaks of the (002) plane and the (004) plane are found.

 29. 嫌 The second element disturbed between layers of graphene, i

6 words S ^ 'ife of electron emission sheet material of E¾

30. Kenonore concentration of the second element, 0.001 atomic _^0/0 to 3 atoms _^0/0 or less, the production of electron-emitting sheet material of the knitted E¾i 6 wherein Hiroshi

31. the concentration of the second element is not less than 0.005 atomic% and not more than 2 atomic%;

Production of the electron emission sheet material described in 6

 32. The method for manufacturing an electron-emitting sheet material according to item 16, wherein the concentration of the second element is 0.01 atomic% or more and 1 atomic% or less.

 33. The thickness of the sheet is 10 μm or more and 1000 μm or less ||

 34. Part or all of the second element Force The method for producing an electron emission sheet material according to item 16, wherein the surface layer is formed from the sheet surface to a depth of 10% of the sheet thickness.

 35. The second element is at least one of an alkali metal element and an earth metal element. | Ίί ¾16.

 36. The electron emission sheet material according to item 16, wherein the second element is at least one of Li, Na, K, Cs, Rb, Ca, 3]: and 8 &

37. The second element is at least one of nitrogen and old ΙΐΒΐΙ 16 Of electron emission sheet material

 38. The second element is at least one of the noble gas elements.

 39. The material for an electron emission sheet of item 16 above, wherein the second element is at least one of Ne, Ar, Kr, and Xe.

 40. The second element is 1) to 3) below;

 1) At least one of the male element and the earth element ^ M element

2) at least one of nitrogen and

 3) At least one rare gas element

 Item 17. Manufacturing of the electron-emitting sheet material according to item 16, which is a combination of two or three of the following.

 41. An electron-emitting device comprising an electron-emitting sheet material, a conductive gate layer and one or more

 The disgusting electron-emitting sheet material includes & (102) and a graphite sheet (101) laminated on ffl ¾¾ (102),

 (1) Graphite sheet (101) Force It has a structure in which graphite consisting of a plurality of hexagonal carbon mesh layers is laminated in layers.

 (2) Each dalafen is stacked so that the c-axis direction of each dalafen is substantially perpendicular to the ffffSSS (102) plane.

 (3) The graphite sheet (101) is placed on the SS plate (102) so that the c-axis direction of each graphene is substantially perpendicular to the ΙίΤΪΕ¾¾ (102) plane,

 (4) ttit self-graphite sheet (101) 1 Including elements other than carbon as the second element,

 が The graphite sheet (101) and the conductive gate layer (106)

(105) are located through

 An electronic wisteria element that makes this possible.

42. Including the anode section having the phosphor layer and the electron W element, the electron section and the electron leakage element are arranged such that the electrons emitted from the self-emitting electron emitting element cause the tilt self phosphor layer to emit light. Phosphor light emitting device, A phosphor light emitting device whose device is a device of Ιίί Ιίί4 II ^.

 4 3. An anode part having a phosphor layer and a plurality of two-dimensionally arranged electrons

An image drawing apparatus including a ¾Ιί element, and a tiilB node portion and an ¾ element arranged so that electrons emitted from the ¾lt element cause the phosphor layer to emit light. An image drawing device in which the element is an element described in tiite¾41.

4 4. A three-dimensional image element that controls the amount of phosphor emission based on the amount of electron emission from each of the plurality of electron-emitting elements. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a process cross-sectional view of an electron-emitting material according to a first embodiment of the present invention, an electron-emitting device manufactured therefrom, and an electronic device using the same.

 FIG. 2 shows a measurement result of an emission current of the electron-emitting device according to the first embodiment of the present invention in response to an applied voltage of 1 KB.

 FIG. 3 is a Fowler-Nordheim plot of the results shown in FIG. FIG. 4 is a process cross-sectional view of an emission region in manufacturing and removing an electron emission material according to Difficult Example 3 of the present invention.

 FIG. 5 is a process cross-sectional view of an electron-emitting material of Example 5 of the present invention and a sculpted emission region in a method for producing the same.

 FIG. 6 is a diagram showing a crystal structure of graphite.

 FIG. 7 is a schematic diagram showing a graph of a graph sheet.

 FIG. 8 is a diagram showing a typical X-ray diffraction pattern of graphite.

 FIG. 9 is a schematic diagram showing a layer structure of a conventional graphite sheet.

 FIG. 10 is a cross-sectional view showing an example of an image forming apparatus in which a plurality of electron leakage elements are two-dimensionally arranged.

 Explanation of reference numerals

 1 0 1 Graphite sheet

 1 0 2

 1 0 3 Adhesive layer

 1 0 4 Rough structure

1 0 5 106 conductive gate layer

 1 0 7 Glass s¾

 1 0 8

 1 0 9 Phosphor layer

 4 0 1 Graphite sheet

 4 0 2 Surface defect

 4 0 3

 5 0 1 Graphite sheet

 5 0 2 Mo fine particles

 5 0 3 Cs, area

 5 0 4 Cs Wei area

 6 0 6 carbon atom

 6 0 7 Graphene shakuzo

 6 1 3 Molded body (Graphite iBg ^ body, diamond: union)

6 1 4 Carbon material (Graphite powder, diamond, particles)

 6 1 5 Highly oriented '14 Graphite sheet

 6 1 6 Dalaphen structure

 7 0 1 Xie

 7 0 2 Electrode layer

 7 0 3 Electronic layer

 7 0 6 Control ¾® (conductive gate layer)

 7 1 3 Phosphor layer

 7 1 4 Anode

 7 1 5 words IJDS¾I

 7 1 8, 719 Dryokuku Best mode for carrying out the invention

 <Electron emission sheet material>

The electron emission sheet material of the present invention comprises: (102)

(102) a graphite sheet (101) laminated thereon; (1) ΙίίϊΕGraphite sheet (101) has a structure in which it is laminated in a graphene force composed of a plurality of carbon hexagonal mesh planes,

 (2) Each graphene is aligned so that the c-axis direction of each dalafen is substantially perpendicular to the finest (102) plane.

 (3) The graphite sheet (101) is laminated on the front IES plate (102) so that the c-axis direction of each dalafen is substantially perpendicular to the (102) plane,

 (4) Guilty Graphite Sheet (101) Force Contains elements other than carbon as the second element.

 (Graphite sheet)

 As shown in Fig. 6, a Dalaphite sheet is a crystal sheet in which carbon atoms 606 constitute a hexagonal carbon plane, and a plane structure composed of a plurality of hexagonal carbon planes. means.

 ^ S ^ f removal of the graphite sheet will be described in detail later. ^ SIJ is used to (1) heat-treat a polymer sheet such as polyimide, and (2) graphite particles together with a polymer binder. β can be mentioned.

 In each of the graphite sheets (1) and (2) described above, since the dalaphen is layered in a layer, the surface of the graphite sheet and the c-axis direction of each dalaphen are substantially perpendicular. In other words, each Dalaphen layer is laminated so that it is almost TO. In addition, (1) and (2), the graphite sheet manufactured by the manufacturing method of (a) and (b) is commercially available.

 In the electron emission sheet material of the present invention, the above graphite sheet constitutes an electron emission region. The above graphite sheet is laminated on a curtain. In this case, (graphite sheet) is laminated on the above-mentioned sheet so that the c-axis direction of each dalafen constituting the graphite sheet is substantially perpendicular to the front IBS plate (102) plane. ing. In other words, the two layers are laminated so that the fiber surface and each graphene layer become almost TO.

The thickness of the graphite sheet of the present invention is not limited, and it can be determined appropriately according to its use, use mode, and the like. For example, for the age used for electron wisteria elements, etc., it is usually 10 m or more and 1000 μm or less, especially It is desirable that

 The graphite sheet is desirably formed with irregularities on its surface. Separation of irregularities is suitable for the desired characteristics! I can decide. It is preferable that the graphite sheet has an uneven structure provided by the following manufacturing method. More specifically, 1) irregularities formed by implanting ionized atoms, molecules, or clusters into a graphite sheet; 2) formation by illuminating radicalized atoms, molecules, or clusters on a graphite sheet Or 3) It is desirable that an uneven structure formed by causing electrically neutral atoms, molecules or clusters to reach the graphite sheet is formed on the surface of the Dalafite sheet.

The sickle can be made from the material of the sickle. For example, glass, ceramics _{(A 1 2 0 3, Z} r O 2 oxide such as ceramics, non-oxide ceramics such as S i ₃ N _4, BN) absolute椽性material such; low resistance silicon, metal ' It is also possible to use conductive materials such as alloys and depleted ^). The thickness of the employment is not limited, and is generally 0.5 to 2 rnm.

 The wisteria and the graphite sheet can be provided with or without a separate layer between them. As another layer, for example, an adhesive layer, m (lower layer, etc.) can be interposed.

 (About the second element)

 The view of the second element can be scaled from elements other than carbon depending on the desired sheet properties.

 For example, at least one of an alkali ^ S element and an alkaline earth element can be used as the second element. In particular, at least one of Li, Na, K, Cs, Rb, Ca, Sr, and Ba can be used. The alkali metal element and the alkaline earth metal element are chemically adsorbed or physically adsorbed on the interlayer or on the surface of Daraphite, so that the work function is reduced and electron emission can be started at a low level.

For example, at least one of nitrogen and nitrogen can be used as the second element. Nitrogen and wisteria not only chemisorb or physically adsorb on the interlayer or decaying surface of Dalaphite, but also change the electronic state by bonding with carbon atoms. be able to.

 For example, at least one of rare gas elements can be used as the second element. In particular, at least one of Ne, Ar, Kr, and Xe can be used for ¾¾. The rare gas element can change the electronic state of graphite by forming carbon atoms and conductive layers between or in layers of graphite. The electron-emitting sheet material of the present invention includes, as a second element, the following 1) to 3);

1) at least one of the elements

2) at least one of nitrogen and wisteria,

 3) At least one rare gas element

 It is preferable to use two or three pairs of ^ :. By using these sets ^ :, it is possible to control the electronic state of graphite more effectively. In particular, by adopting these pairs ^ :, dipole polarization is formed between adjacent elements, the electronic state of graphite changes, the work function decreases, and electron emission starts at low The effect is obtained.

 The content of the second element can be appropriately determined according to the desired sheet properties of the second element, but generally, the content of the second element in the graphite sheet is not less than 0.001 atomic% and not more than 3 atomic%. In particular, it is desirable that the content be contained in the range of 0.05 atomic% to 2 atomic%, and more preferably 0.01 atomic% to 1 atomic%.

 The second element may be present anywhere in the sheet material, but is preferably present on the sheet surface. More specifically, it is preferable to cover the surface layer from the sheet surface to a depth of 10% (particularly 1%) of the sheet thickness (hereinafter, also simply referred to as “surface layer”). For example, if the sheet thickness is 100 μm, it is desirable that the second element be present within a range from the sheet surface to a depth of 1 μπι. If the content of the second element in the surface layer is in the above range, it means that a graphite intercalation compound is formed, while the second element is deposited on the interlayer or the surface of the graphite or physically. Due to the adsorption, the electronic state at or near the surface of the graphite is changed, and the work function value can be reduced. If the concentration of the second element is too low, the decrease in the work function value will be small, and will be close to the original value of the graphite.

In addition, if the content of the second element is within the upper male box, the 及 »r nature and mature nature. Therefore, due to the reduced electrical conductivity, i¾f conductivity, etc., the crane due to the ユ ー 小 さ く is small, the force and the difficulty are fast, and the spatter resistance of positive ions It is possible to use an electronic device that is excellent in performance and does not deteriorate even in the sky.

 <Removal of electron emission sheet material>

 The electron-emitting sheet material of the present invention may be manufactured by any method as long as the constituent force S like ffjf can be obtained. In particular, the electron-emitting sheet material of the present invention can be obtained by a production method including a step of applying a second element other than carbon as atoms, molecules, or clusters thereof to a graphite sheet.

 (Regarding manufacturing of graphite sheet)

Graphite sheets (ΙίίΙΒ that do not contain the second element) can be used or commercially available. Further, a graphite sheet obtained by the method described in (1) can also be used. In particular, a sheet obtained by substituting a polymer sheet can be used. The polymer sheet is not limited as long as it can obtain Graphiteca S by reason. Polyphenylene oxadiazole, polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polyben At least one of zobisoxazole, polythiazole, polyamide, polyamideimide, polyimide and polyacrylonitrile can be used for. Among them, polyimide is preferred. More preferably, it is polyimide. For example, in the case of: 翻 Polyimide: ^, the sheet is in an inert gas, its polymer power S! ^ 军, and after passing through a carbon precursor, it becomes almost 100% carbonized 100 ° Temperature rise from room temperature until separation of C or more (preliminary, then graphite finish) 25 Temperature rise from room temperature to 5 oo ° C or more (two-step process of performing MM) The graphite sheet obtained in this way can form a foamed state more reliably than a sheet not subjected to such a process. Depending on the density, surface condition, etc., the maximum value of pre-baking and final baking can be determined appropriately according to the view of the polymer, etc. This polyimide sheet is one of the aromatic ^! The best quality graphite You can give a build.

 The thickness of the polymer sheet is not limited, but may be set so as to be the desired thickness of the electron emission sheet material of the present invention. In terms of ^, 5 μm or more and 300 μm or less are preferred, and preferably 25 μm or more and 125 μηι or less.

 It is only necessary that the ox cow be set so as to obtain a predetermined graphite structure. Generally, a heat treatment temperature of 100 ° C. or more and 300 ° C. or less in an inert gas and a heat treatment time of 10 minutes or more and 600 minutes or less may be appropriately determined. .

 More specifically, the first departure in inert gas from ^ g to the first ¾¾? Then, the first treatment step of applying a pressure of 1000 g or more and less than 250 ° C. and a second treatment in an inert gas after the first heat treatment step. It is preferable to employ a method comprising a second heat treatment step in which the temperature is raised to 250 ° C. or more at an increase of 2. By such a process, unnecessary component atoms in the graphite sheet can be removed by gasification and gasification, and a graphite sheet having large and uniform physical properties can be formed efficiently and reliably. it can.

 It is good to determine the starvation according to the view of the sheet (resin) to be used and the sheet thickness. The first value of firiB is usually from 1 ° C to 20 ° C, and preferably from 5 ° CZ to 10 ° C / min. Also, the second ascension of Kenmi

The content of Si is usually preferably 1 ° CZ or more and 20 ° CZ or less, particularly preferably 5 ° 0min or more and 10 ° CZ or less.

 By giving the second element as an atom, a molecule or a cluster thereof to the sheet thus obtained, the electron-emitting sheet material of the present invention can be suitably obtained.

 Such a graphite sheet is shown in FIG. 7 as an image diagram. The graphite sheet 615 is composed of a laminate of a plurality of graphenes 616.

In addition, such a graphite sheet has a peak at (002), where n indicates its own, as shown in the X-ray diffraction pattern of FIG. For example, it has a peak only at (0 2 ⁿ ) (n is a natural number), and typically has peaks only at (0 2) and (0 4). The diffraction angle of (0 2) is around 26.5 °. In addition to the above-described graphite sheet, ^ of the graphite sheet used in the present invention includes a journey of reading and molding graphite particles (graphite flakes) together with a polymerized sculpture material. This is described in detail in Japanese Patent Application Laid-Open No. 11-161 (US Pat. No. 5,866,467, which is incorporated herein by reference). ing. Examples of the polymerized filler include epoxy and fat. As an example, the filling ratio between the graphite rod and the polymer mixture is 6: 4. Such a graph item sheet is shown in Fig. 9 as an image diagram. As shown in FIG. 9, the sheet 6 13 is in a state where the graphite powder 6 14 is arranged in an S layer. The pressure during molding may be, for example, 140 psi or more and 160 000 psi or less. The X-ray diffraction pattern of such a graphite sheet, unlike FIG. 8, shows peaks everywhere, and as a result is described as “broad”.

 (About the addition of the second element)

 The method of adding the second element is not particularly limited as long as the second element can be fixed to the graphite sheet, and the method described in (1) can be applied. In particular, in the present invention, the second element is provided in the form of atoms, molecules and clusters thereof. The second element may be applied before the graphite sheet is laminated on the contrary, or a certain element may be added even after the graphite sheet is laminated on the graphite sheet. The second element is a second element alone or a compound of two or more ^! It is also possible to apply in the form of (molecule). Force It is particularly desirable to apply the second element as a single atom, molecule or cluster.

 In particular, the following steps a) to c):

 a) A step of implanting at least one kind of atoms and molecules ionized as a second element and their clusters into a graphite sheet (ion implantation b) A b) Radical-cancelled atoms and molecules as second elements and A step of irradiating at least one species with a graphite sheet (radical irradiation process D, and

c) a step of causing electrically neutral atoms as the second element and at least one of these clusters to reach the graphite sheet (neutral reaching: m) It is preferable to employ at least one type of process.

 More preferably, at least two or more steps are employed. By carrying out two or more steps, in the second manufacturing step, the concave fit structure is already formed on the surface of the graphite sheet in the first step, so the interlayer or area of the graphite sheet is formed. Chemical or physical adsorption on the surface · Fiber and graphite can be easily formed to promote Si ^ with carbon atoms.

 In the above a), for example, the ion, atom, molecule or cluster containing the second element is ionized at the ion position I ^ of ^], and then mass spectrometry is performed. Retrieving the cluster ^ ¾ ^ can be employed favorably. According to this method, it is possible to form an uneven structure on the surface of the graphite sheet by colliding atoms and molecules or clusters thereof on the surface of the graphite sheet. Since the projection-like structure with small curvature is covered with high density in the uneven structure generated by ion irradiation, an emission part that can emit electrons with a low voltage is formed on the surface of the graphite sheet irradiated with ions. Is done. Furthermore, in ion implantation, the concentration distribution in the surface shape and material can be controlled by changing the atomic species, the calo speed mffi, and the implantation.

 As for (IEb), a known method such as a method of irradiating an rf band electromagnetic wave to the gas phase of an atom, molecule or cluster containing the second element can be preferably employed. Radicals have less change in their original state due to collisions as compared with ions, but are superior in iridical activity. For this reason, by illuminating the radicals, ^ "or their clusters on the graphite sheet, the atoms, molecules or their clusters are adsorbed or physically adsorbed to the interlayer or surface of the graphite. In addition, an uneven structure is formed by the sublimation or destruction of an object with the carbon atoms constituting the graphite, and the uneven structure generated by the radical irradiation has a small curvature that easily occurs due to the sculpting power. In other words, a high-density release is formed, that is, an emission portion capable of emitting electrons at a low applied voltage is formed on the surface of the graphite sheet irradiated with the radioactive ray.

As the above-mentioned method c), for example, a method disclosed in Japanese Patent Application Laid-Open No. 8-169691 can be preferably employed. According to this method, the graph eye By making electrically neutral atoms, molecules or their clusters reach the sheet and depositing them on the graphite surface, irregularities with small curvature can be formed. Thereby, the electron emission portion can be configured for a woman. In addition, the atoms, molecules, or their clusters that have reached the graphite surface are attached or physically adsorbed to the interlayers or surfaces of the graphite, or are formed as carbon atoms constituting the graphite, thereby providing an uneven structure or carbon. It is a compound compound. The uneven structure has a small curvature ^^, and the separation becomes the emission part. In addition, the electronic state near the surface can be changed by the surface adsorbate, the original clusters, and the carbonization that enter the graphite.

 (About the processing with the second element)

 In the present invention, the sheet to which the second element has been added may be further processed as necessary. By this process, the chemistry between the second element and the graphite in the vicinity of the surface can be uniformed in the plane of uneven carbonization ^ !, and the concentration distribution of atoms, molecules, or their clusters in the depth direction can be achieved. Can be made uniform or controlled.

 »A ^ Cases are not limited. For example, if the temperature is 30 o ° c or more and 1000 ° C or less and 5 minutes or more and 60 minutes or more ras in inert I. raw gas, it is good.

 GU Electronics>

 The electronic arm element of the present invention is an electronic element including an electron emission sheet material, a conductive gate layer and a crane.

 A key self-emissive sheet material comprising R (102) and a graphite sheet (101) laminated on ffitBSt (102),

 (1) Graphite sheet (101) Force \ has a structure in which graphite consisting of a plurality of carbon hexagonal mesh layers is laminated in layers,

 (2) Each dalafen is stacked with each other so that the c-axis direction of each dalafen is substantially perpendicular to the tfitfiSS (102) plane.

 (3) A tilt-graphite sheet (101) is laminated on the ダ »(102) such that the c-axis direction of each dalafen is substantially perpendicular to the plane of the a-plate (102). ,

(4) Graphite sheet (101) Force \ Elements other than carbon are used as the second element. Including

 Ι ΙΞ Graphite sheet and conductive gut layer are arranged via »

 This is called glue.

 In other words, the electronic thigh element of the present invention can use a squash (a spacer or the like) employed in the remote emitting device of the present invention, except for using the electron emitting sheet material of the present invention as the electron emitting region. . FIG. 1 (c) shows U of the electron element according to the present invention.

 The electron emission region is formed by an electron rising sheet material including 02 and graphite sheet 101. In FIG. 1 (c), the sickle and the graphite sheet are separated via the adhesive layer 103.

Xie is suitable for the material of: ffl. For example, glass, ceramics _{(A l 2 O 3, Z} r 0 2 oxides such as ceramics, non-oxide ceramics such as _{S i 3 N 4, BN)} « material such as; low resistance silicon, metal 'alloy , Intermediate ^! It is also possible to use a conductive material such as The thickness of the letter is not limited, and may be about 0.5 to 2 mm apart. As the adhesive, for example, a commercially available conductive adhesive or the like can be used. The thickness of the adhesive layer using an adhesive can be set to 1: 1 according to the adhesive or the like.

 In the electron-emitting device of the present invention, a lower portion for supplying electrons to the electron-emitting region may be provided as necessary. That is, a lower electrode ffii can be formed between the elongation and the electron emission region. The lower layer is made of, for example, aluminum, titanium, chromium, nickel, chromium, gold, tungsten, and other gold materials; a composite material obtained by laminating a metal with a low-resistance n-type semiconductor, such as silicon or gallium nitride, and a metal. Can be used. The thickness of the lower part is generally:! ~ 50 m.

The conductive gout layer 106 has a function of giving a chunk to the electron emission region by application and controlling the amount of electrons by its jealousy. The material is not limited as long as it has such a function. In particular, a material having excellent processability such as close contact with a layer to be formed and a pattern win can be preferably used. Generally, II, copper, anolem, nickel can be used for female. Conductive gate The thickness of the layer is usually 0 .:! ~ 3 ππι¾¾.

 In the electron emitting device of the present invention, as long as the electron emitting region (especially the graphite sheet 101 of the electron emitting sheet material of the present invention), the conductive gate layer 106 and the force S sword are not used, You may adopt the arrangement. The space between the electron emission region and the conductive gate layer should be at least one of a space and a body. For example, as shown in FIG. 1 (c), the conductive gate layer 1

06 may be arranged to face. Specifically, Spindt-type electron

This can be done in the same way as the gate and emitter of the device. The space is preferably in a vacuum or a state close thereto. The distance between the two layers can be determined as appropriate according to the desired performance, jealousy, and the like. In general, the shorter the pur, the lower the mm. In addition, the electron emission region (electron emission layer) and the conductive gate layer are substantially arranged in the TO, and the power is preferably higher.

 "The electron emission region and the conductive gate layer and the force S are not removed" means that the electron emission region and the conductive gate layer 106 are located between the gate and the sea, as illustrated in FIG. 1 (c). Means that the edge is kept.

 The electron emission region and the conductive gate layer 106 can be disposed so as to stand apart. Further, both may be fixed to each other via a spacer (thread edge). As the spacer, an insulating material such as alumina, zirconia, and silicon dioxide can be preferably used.

The electron leak element of the present invention can be hung in the same manner as the electronic thigh element of the present invention. For example, a predetermined voltage may be applied between the lower gate or the electron emission region provided on the sickle and the conductive gate layer. n electron emission regions may be adjusted as your power to the electric field bow daughter 1 1 0 ⁶ VZm or more of the electric field. It is generally preferable that the ^, 麵 atmosphere be in a vacuum or a state close thereto. Although the driving temperature is not limited, it is usually preferable to set the driving temperature to about 0 to 60 ° C. Further, the current may be DC or pulsed (倾), or may be shifted.

 <Phosphor light emitting device>

The phosphor light-emitting device of the present invention includes an anode portion having a phosphor layer and an electron; a W device, and a tiff self-anode portion and an electron such that electrons emitted from the junkie electronic thigh element cause the phosphor layer to emit light. The phosphor light emitting element in which the element is arranged The electron emitting element is the electronic element of the present invention.

 The phosphor light emitting device of the present invention uses the electronic w device of the present invention as an electronic device. Other elements (woven or housing, etc.) can be used in the phosphor light emitting element of the present invention. One example of the fluorescent element of the present invention is shown in FIG.

 The anode part can be used as a bell, which is similar to an electron simpler, and in this order, the phosphor layer 109, transparent »(anode 108 and glass holding layer 107) The structure of each layer β and its formation may be in accordance with the following technique.

 Each layer constituting the anode portion takes out light from the front surface (the anode node), and is shelved with phosphor light-emitting elements, and eliminates the use of transparent materials. Examples of the anodic electrode include indium tin oxide (ITO), tin oxide, and an oxide port.

The phosphor layer 109 may be appropriately formed according to a desired color development or the like. That is, various phosphors (chemical formulas) can be applied according to each of the three primary colors of red (R), blue (B), and green (G), and intermediate colors thereof. For example, Y ₂ 0 ₃ system, the red phosphor of G d beta 0 ₃ system or the like; Z n S system, the phosphor of the Zeta eta theta system like; Y ₂ S i 0 ₅ system, the blue fluorescence of Z n S system, etc. Body. The phosphor layer may be formed, for example, as a thin film by printing or coating a transparent layer containing these on a transparent substrate or on a transparent substrate 108.

 The electron simplicity and the anode (particularly, the phosphor layer) may be arranged so that electrons emitted from the electron emission region of the knitted device collide with the phosphor layer of the anode to emit light. Preferably, the electron emission region and the anode section (phosphor layer) are arranged so as to face each other. It is preferable that a space (especially a vacuum space) is provided between the two. In addition, it is desirable that the electron emission region (electron emission layer) and the phosphor layer are arranged in the TO. The distance between the electron emission region and the phosphor layer is generally within the range of 100 m to 2 mm, and can be appropriately adjusted according to desired performance and the like.

<Image drawing device> The image forming apparatus according to the present invention includes an anode portion having a phosphor layer and a plurality of two-dimensionally arranged electronic thigh elements, so that electrons emitted from the tiitS electronic element cause the phosphor layer to emit light. An image drawing apparatus in which an IB node section and an electronic element are arranged, wherein the electronic element is the electronic wister element of the present invention. In this image drawing device, electrons that are extracted from the electron emission region and reach the vicinity of the gate cage are accelerated by the light applied between the phosphor layer and the gate, and are irradiated on the phosphor layer. The phosphor layer emits light. Since the key of light emission can be controlled by ¾ff applied to the gate healing, an image drawing device capable of displaying images and characters on a large scale by extending the gate of each electronic thigh element by Φ legs is used. it can.

 In the image drawing apparatus of the present invention, the electronic element of the present invention is used as an electronic element. For other elements (housings, driers for sleep, etc.), the following elements can be used in the image drawing device. FIG. 10 shows an outline of the male and female painting apparatus of the present invention.

 A plurality of electronic devices 703 are arranged two-dimensionally. That is, electronic thigh elements are arranged on the same plane to form an array of electronic thigh elements. As such an array, for example, a configuration (that is, a matrix or the like) having a pattern of a plurality of conductive gate layers 706 so as to be orthogonal to the pattern with respect to a plurality of electrically totalized turns is exemplified. This is useful for performing the large box equipment.

 The phosphor layer may have the same configuration as the phosphor layer of the phosphor light emitting device. The number 'type' of the phosphor layers may be determined as appropriate according to the number of pixels, the size of 麵, and the like. The number of electronic thigh elements corresponding to one pixel varies depending on the desired degree of incidence and the like, but it is usually 1 to 50 grains! ^.

In particular, in order to display a color image, each of the phosphor layers (one pixel) having a set of the three primary colors R, G, and B corresponds to each electronic thigh element 703, respectively. mfei: You just need to arrange it. Various arrangements such as a vertical stripe and a horizontal stripe can be applied to the arrangement of the three primary colors. The number of electronic elements corresponding to one pixel in a color image is usually 1 to: I 0 0! ^ The anode part 7 14 including the phosphor layer 7 13 and the layer of each electronic thigh element 7 03 The size of the phosphor layer should be such that the amount of light emitted from each phosphor layer can be individually controlled based on the amount of electronic knees from each electron beam device 703. In particular, a part of the phosphor layer in the anode section Alternatively, it is preferable that the electronic thigh region and the electronic thigh region of the electronic thigh element face each other while maintaining the φί state.

 The removal of the image forming apparatus of the present invention may be performed in the same manner as a known field emission display or the like. For example, driving driers 718 and 719 are respectively attached to the lower mm 2 or the electron emission region of the electronic device and the conductive gut layer 706, and a predetermined ME is applied to both layers.

 Example

 Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to the examples.

 Example 1

 ii A polyimide sheet of ¥ 75 / m (trade name Kapton (registered trademark): Toray DuPont Ring) was used.誠 Crying is performed at a temperature of 4 ° C / min from room temperature in an inert gas atmosphere, and is performed for 2 hours at 1100 ° C in the carbonization region. The temperature is raised at 1¾20 ° C / min, and it is 2700, a graphite area. In C for 1 hour. After the completion of this work, a graphite sheet was obtained by rolling. The thickness of the graphite sheet 101 was about 10 μππ which was thicker than the polyimide sheet (FIG. 1 (a)). Since the graphite sheet 101 is highly flexible, it can be easily handled in the subsequent device fabrication process. In addition, in order to operate stably as an electron; W element, it is desirable to fix it with a ^^-based or ^^-based adhesive in contrast to a flat Δt. Therefore, in the present example, the graphite sheet 101 was fixed on the glass wrist 102 having a high flatness and high efficiency using an adhesive layer 103 (Alecom Cerama Bond 503) which is composed of anoremina. .

Next, Li ions were implanted into the graphite sheet at 200 ° C under the condition that the distribution was in the range of 0. 1 to μm centering on the 0.4 m depth region. Implantation in three rows Rere, force 0 speed ME 45 k V, in the order 25k V and 10k V, respectively 1 square cm per ^{1. 5X 10 16, 1. 2 10} 16 and 1. 0X 10 ¹⁶ pieces I typed it in. As a result of observing the structure near the surface with a Zen electron microscope ^^, ion implantation The more uneven structure 104 force S was formed (Fig. 1 (b)). In addition, as a result of measuring the distribution of Li atoms in the depth direction by secondary ion mass spectrometry (SIMS), the Li atoms are distributed almost in the form of ^ j cattle. No change was observed in the axial spacing, and it was confirmed that the interlayer was formed and that the thickness was large. Next, after blanking the blank 105, which is a mixture of alumina powder and the binder ^), by screen printing, the silver fine particles and the conductive gut layer 106, which is the binder of the binder, are also screen-printed. Cr formed by IJ (Fig. 1 (c)). The gap between the graphite sheet 101 and the conductive '14 gate layer 106 and between the adjacent conductive gates 106 was 350 μm and 500 / zm, respectively.

 Each of the graphite sheet 101 and the conductive gate layer 106 has its own positive

(4) When applied with the negative electrode, emission started at 1.2 kv, and the emission current β was small and showed good emission characteristics with little location dependence. FIG. 2 shows the results of measuring the emission current with respect to the applied voltage. In Fig. 2, the horizontal axis represents applied voltage (unit: kV), and the vertical axis represents current value (unit: mA). “SG” stands for Super Graphite (S

The measurement results when G) was used as the electron-emitting portion, and the Li illuminance concentration show the measurement results in this example.

 In the electronic thigh element (lutes G), which has the same structure as that of Kamaki, except that a graphite sheet not implanted with ions is used as the electron-emitting material, the emission start ¾EE is about 1.7 kV¾¾ Was reduced by 0.5 k. This value is almost the same as the value when carbon nanotubes are used as the electron-emitting neo-material. This indicates that the effect of irradiation with Li ions is very large, and that a high-performance electron leakage element force S can be obtained.

 FIG. 3 shows the result of FN (Fowler-Nordheim) plotting of the measurement result of FIG. The horizontal axis is the reciprocal of the electric field bow daughter calculated from the applied ¾1 £ and the gap length, and the vertical axis is the value obtained by dividing the measured 測定 by the square of the m daughter. The slope of the graph indicates the magnitude of the apparent work function, and the smaller the slope, the more easily the electrons are extracted. Also, the size of iSi is proportional to the amount of current, and is proportional to the density of the structure that contributes to electron emission.

As shown in Fig. 3, the magnitude of the work function of ^ Type /, Nare, graphite sheet (indicated by “SG” in Fig. 3) 2 harm ij smaller than ij. This decrease in work function can be attributed to the uneven structure formed by ion irradiation and changes in the surface electronic state due to lithium atoms ¾λ.

 In FIGS. 2 and 3, the ion implantation amount was reduced by a factor of 10 compared to the case of the Li irradiation high concentration: the result of ^ is shown as “L ifa &}. The release of m is even lower than that of, but the work function value is larger, which is the same as the value of the non-implanted resin supergraphite sheet. Although the onset of nm is decreased by the shape change, the work function is considered to have hardly changed because the Li force applied to the vicinity of the surface is small, and the Li ion irradiation was further reduced by a factor of 10. ^^, The start and work function are almost the same as the graphite sheet, so using Lion to change the work function of the graphite sheet requires a certain amount of ¾λ of Li ion is required. In the case of, the concentration of Li atoms present in the graphite is 0.06% fiber, and the Pnote under the irradiation amount is considered to be 0.01% apart. It is considered that the quantity P is 3 in terms of quantity.

 The graphite sheet, which is the base material of the electron-emitting material, has uniform characteristics over a large area, so that a large and uniform electronic thigh element can be easily formed without being restricted by the element size. You can manifest. In addition, in order to operate each element individually, as shown in FIG. 1 (d), adjacent conductive gates 106 are connected to each other.

»I do.

 Furthermore, a phosphor light emitting device in which a phosphor layer 109 emitting light by irradiation of electrons is arranged on a transparent basket 108 formed on a glass screen 107 facing the electron leakage element. Fluorescent materials used for the phosphor layer include fluorescent materials such as ZnO: Zn and ZnS based phosphors corresponding to the energy value of the It ’s good to measure it. In the present example, a ZnS-based phosphor was applied as a phosphor layer on a transparent conductor (ITO) which was a caro-speed.

The phosphor light-emitting device obtained in the above manner is placed in a vacuum chamber, and electrons are extracted by applying Effi between the gate layer 106 and the graphite sheet 101, which is an electron-emitting material. , A transparent sword that functions as a fast-paced jog A 3 kv acceleration mi was applied between the gates m¾. When the t¾ is measured ^

The power S of 300 to 400 c dZm ² was obtained. The luminous bow girl must use a gut between the electron emitting materials to illuminate the work irradiating the phosphor, or ISS the energy of the electrons irradiating the phosphor by the voltage between the acceleration electrode and the gate electrode. Was completed.

 Further, by arranging a plurality of the phosphor spreaders two-dimensionally and controlling the amount of light emitted from each phosphor, it is possible to obtain an image drawing apparatus for displaying an image of an arbitrary shape / arbitrary brightness.

 In Example 1, the graphite sheet 101 was bonded to the substrate 102 before the Li ion was implanted. However, the graphite sheet 101 was bonded to the graphite sheet 101 after the ion implantation was performed. The same effect was obtained even when the film was adhered to the film. Similar effects were obtained by implanting Li ions after forming m 105 and the conductive gate layer 106.

 Also, in Example 1, i was implanted, but at least Li, Na, K, Cs,: Rb of alkali metal and alkali: at least Ca, Sr, Ba of t ^^ S A similar effect was obtained by hitting either one. Nitrogen and silicon have a rough structure, but their work function has been slightly reduced due to the change of electronic state due to penetration between graphite layers and fiber-bonding with carbon atoms. In addition, for example, in ^^ in which rare gases He, Ne, Ar, Kr, and Xe were injected, the field emission started from low 低 due to the formation of the uneven structure. The effect of reducing the work function was smaller than that of implanting Al-Li metal or Al-earth metal.

 Furthermore, the ions to be implanted were not limited to atoms, and the same effect was obtained for those clusters. The same effect was obtained even when the valence of the ions was changed. The same effect was obtained when the temperature of the substrate at the time of ion implantation was 100 ° C. or less. Further, by performing the treatment at a temperature of 100 ° C. or less after the ion implantation, the chemistry between the second element and the graphite in the vicinity of the surface is promoted, and the unevenness in the plane of the uneven structure is enhanced. Uniformization, uniformity or control of the it ^ distribution of atoms, molecules or their clusters could be achieved.

In addition, the graphite sheet 101 was adhered on glass 02. If there is enough power leaky bow daughter, regardless of material and electrical conductivity, i.

It could be used instead of 102.

 In Example 1, a bonding agent composed of alumina was used for bonding graphite sheets 102 and 05 together. Other adhesives can be used without any hindrance in terms of conductivity, material, etc. if they have sufficient adhesive strength.

 In Example 1, は i is required when the temperature exceeds 100 ° C. at which the polyimide sheet is sufficiently carbonized. Needle 2 500 ° C or higher.

 In addition, since the distance between the temples depends on the best of Makoto and Makoto Makoto, it is not limited to the combination of the present embodiment.

 The ID of the starting polyimide film is not limited to 75 μm. For example, similar results were obtained for commercial products in the range of 25 to 300 / x ni. Similar results were obtained when the thickness of the wheat graphite sheet was 1 μμπι or more.

 After changing the # time, the graphitica S, which is not a sheet shape reflecting the shape of the raw material but a powdery shape smaller than 1 mm, is formed, but this powder is irradiated with ions. When the field emission characteristics were measured, the same results as in the graph sheet: ^ were obtained. Furthermore, the ion-irradiated powder was mixed and applied to a binder of a mechanical system, and the electron emission characteristics from a region subjected to a predetermined treatment were not affected by non-inter, one, or substituting. Similar results were obtained using powdered Dalaphite prepared by cutting or pulverizing a graphite sheet regardless of the presence or absence of elements other than carbon.

 Example 2

 In this embodiment, the step of irradiating radicalized nitrogen onto a graphite sheet instead of the step of implanting Li ions is performed by the same steps as in Example 1 except that the electronic device is built up. In a way to release and release ^ 4.

By irradiating a 200 W microphone mouth wave to a nitrogen-filled cylinder made of nitrogen gas, highly reactive nitrogen radicals are generated, and the hole force 開 け opened at one end of the cylinder is used to generate a true nitrogen radical. A nitrogen radical was introduced into the vessel. Set ^ I of the graphite sheet in the vessel to 950 ° C, and set the nitrogen The surface was irradiated 10 ²² per square cm.

X-ray measurements showed that no interlayer ^^ was formed. Surface analysis revealed that nitrogen atoms and the formation of carbon and nitrogen ^ ^ were present near the surface. As a result of measurement of a distribution in the depth direction of the nitrogen atom, up to 1 per cubic cm 0 ^{1 9} nitrogen atoms at a density of not distributed in the range up to a depth Ι μ πι

•

 When the release characteristics were measured in the same manner as in Example 1, it was found that 1.2 1 ^ \ ^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^^^^^^^^^^^^^ '小 さ く' 示 し 、 'n given', and 'n' ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^ Long, which is good Was. It is considered that the work function was reduced by the nitrogen entering the graphite or forming carbon and nitrogen into the graphite, and the electrons were released, and the field emission was started at low 低! £.

 In this example, nitrogen was used as the radical source for illuminating the graphite sheet. However, alkali metals L i, Na, K, C s, R b, alkali d ^^ C a, S r , Ba, and at least one of the rare gas elements Ne, Ar, Kr, and Xe provided the same effect. Similar effects were obtained not only for irradiated radionuclide or molecules but also for their clusters. Similar effects were obtained when the temperature of the substrate when radiating the radicals was 100 ° C. or lower. Further, by treating the radical irradiation at a temperature of 100 ° or less, the chemistry between the second element and the graphite in the vicinity of the surface is promoted, and And the concentration distribution of atoms, molecules or their clusters in the depth direction could be uniformed or controlled.

 In addition, in the case of irradiation with 赚 radical, by setting the texture to the sublimation of oxide or more, the carbon atoms on the surface are changed from the surface to silicon oxide and carbon dioxide as ¾. Since these are preferentially advanced from surface defects on the graphite surface, sharp uneven structures are formed at a high density. Therefore, ® release start ¾Ε became smaller than ^ which was irradiated with nitrogen radicals. .

Similar results were obtained by irradiating a powdery graphite powder having a particle size of less than 1 mm with radioactive cane and measuring the electric field emission characteristics14. Further, this powder is mixed and applied to a binder of a shelf system, and an electron from a region where a predetermined substitution is performed. The release characteristics are the same. Also, regardless of the presence or absence of elements other than carbon, powdered graphite obtained by cutting or powdering graphite sheet is used.

V, a similar result was obtained.

 Example 3

 In the third embodiment, the step of irradiating an electrically neutral Cs metal with a graphite sheet is performed instead of the step of implanting a L ion. «Similar: ^ I've recently identified 14 release characteristics.

 As shown in FIG. 4 (a), the graphite sheet 401 before the step of impregnating the graphite sheet with Cs 麵 is almost flat except for the Tsuruta surface defects 402. In the Dalafite sheet 401 produced in this example by adding a polymer sheet, the layer spacing is very uniform. The domain size in that plane is small compared to highly oriented graphite (HOPG). As a result, the surface is densely packed with various surface defects that serve as entry points for atoms to enter the graphite.

Next, the graphite sheet 401 was opposed to the Norrebo with Cs atb in vacuum, and the keys were set at 194 ° C and 350 ° C, respectively. Evaporated from the crucible †: C s atoms reached ^{10 16} per square cm on the graphite surface, and from the surface defect 402, the gloves of the graphite were pushed out and spread, and C s included ^ I region 4003 was formed (Fig. 4 (b)).

X-ray measurement clearly forms interlayer ^ J! /, No power S leaked. By surface analysis, it was confirmed that the surface was near the C s nuclear S surface. Also, C s depth distribution results of measurement of the atoms, and range distribution C s atoms at most 1 cubic 1 0 ²² density per cm in the depth 2 mu m! /, Was.

 The emission characteristics were measured in the same manner as in Example 1. As a result, the emission power S was started at 0.7 kV, and the fluctuation of the field emission current was small, and the sculpture emission characteristic was small with little place dependence. Since the uneven structure is almost unchanged before and after the irradiation of Cs atoms, it is considered that the work function is lowered by Cs adsorbing on graphite, the electrons are easily emitted, and the emission output is started at low.

In this example, the Cs atom was used as the element in the graphite sheet, but nitrogen, alkali metals Li, Na, K :, Cs, Rb, and a Similar effects were obtained for at least one of Ca, Sr, and Ba of iHl males. The same effect can be obtained not only for atoms and molecules but also for clusters of these elements.Furthermore, when the fiber is irradiated with a neutral element at a temperature of 100 ° C or less, the same effect can be obtained. The effect was obtained. In addition, by applying heat treatment at a temperature of 100 ° C. or less to the medium 14 ° C., it is possible to promote the chemistry of graphite other than carbon with an element other than carbon by applying a treatment in the vicinity of the surface, and to make the surface uneven. The uniformity in the plane of ^^ and the uniformity or control of the concentration distribution in the depth direction of an atom, a molecule, or a cluster thereof could be performed.

 The same results were obtained when field emission characteristics were measured by irradiating powdery graphite with a particle diameter of less than l mm with nitrogen. Further, the powder was mixed with an inorganic or shelf-based binder and applied, and the electron emission characteristics from the region where the predetermined processing was performed were not affected by the binder or the processing. Similar results were obtained when powdered Dalaphite was used by cutting or pulverizing the graphite sheet regardless of the presence or absence of the carbon element.

 Male example 4

 In Example 4, the electronic thigh element was illuminated in the same process as in Male Example 3 by illuminating the argon ion before irradiating the graphite sheet with electrically neutral Cs metal. In the same way, we evaluated the emission characteristics.

As in Example 1, the graphite sheet is fixed to the glass, it was implanted in the grayed La Fight sheets at room temperature in 1 square cm per 4.5 accelerates X 1 0 ^{1 6} amino Anoregonion flffi 1 8 0 k V. Next, the same method and conditions as in Example 3 were applied to a graphite sheet irradiated with ions. s metal impregnated.

X-ray measurement showed that no interlayer was clearly formed. From the surface analysis, it was confirmed that the force S was in the vicinity of the C s atom and the argon nuclear S surface. Also, C s depth distribution results of measurement of the atoms are distributed at a maximum 1 cubic cm 1 0 ^{2 2} pieces of density per a range to a depth of 2 μ ιη, argon atoms is zero depth. It was distributed over a range of 0.2 μm centered on 25 μm.

The field emission characteristics were measured in the same manner as in Example 1. As a result, the emission power S started from 0.4 kV, and a good m emission pattern with little fluctuation in emission current and little place dependence was exhibited. Argon ion irradiation process, Cs ion irradiation process, described in Example 3. The release and release start Sffi of the age at which the above-mentioned C s atom process was performed by the occupational worker was 1.O kV and 0.ek V ^ O .7 kV, respectively.The C s atom impregnation process was performed after the anoregon ion irradiation process. By doing so, it was possible to further reduce the release of Kaimedai®. The concentration of Cs atoms in the vicinity of the surface is almost the same, and the same result can be obtained if the »energy and irradiation amount of the ions are almost the same even if the ion is changed in the ion irradiation process. It is considered that Cs atoms easily enter the graphite between the graphite layers due to the concave-convex structure caused by the ion irradiation process.

 In the present example, the cs atom was used as the element in the graphite sheet. (^ Element, but the alkali metals Li, Na, K, Cs, Rb, and the alkali metal C A similar effect was obtained if at least one of a, Sr, and Ba was eaten.The same effect was obtained not only for atoms and molecules but also for clusters of them. The same effect S was obtained when the temperature of the element J was not more than 100 ° C. By performing the treatment at a temperature of 0 0 0 C or less, the chemistry between the element other than carbon and dalaphite near the surface is promoted, and the uneven structure Uniformization, uniformization or control of the concentration distribution of atoms, molecules or their clusters in the depth direction could be achieved.

 The same results were obtained when the field emission characteristics were measured by irradiating medium graphite with powdery graphite having a particle size of less than 1 mm. Further, this powder was mixed and applied to a binder of a binder system, and the effect of electron emission from a region subjected to a predetermined treatment, in particular, a binder treatment was not affected. Similar results were obtained by using powdered graphite obtained by cutting or pulverizing the Dalaphite sheet regardless of the presence or absence of the carbon element.

 Example 5

 In the present embodiment, the step of irradiating the graphite sheet with electrically neutral Mo metal before the anoregon ion irradiation step is performed in the same manner as in the fourth embodiment except that the electronic element is removed. The emission characteristics of m were improved.

A graphite sheet was fixed to a glass substrate 501 prepared in the same manner as in Example 1, and a Daraphite sheet was opposed to a knuckle voluminized with Mo S in vacuum. The temperature of the graphite sheet was set to 500 ° C. Mo atoms evaporated from the crucible, and fireman's standard while diffusing surface 30 nm of Mo械微particles 502 are uniformly formed on the graph Ai preparative surface (FIG. 5 (a)) ₀ Next, similar to the flame Example 4 The mochi was subjected to argon ion irradiation (Fig. 5 (b)) and C s annihilation impregnation (Fig. 5 (c)). In the same way as Argon ion irradiation, the Mo recording particles 502 serve as a mask.

0 Fine particles with a force of 502 were not etched, and the area was professionally etched (Fig. 5 (b)), forming a roughly 503 force S in a circular structure. On the other hand, in the C s impregnation step, C s atoms were impregnated into the preferential graphite sheet from the side surface of the circular convex structure 503, and the C s impregnated region 504 was extinguished.

X-ray measurements confirmed that no intercalation compound was clearly formed, and surface analysis confirmed that Mo atoms, Cs atoms, and argon nuclear S were near the S surface. Also, C s depth distribution results of measurement of the atoms are distributed in 1 0 ²² density per maximum 1 cubic cm in a range to a depth of 2 mu m, § argon atoms depth 0. When the distribution of the 寸 m release characteristic was measured in a range of 0.2 μm with the center at 25 μm, the release of 0.4 kv was started in the same manner as in Example 4. The width and the location dependency were greatly improved as compared with Example 4.

 In addition, the field emission characteristics from the graphite sheet 501 before the Argon ion irradiation step and the C s ^^ impregnation step are not as good as those of Cs metal-impregnated: ^, but the nanometer-sized structure is high on the surface. Because of the density of the castle, the release of the pen is improved as compared to the 鄉 立 子 が な レ, な お, and Mo ^ «÷ 502« C s Wei region 504 It was easily removed by performing 赚 ® sound wave 赚 (Fig. 5 (d)). Since the sculpture emission characteristics I "at this time are not affected by the work function of Mo, the emission characteristics 14 are higher than those in Fig. 5 (c).

In addition, the diameter and density of the fine particles can be easily controlled by the Si reaction g and the amount of Mo atoms per unit time (flux density). Also, in this example, the type of male is not limited if the etching depth in the force ion irradiation step (b) using Mo fine particles is slower than the etching wedge of the graphite. If it is faster than the etching rate of graphite, Typically, it is desirable that the fine particles be capable of forming a columnar convex structure having a height of 30 nm or more. In the present example, 掷 is supplied to the surface opposite to the surface by evaporation, but ^ particles can also be generated by supplying a 棚 containing a predetermined amount and leaking on a sickle. Was possible.

In addition, in the ion irradiation step (b), the force S of irradiating 4.5 × ^{10 16} argon ions per square cm at room temperature at a caro-speed of 180 kV, Even if the ion species is changed, the same result can be obtained if the kinetic energy of the ion and the irradiation amount are almost the same, and it is also possible to form a circular structure with an irradiation amount of 30 nm or more in height. desirable.

 In this example, the graphite sheet 501 is used as the tt element in the Jt "

The same effect can be obtained by using at least one of Li, Na, K, Cs, Rb of alkali and Ca, Sr, and Ba of anorecali ^. Was. The effect was not limited to atoms and molecules, and similar effects were obtained with those clusters. The same effect was obtained when the temperature of the fiber when illuminating the neutral element was 100 ° C or lower. In addition, by subjecting the neutral element Jt¾ to a temperature of less than 1000 ° C, the chemistry between the carbon element and the graphite is promoted near the surface, and the uneven structure is increased. It was possible to uniformize or control the distribution of atoms, molecules or their clusters in the depth direction in the plane of ^).

 The same result was obtained when the powdery graphite particles having a particle size of less than l mm were irradiated with a neutral element and the field emission characteristics were measured. Furthermore, this powder was mixed with an organic binder and applied, and the electron emission characteristics from the region subjected to the predetermined substitution were not affected by the binder treatment. Similar results were obtained using powdered graphite, which was obtained by cutting or pulverizing the graphite sheet regardless of the presence or absence of the powder.

 Example 6

 In this example, the electron emission device was used in the same process as in Example 3, except that the radical was irradiated before the C s annihilation impregnation deposition process, and the m emission characteristics were described in the same manner. did.

Glass prepared in the same manner as in Example 3 By irradiating a boron nitride cylinder filled with elemental gas with a microphone mouth wave of 400 W, ^^ radicals are generated, and 真 | £ is used through a hole drilled at one end of the cylinder.赚 radical was introduced into the T vessel. Oxide of graphite sheets in the vessel is set below sublimated Rere was irradiated 1 0 ^{2 2} or Ah 1 square cm of Lin radicals. Next, a C s impregnation step was performed under the same conditions as in Example 3. In the X-ray measurement, no interlaminarization ^) force S was formed, and in the surface analysis, the enzyme and carbon oxide forces s

 When the amount of release was measured in the same manner as in Example 3, the release of ¾ started from 0.3 1 ^, the release of the release was small, and the dependence on the location was small. Irradiation with rice cake also showed good m release. The result is that he entered graphite or converted carbon and nitrogen ^! Not only to form but also to have a small electron affinity, and to be positively ionized, and the work function is effectively reduced by the dipole moment formed by the transfer of electrons between the Cs atom It is considered to be.

 In this example, 瞧 was used as the radical source for illuminating the graphite sheet, but nitrogen, alkali metals L i, Na, K, R b, alkaline earth metals C a, S r, At least one of Ba, the rare gas elements N e, Ar, K r, and X e 同 様 T ^ The same effect S was obtained, but the electronegativity of the element covered near the surface The difference is large, the more desirable, the better. The same effect was obtained not only for the irradiated radionuclide but also for the atom or molecule clusters. The same effect was obtained when the temperature at the time of irradiating the radicals was 100 ° C. or less. In addition, by applying 1W treatment to the surface of the canola at a temperature of 100 ° C. or lower, the chemistry between the element other than carbon and graphite and the graphite can be promoted in the vicinity of the surface. It was possible to equalize or control the concentration distribution of atoms, molecules or their clusters in the depth direction in the plane of the surface.

In this example, the Cs element was used as a neutral element for irradiating the graphite sheet. However, the alkali metals Li, Na, K, Cs, Rb, and the alkaline earth metal Cs Similar effects were obtained if at least one of a, Sr, and Ba was included. The effect was not limited to atoms and molecules, but similar effects were obtained with those clusters. In addition, the temperature of the sickle when illuminating the neutral element is 100 ° C or less. If so, a similar effect was obtained. In addition, by applying heat to the carbon fiber at a temperature of 1 ooo ° C or less, the key to the chemistry of the carbon element and graphite covering the surface near the surface and the unevenness of the surface It was possible to homogenize or control the concentration distribution of atoms, molecules or their clusters in the depth direction.

 The same result was obtained when the powdery graphite smaller than 1 mm was irradiated with medium-sized hydrogen and the field emission characteristics were measured. Further, the powder was mixed and applied to a binder of the 及 and 系 systems, and the electron emission characteristics from the region subjected to the predetermined treatment were not affected by the イ ン タ イ ン タ 理 理. Similar results were obtained by using powdered dalarite obtained by cutting or pulverizing a graphite sheet regardless of the presence or absence of elements other than carbon.

 In the present invention, the second element is added to a graphite sheet (particularly, a surface layer) in the form of atoms, molecules, or clusters thereof, thereby improving the electron emission characteristics while utilizing the inherent characteristics of the carbon material. Can be achieved. In other words, the carbon material has excellent electrical conductivity, conductivity, corrosion resistance '14, etc., has a smaller field emission start efficiency or work function than conventional products, and can reduce the electron emission material. As a result, it is possible to carry high-efficiency electronic thigh elements and Oran display freshness.

 Industrial applicability

 The electron-emitting sheet material of the present invention is expected to be particularly applicable to various uses other than those in which an electron-emitting material is conventionally used. The electron emission sheet material of the present invention can be suitably used for, for example, a display, a tube, an emitter, a lamp, an electrode, and the like.

Claims

The scope of the claims

1. An electron emitting sheet material comprising (102) and a graphite sheet (101) coated on fflte (102),

 (1) tllB graphite sheet (101) has a structure formed in a graph enca S layer composed of a plurality of hexagonal carbon planes,

 (2) The forces of each dalaphen are such that the c-axis direction of each graphene is substantially perpendicular to the tiltESt anti- (102) plane.

 (3) The graphit sheet (101) is placed on the counter (102) so that the c-axis direction of each graphon is substantially perpendicular to the Shusu ESt and the (102) plane.

 (4) tiflE graphite sheet (101) Force Including elements other than carbon as the second element,

Electron emission sheet material.

2. The electron emission sheet according to claim 1, wherein a peak of the (002 ⁿ ) plane (where n is a natural number) appears in the X-ray diffraction pattern of the self-graph graph sheet. 2. The electron-emitting sheet material according to claim 1, wherein in the X-ray diffraction pattern of the terrible graphite sheet, the peak force of the (002) plane and the (004) plane is different.

4. The electron emission sheet material according to claim 1, wherein a second element of tin exists between the layers of the dalaphen.

5. Touch S The concentration of the second element is 0.001 atom. /. More than 3 atoms. /. The electron emission sheet material according to claim 1, wherein:

6. The electron emission sheet material according to claim 1, wherein the concentration of the second element is 0.005 atomic% or more and 2 atomic% or less.

7. concentration of 2 elements, o. Oi atoms is _^0/0 or 1 atom _^0/0 or less,請Motomeko 1纖electron emitting sheet material.

8. The electron emission sheet material of fEife, wherein the thickness of the sheet is 10 μm or more and 1000 ^ m or less. ·

9. The electron-emitting sheet material according to claim 1, wherein the second element has a surface layer extending from the sheet surface to a depth of 10% of the sheet thickness.

10. The electron emission sheet material according to claim 1, wherein the second element is at least one of an element and an earth metal element.

11. The electron emission sheet material according to claim 1, wherein the second element is at least one of Li, Na, K, Cs, Rb, Ca, 31: and 8 &.

12. The electron emission sheet material according to claim 1, wherein the second element is at least one of nitrogen and wisteria.

13. The electron emission sheet material according to claim 1, wherein the second element is at least one of rare gas elements.

14. The electron-emitting sheet material according to claim 1, wherein the second element is at least one of Ne, Ar, Kr, and Xe.

15. The second element is 1) to 3) below;

 1) At least one of the elements and earth metal elements

2) at least one of nitrogen and

 3) At least one rare gas element

2. The electron emission sheet material according to claim 1, wherein the electron emission sheet material is a set of two or three of:

16. Manufacturing of the electron emission sheet material, which is called the warehouse (102) and the graphite sheet (101) laminated on the glass (102),

(1) The tirlE graphite sheet (101) has a structure formed into a graphlinker layer composed of a plurality of carbon hexagonal mesh planes,

 (2) Each graphene is stacked so that the c-axis direction of each dalafen is substantially perpendicular to the ffHBS ^ (102) plane.

 (3) The graphite sheet (101) is placed on the front IBS plate (102) so that the c-axis direction of each dalafen is substantially perpendicular to the | ίΠΒ¾Κ (102) plane. Things

 An electron emission sheet material method, comprising a second element providing step of providing a second element other than carbon as an atom, molecule or cluster to an IS graphite sheet.

17. The electron emission sheet material according to claim 16, further comprising a step of further heat-treating the graphite sheet after the fifia second element providing step.

18. fiJlB 2nd element application process,

 a) an ion implantation step of implanting at least one of atoms, molecules, and clusters ionized as a second element into a dalaphite sheet;

 The production of an electron emission sheet material having a texture of 16 f, comprising:

19. The second step of applying the second element

 b) A radical irradiation step of irradiating at least one of the atoms, molecules, and clusters which have been subjected to radioactive ray as a second element on a graphite sheet.

 17. The method for producing an electron-emitting sheet material according to claim 16, comprising:

20. The second element addition process

c) Neutral substance reaching process in which at least one kind of electrically neutral atoms, molecules and clusters as the second element reaches the graphite sheet. Claim 16: Manufacturing of a 6-fiber electron emission sheet material.

The 21.2 element providing step includes the following steps a) to c);

 a) an ion implantation step of implanting at least one kind of atom, ^ "and cluster ionized as a second element into a graphite sheet;

 b) a radical irradiation step of irradiating the graphite sheet with at least one of atoms, molecules and clusters radicalized as a second element, and

 c) A process for reaching at least one of electrically neutral atoms, molecules and clusters as the second element to the graphite sheet.

 17. The method for producing an electron-emitting sheet material according to claim 16, comprising two or three steps of:

22. The method for producing an electron emission sheet material according to claim 16, wherein the test Daraphyte sheet is obtained by treating a polymer sheet.

2 3. Key sheet polymer polyphenylene oxadiazonole, polybenzothiazole, polybenzobisthiazole, polybenzozoxazole, polybenzobisoxazole, polythiazole, polyamide, polyimide, polyamideamide 22. The method for producing an electron emission sheet material according to claim 22, which is at least one of polyacrylonitrile and polyacrylonitrile.

2 4. The electron emission sheet material according to claim 2, wherein the polymer sheet is a polyimide.

22. The method according to claim 22, wherein the knitted polymer sheet is an aromatic polyimide.

2 6.mm ^ The first heat treatment step in which the temperature is raised from the start of the ι in the inert gas to the 第 th rise and baked at 100 ° C or more and less than 250 ° C. ΙίίϊΕ After the first processing step, inactive 't ^' The second heat treatment step is performed at a temperature of ^ ii degrees and a temperature of 250 ° C. or more.

In X-ray diffraction pattern of 2 7. The graph eye tosylate Ichito, (0 0 2 ⁿ⁾ plane (where, n represents the self-bell.) To the peak force S of electron emission of claims 1 to 6, wherein Sheet material lining method.

2 8. The electron emission sheet according to claim 16, wherein in the X-ray diffraction pattern of the graphite sheet, the peak force of the (0 2) plane is (0 4) plane.

2 9. The electron emission sheet material according to claim 16, wherein the second element is interposed between the layers of flalafene.

30. The method for manufacturing an electron-emitting sheet material according to claim 16, wherein the concentration of the second element is 0.01 to 3 atomic%.

3 1. Concentration of the second element, 0. is 0 0 5 atomic% or more and 2 atomic _^0/0 or less, Oh manufacturing the electron-emitting sheet material according to claim 1 6, wherein

3 2. The method for producing an electron-emitting sheet material according to claim 16, wherein the concentration of the second element is not less than 0.01 atomic% and not more than 1 atomic%.

3 3. The production of the electron-emitting sheet material according to claim 16, wherein the sheet has a thickness of 10 m or more and 100 μm or less;

3. The method for producing an electron-emitting sheet material according to claim 16, wherein a part or all of the second element forms a surface layer from the sheet surface to a depth of 10% of the sheet thickness.

35. The fibrous electron emission sheet material $ ¾ ^, wherein the second element is at least one of an element and an earth element.

36. The electron emission sheet material according to claim 16, wherein the second element is at least one of Li, Na, K, Cs, Rb, Ca, Sr, and Ba.

37. The method of claim 16, wherein the second element is at least one of nitrogen and nitrogen.

38. The electron emission sheet material according to claim 16, wherein the second element is at least one of rare gas elements.

39. The material of claim 16 | 5, wherein the second element is at least one of Ne, Ar, Kr and Xe.

40. The second element is 1) to 3) below:

 1) at least one of the elements and elements

2) at least one of nitrogen and

 3) At least one rare gas element

 17. The method for producing an electron-emitting sheet material according to claim 16, which is a set of two or three of the following.

41. An electron element including an electron emission sheet material, a conductive gate layer and

 The feeble electron emission sheet material includes a tomb (102) and a graphite sheet (101) stacked on the cafeteria (102),

 (1) Kamami Graphite Sheet (101) Force A graphite sheet consisting of a plurality of carbon hexagonal mesh planes has a layered structure,

(2) c-axis force of each dalafen ftllSSS Each graphene is laminated so that it is substantially perpendicular to the (102) plane. (3) The tiif self-graphite sheet (1 0 1) is stacked on 1 (1 0 2) so that the c-axis direction of each graphene is substantially perpendicular to the | ίίίΒ¾¾ (1 0 2) plane. Has been

 (4) fflfB graphite sheet (101) containing carbon element as a second element,

 て い る It is arranged via the graphite sheet (101), the conductive gate layer (106) and the power leakage (105),

 An electronic device that has the following characteristics: W element.

4 2. The anode section and the electron tread element having the phosphor layer, the anode section and the electron leakage element are arranged so that the electrons emitted from the key electron emission element emit the tins phosphor layer. 41. A phosphor light emitting device, wherein the electronic device is a device according to claim 41.

4 3. An anode part having a phosphor layer and a plurality of two-dimensionally arranged electrons

An image drawing apparatus including a ¾lt element, an electron force emitted from a tiff self-electron element, and a tut self-anode section and an electronic element arranged to emit light from a phosphor layer. The image drawing device according to claim 41, wherein the amount of phosphor emission is controlled by the amount of electron emission from each of the plurality of electron-emitting devices.