JP2015095340A - Electron emission element and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron emission element which can obtain a high electron emission amount, which can prevent a surface electrode from being excessively destructed or can reduce destruction, and which can prolong its life.SOLUTION: Disclosed is an electron emission element which includes a first electrode, a second electrode, and an intermediate layer between the first electrode and the second electrode and emits electrons from the second electrode by applying voltage between the first electrode and the second electrode. An electrode adhesion layer is provided between the second electrode and the intermediate layer.

Description

  The present invention relates to an electron-emitting device that emits electrons by applying a voltage, and a method for manufacturing the same.

  As a conventional electron-emitting device, an electron-emitting device composed of a Spindt type electrode, a carbon nanotube (CNT) type electrode or the like is generally known. This electron-emitting device can apply a high voltage to the sharp protrusion to form a strong electric field of about 1 GV / m, and can emit electrons by the tunnel effect.

  However, since these two types of electron-emitting devices generate a strong electric field in the vicinity of the surface of the electron-emitting portion, the emitted electrons obtain large energy by the electric field and easily ionize gas molecules. The cation generated by ionization of gas molecules is accelerated and collides toward the element surface by a strong electric field, and there is a problem that element destruction occurs due to sputtering. Moreover, the dissociation energy of oxygen in the atmosphere is lower than the ionization energy, and ozone is easily generated by these strong electric fields when electrons are emitted in the atmosphere. Ozone is harmful to the human body and oxidizes a wide variety of substances with its strong oxidizing power. Therefore, there is a problem of damaging members around the element. There has been a restriction that materials with high properties must be used.

  Against this background, electron emitters of a different type from those described above include MIM (Metal Insulator Metal) type, MIS (Metal Insulator Semiconductor) type, BSD (Ballistic electronic Surface-emitting Device) type and the like. Has been developed. These are surface emission type electron-emitting devices that accelerate electrons using the quantum size effect and strong electric field inside the device to emit electrons from the planar device surface. Since these electron-emitting devices emit electrons accelerated by an electron acceleration layer inside the device, a strong electric field is not required outside the device. Therefore, the problem of element destruction by sputtering and the problem of generation of ozone are overcome. In recent years, a device capable of overcoming the above-described problems and stably emitting electrons in the atmosphere has been reported as in Patent Document 1.

  FIG. 7 is a schematic diagram showing the configuration of the electron-emitting device disclosed in Patent Document 1. As shown in FIG. The electron-emitting device 70 includes a substrate 71 serving as a lower electrode, an upper electrode 72, and an electron acceleration layer 73 that is sandwiched therebetween. Further, the substrate 71 and the upper electrode 72 are connected to a power source 74, and a voltage is applied between the substrate 71 and the upper electrode 72 that are arranged to face each other. The electron acceleration layer 73 includes conductive fine particles 731 made of a conductor and having a high anti-oxidation power, and an insulator material 732 larger than the size of the conductive fine particles 731. Since a conductive material having a high anti-oxidation power is used as the conductive fine particles 731, it is difficult to cause element deterioration due to oxidation by oxygen in the atmosphere, so that it can be stably operated even under atmospheric pressure.

  The electron-emitting devices having these surface electrodes generally have three common features. One is that the surface electrode is very thin. This is because an electron-emitting device having these surface electrodes is required to have a thin surface electrode that causes electron scattering because electrons accelerated in the device can break through the vacuum barrier to emit electrons. It depends. The second feature is that part of electrons flowing in the device are emitted to the outside. That is, the electrons that are not emitted lose all energy in the device and are converted into heat, light, chemical energy, or the like. As a third feature, it is necessary to experience a semi-insulation breakdown process called forming for electron emission. For this reason, the cross-sectional area of the current path tends to be small and the current density tends to be high.

JP 2009-146891 A

  However, an electron-emitting device having a surface electrode combines the above three characteristics, and in principle, energy deactivation of electrons is concentrated locally on the surface electrode, causing a problem of destruction of the surface electrode that is a thin film. ing. It has been a problem to suppress the destruction of the surface electrode.

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is to obtain a high electron emission amount in an electron-emitting device having a surface electrode and to prevent excessive destruction of the surface electrode. An object of the present invention is to provide an electron-emitting device capable of preventing or destroying and extending the lifetime.

  In order to solve the above problems, an electron-emitting device according to the present invention includes a first electrode, a second electrode, and an intermediate layer between the first electrode and the second electrode, and the first electrode An electron-emitting device that emits the electrons from the second electrode by applying a voltage between the electrode and the second electrode, and having an electrode adhesive layer between the second electrode and the intermediate layer It is characterized by.

  The bond distance of molecules constituting the electrode adhesive layer may be a value between the bond distances of molecules constituting the second electrode and the intermediate layer, respectively.

  The electrode adhesive layer may be a metal.

  The electrode adhesive layer may have a thickness of 5 nm to 20 nm.

  The electrode adhesive layer may be partially disposed between the second electrode and the intermediate layer.

  The method for manufacturing an electron-emitting device according to the present invention includes a step of forming an intermediate layer on a first electrode, a step of forming an electrode adhesive layer on at least a part of the intermediate layer, and at least on the electrode adhesive layer. Forming a second electrode.

  According to the electron-emitting device of the present invention, in an electron-emitting device having a surface electrode, a high electron emission amount can be obtained, and excessive destruction of the surface electrode can be prevented or reduced, thereby extending the life. An electron-emitting device can be obtained.

It is a schematic diagram which shows the structure of the electron emission apparatus which concerns on Embodiment 1 of this invention. It is a schematic diagram of the peripheral device which measures the electron emission apparatus in an Example and the discharge | released electron discharge | released from this electron emission element. It is the table | surface which showed the result of having done the initial amount of electron emission of the electron-emitting elements 1a-1c and 5, and the endurance test. It is a schematic diagram which shows the structure of the electron emission apparatus which concerns on Embodiment 2 of this invention. It is a top view which shows the structure of the electron emission apparatus which concerns on Embodiment 3 of this invention. It is a schematic diagram which shows the structure of the electron emission apparatus which concerns on Embodiment 3 of this invention. It is a schematic diagram which shows the electron-emitting device of patent document 1.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, the same members are denoted by the same reference numerals. The following embodiment is an example embodying the present invention, and does not limit the technical scope of the present invention.

(Embodiment 1)
FIG. 1 is a schematic diagram showing a configuration of an electron emission device A1 in the present embodiment. The electron emission device A1 includes an electron emission element 1 and a power source 2. Electrons are emitted when a desired voltage is applied to the electron-emitting device 1 by the power source 2.

  The electron-emitting device 1 includes a first electrode 11 serving as a substrate electrode, an intermediate layer 12, an electrode adhesive layer 13, and a second electrode 14 serving as a surface electrode, and has a laminated structure as shown in FIG. The power source 2 is electrically connected to the first electrode 11 and the second electrode 14.

  The 1st electrode 11 consists of a support body provided with electrical conductivity, such as a metal plate. The material only needs to have sufficient electrical conductivity. Specific examples include a metal plate such as an Al plate, a Cu plate, and a SUS plate, a semiconductor substrate that is highly doped with impurities such as B, Al, N, and P, and An insulating substrate such as a glass plate, an acrylic plate, or a ceramic plate on which a metal or conductive material is formed can be used. The plate thickness is not particularly limited as long as the rigidity as the element and the relaxation of the temperature rise due to element heat generation are sufficient. The surface roughness on the intermediate layer 12 side is sufficiently smaller than the layer thickness of the intermediate layer 12, and it is sufficient that no short circuit occurs between the first electrode 11 and the second electrode 14, for example, Ra is 0.1 μm or less. If so, it can be appropriately adjusted. In addition, a flexible substrate may be used as long as the intermediate layer 12 and the second electrode 14 can withstand.

  The intermediate layer 12 is composed of one or more of insulating resin, conductive resin, and insulating fine particles. Moreover, what added metal microparticles | fine-particles to this structure is more preferable. In the present embodiment, as shown in FIG. 1, a mixture of an insulating resin 121 and metal fine particles 123 is used as the intermediate layer 12. The layer thickness of the intermediate layer 12 is preferably 0.3 to 5.0 μm.

  Since the insulating resin 121 is not particularly limited as long as it is an insulating material, most of the resin can be used. For example, a silicone resin can be used, and its curing type is not particularly limited.

  For the metal fine particles 123, any metal species can be used without limitation, and for example, Au, Pt, Pd, Ag, and the like are more preferable because they are resistant to oxidation. Further, the particle size needs to be smaller than the insulating fine particles 122, and the average particle size within the range is preferably 3 to 20 nm.

  The electrode adhesive layer 13 is made of a material in which a typical bond distance X of molecules constituting the material is a value between the typical bond distances X of molecules constituting the second electrode 14 and the intermediate layer 12, respectively. In the case of a complex molecule, the bond distance between the first adjacent atoms at the site characterizing the structure of the molecule may be a numerical value X. For example, a polymer such as a resin has a first adjacent atom in the main chain as a skeleton. The inter-bonding distance may be used.

  The reason for adopting the configuration as described above is that the numerical value X is a main parameter that determines the adhesion of each boundary between the second electrode 14 and the electrode adhesive layer 13, and the electrode adhesive layer 13 and the intermediate layer 12. This is because the closer the logarithmically converted value logX of the numerical value X is, the better the adhesion is.

  Here, the principle of improving adhesion will be described. A material having a periodic structure as a whole does not have a portion where strain is concentrated, and cracks and separation are unlikely to occur. However, there is no continuity at the interface between one periodic structure and one different periodic structure, and the structure has a disordered defect. For this reason, strain is concentrated locally, and cracks, peeling and the like are likely to occur. An important parameter of the periodic structure is the lattice constant. The interface between the periodic structures having a lattice constant close to each other has the continuity of the structure, and the strain applied to the interface is dispersed, so that cracks, peeling, and the like do not easily occur. Since the material does not necessarily have a periodic structure, this is generalized, and the parameter having a property close to the lattice constant is the bond distance between the first adjacent atoms. Adhesion is dominated by atomic forces at the interface. For this reason, when the logarithmic value of the bond distance between the first adjacent atoms of the material of each layer, that is, the value logX is close, the number of adjacent atoms increases between layers, and the adhesion is improved as the sum of atomic forces. become.

  As described above, as the electrode adhesive layer 13, the typical bond distances of molecules constituting the material are representative of the molecules constituting each of the second electrode 14 and the intermediate layer 12 which are the upper and lower layers of the electrode adhesive layer 13. It is desirable that the value be between a certain coupling distance. In such a case, high adhesion can be obtained.

  When the main material of the intermediate layer 12 is the insulating resin 121 as in this embodiment, the electrode adhesive layer 13 is preferably a metal, and third and fourth periodic metal elements such as Ti, Cr, Ni, and Al are used. Particularly preferred.

  As the layer thickness of the electrode adhesive layer 13 increases, the adhesion between the second electrode 14 and the intermediate layer 12 increases, so that the fracture life of the second electrode 14 is improved. At the same time, however, the amount of electron emission with respect to a certain voltage of the power supply 2 tends to decrease slightly. This is considered to be due to the following two conflicting actions caused by the increased adhesion between the second electrode 14 and the intermediate layer 12. The first function is that the contact resistance at the boundary between the second electrode 14 and the intermediate layer 12 is suppressed, and the current flowing through the electron-emitting device 1 is increased, whereby the amount of electron emission is increased accordingly. Second, the destruction of the second electrode 14 is excessively suppressed, and the defect region of the second electrode 14 is reduced, so that electrons conventionally emitted to the outside are scattered and relaxed by the second electrode 14, and vacuum It is an action that cannot be released because it cannot break through the barrier. These two effects generally tend to be stronger in the latter. Therefore, in consideration of the compatibility between a high emission amount and a long life, the layer thickness of the electrode adhesive layer 13 is preferably 2 to 30 nm, and particularly preferably 5 to 20 nm. Within this range, it is possible to realize a high-quality electron-emitting device from the viewpoint of electron emission amount and lifetime.

  The second electrode 14 is made of a thin film of a conductive material. The material only needs to have high electrical conductivity, and is preferably a metal material. As a specific example, a metal containing Au, Pt, Pd, Ag, or the like can be used. Of these, Au, which does not cause a chemical reaction such as oxidation, is most preferable when driving in the atmosphere is assumed. When the layer thickness is too large, the destruction of the second electrode 14 is excessively suppressed, and the amount of electron emission is reduced by reducing the defect region. On the other hand, if it is too small, the in-plane electrical conductivity of the second electrode 14 is lowered, and the electron-emitting device 1 has a resistance that cannot be ignored. Then, a uniform voltage is not applied between the first electrode 11 and the second electrode 14, and the in-plane uniformity of the amount of electron emission is reduced. In addition, the destruction resistance is reduced, and the second electrode 14 is destroyed by a short drive. Furthermore, if the film thickness is too small, problems such as cracks and peeling occur. For this reason, the layer thickness of the second electrode 14 is preferably in the range of 20 to 100 nm.

  Next, a method for manufacturing the electron-emitting device 1 in the present embodiment will be described. First, Ag nanoparticles treated with alcoholate and a silicone solution in an isopropyl alcohol solvent are weighed and mixed in a reagent bottle in a desired amount, and if necessary, further diluted with isopropyl alcohol. Disperse and mix for about 5 minutes. At this time, the mass ratio of Ag nanoparticles and silicone solids is approximately 1: 5. After confirming that the Ag nanoparticles in the solution are sufficiently dispersed, the intermediate layer 12 is applied on the Al substrate to be the first electrode 11 by spin coating. The rotation speed at this time is 3000 rpm.

  The substrate 11 on which the intermediate layer 12 is uniformly applied is stored in the air at room temperature for one day or more until the coating film is dried and cured. The film thickness after curing was approximately 1.5 μm as a result of measurement using a cross-sectional scanning transmission electron microscope (cross-section STEM), a surface roughness meter, a laser microscope, and the like.

After confirming the curing of the silicone resin, the substrate 11 on which the intermediate layer 12 is formed is introduced into the chamber of the vacuum vapor deposition apparatus with a metal mask for a desired electrode pattern, and the inside of the chamber is evacuated by a rotary pump and a cryopump. Then, when reaching a high vacuum region of about 10 ⁻⁵ Pa, deposition of Ti that becomes the electrode adhesive layer 13 is started. The vapor deposition rate at this time was 0.3 nm / sec, and this film thickness was measured using a crystal resonator. When the Ti film is formed to the desired thickness, it is left for 10 minutes while maintaining a high vacuum without opening to the atmosphere.

Thereafter, deposition of Au to be the second electrode 14 is started in a state where a high vacuum region of about 10 ⁻⁵ Pa is maintained. The vapor deposition rate at this time is 0.3 nm / sec. Since deposition of Au tends to raise the temperature in the chamber, the temperature around the holder holding the substrate is cooled by a water cooling method or the like to control the temperature. The temperature of the substrate at this time was estimated to be 80 ° C. or less. When the film formation of Au and Ti to 50 nm is completed, the film is left as it is for 10 minutes. Thereafter, the vacuum is broken and the atmosphere is introduced, and the completed electron-emitting device 1 is taken out.

<Example>
Next, examples will be described. In the present embodiment, a specific example in which the destruction of the second electrode 14 is moderately suppressed by adding the electrode adhesive layer 13 will be described.

  First, the configuration of the electron-emitting device 1 in the present embodiment will be described. As the first electrode 11, an Al plate having a thickness of 0.5 mm and a surface roughness Ra of 0.01 to 0.02 μm was used. The intermediate layer 12 includes an insulating resin 121 and metal fine particles 123. The insulating resin 121 is a room temperature curable silicone resin, the metal fine particles 123 are Ag nanoparticles having an average particle diameter of 10 nm, and the second electrode 14 is Au. It was used. The electrode adhesive layer 13 used Ti. Three types of electron-emitting devices 1a to 1c having a thickness of the electrode adhesive layer 13 of 5 nm, 15 nm, and 25 nm were manufactured by the above-described manufacturing method. As a comparative example, a total of four types of electron-emitting devices 5 without the electrode adhesive layer 13 were produced, and the amount of each electron emission was measured.

  Here, a method for driving the electron emission device A1 and a method for measuring the amount of electron emission will be described. FIG. 2 is a schematic diagram of the electron emission device A1 and the peripheral device B that collects and measures the emitted electrons emitted from the electron emission element A1 in this embodiment. The electron emission device A1 includes an electron emission element 1 and a power source 2, and the peripheral device B includes an electrode 3 and a power source 4. In this embodiment, the power source 2 has both a high frequency voltage source and an ammeter, and the power source 4 has both a high voltage power source and an ammeter. The electrode 3 was an Al plate.

  First, the first electrode 11 and the second electrode 14 of the electron-emitting device 1 were connected to the power source 2 and the line connected to the second electrode 14 was dropped to ground. Next, a negative pulse voltage having a duty ratio of 30% was applied to the second electrode 14 by the power source 2 as a 5 kHz rectangular wave. In order to measure electrons emitted from the electron-emitting device 1, the electrode 3 is installed at a position 0.5 mm away from the second electrode 14 so as to face the electron-emitting device 1, and one side of the power source 4 is electrically connected to the electrode 3. Connected to the other and dropped to ground. Next, 500 V was applied to the electrode 3 by the power source 4. Most of the electrons emitted from the electron-emitting device 1 are collected by the electrode 3 due to the spatial electric field 1 MV / m between the electron-emitting device 1 and the electrode 3. This was measured with an ammeter of the power source 4.

  The voltage applied to the electron-emitting device was swept from 0 V to −20 V at a voltage increase rate of −0.1 V / sec. When the voltage reached −20 V, the power source 2 was turned off. This driving process is called a forming process and is accompanied by a semi-insulation breakdown. By repeating the same forming process, the electron emission characteristics of the electron-emitting device are gradually stabilized. This process was repeated three times. Further, as a durability test, a negative pulse voltage of −20 V having a duty ratio of 30% was continuously applied from the power source 2 to the first electrode 11 from the power source 2 for 10 hours, and the subsequent breakdown of the second electrode 14 was observed.

  FIG. 3 is a table showing the initial electron emission amount and the durability test results of the electron-emitting devices 1a to 1c and 5. All of the electron-emitting devices 1a to 1c and 5 that have completed the forming process were able to confirm the emission of electrons. The amount of electron emission decreases as the electrode adhesive layer 13 increases. However, a sufficient amount of electron emission was confirmed even in the electron emission element 1c of Au (25 nm) / Ti (25 nm) which is the thickest.

  In addition, as a result of the durability test, all of the electron-emitting devices 1a to 1c in which Ti is formed on the intermediate layer 12 as the electrode adhesive layer 13 have a breakdown area as compared with the electron-emitting device 5 without the electrode adhesive layer 13 provided. It was greatly reduced. The effect of the electrode adhesive layer 13 with respect to appropriate destruction suppression of the second electrode 14 appeared as a significant difference.

(Embodiment 2)
Next, Embodiment 2 will be described. The present embodiment is the same as the above embodiment except that the composition of the intermediate layer of the electron-emitting device used in Embodiment 1 is different.

FIG. 4 is a schematic diagram showing a configuration of an electron emission device A2 using the electron emission element 1d in the present embodiment. In this embodiment, the intermediate layer 12 a is composed of insulating fine particles 122 and metal fine particles 123, and SiO ₂ particles having an average particle diameter of 110 nm are used as the insulating fine particles 122, and Ag nanoparticles having an average particle diameter of 10 nm are used as the metal fine particles 123. .

The insulating fine particles 122 are not particularly limited as long as they are insulating materials. For _{example, SiO 2, Al 2 O 3} , TiO 2 or the like can be used. Further, fine particles made of an organic polymer may be used. The particle size needs to be larger than the metal fine particles 123 described above, and the average particle size within the range is preferably 10 to 1000 nm.

Next, a method for manufacturing the electron-emitting device 1d in the present embodiment will be described. First, Ag nanoparticles treated with alcoholate and toluene are weighed and mixed in a desired amount in a reagent bottle, and dispersed and mixed in an ultrasonic cleaner for about 5 minutes. When fully dispersed, SiO ₂ particles are added to the dispersion in a desired amount, and again dispersed and mixed for about 5 minutes. At this time, the mass ratio of Ag nanoparticles and SiO ₂ particles is approximately 1: 9. After confirming that the Ag nanoparticles and the SiO ₂ particles in the liquid are sufficiently dispersed, the intermediate layer 12a is applied on the Al substrate to be the first electrode 11 by spin coating. The rotation speed at this time is 3000 rpm. The substrate 11 on which the intermediate layer 12a is uniformly applied is naturally dried at room temperature for about 1 hour. At this time, the obtained intermediate layer 12a was also measured in the same manner as in the above embodiment, and as a result, it was approximately 0.6 μm.

Substrate 11 which the intermediate layer 12a has been formed is introduced into the chamber of the vacuum evaporation apparatus by bonding a metal mask for the desired electrode pattern, and vacuum in the chamber by a rotary pump and a cryopump, 10 ^-5 Pa When the high vacuum region is reached, deposition of Ti that becomes the electrode adhesive layer 13 is started. The vapor deposition rate at this time was 0.3 nm / sec, and this film thickness was measured using a crystal resonator. When the Ti film was formed to 5.0 nm, it was left for 10 minutes while maintaining a high vacuum without opening to the atmosphere. Thereafter, vapor deposition of Au serving as the second electrode 14 was started while maintaining a high vacuum region of about 10 ⁻⁵ Pa. The vapor deposition rate at this time is 0.3 nm / sec. Since deposition of Au tends to raise the temperature in the chamber, the temperature around the holder holding the substrate is cooled by a water cooling method or the like to control the temperature. The temperature of the substrate at this time was estimated to be 80 ° C. or less. When the Au film was formed to 45.0 nm, it was left for 10 minutes. Thereafter, the vacuum is broken and the atmosphere is introduced, and the completed electron-emitting device 1 is taken out.

  The electron-emitting device 1d in which the second electrode 14 is Au (45 nm) and the electrode adhesive layer 13 is Ti (5 nm) was manufactured by the above-described method. Further, as a comparative example, an Au (50 nm) element 5a without an electrode adhesive layer was produced by the same production method, and the amount of each electron emission was measured in the same manner as in the above example.

  In the same manner as in the first embodiment, the forming process is repeated three times. Further, as an endurance test, a negative pulse voltage of −20 V is continuously applied to the first electrode 11 from the power source 2 for 10 hours, and then the second electrode 14 thereafter. The degree of destruction was observed.

  The electron-emitting devices 1d and 5a that completed the forming process did not have a difference of more than double in the amount of electron emission. Further, in the durability test, the result appeared as a significant difference, and the electron-emitting device 1d having the electrode adhesive layer 13 was suppressed from being excessively broken as compared with the electron-emitting device 5a.

(Embodiment 3)
Next, Embodiment 3 will be described. This embodiment is different from any of the above embodiments in that the electrode adhesive layer is partially provided on the intermediate layer.

  FIG. 5 is a plan view of the electron emission device 1e in the present embodiment, and FIG. 6 is a schematic diagram thereof. In the electron-emitting device 1e in the present embodiment, the first electrode 11, the intermediate layer 12, and the second electrode 14 are the same as those in the first embodiment. The electrode adhesive layer was not formed on the entire surface, but was partially formed in a stripe pattern as shown in FIG. In FIG. 5, the electrode adhesive layer 13 a is formed in a lower layer than the second electrode 14, but is in a state of being seen through because the second electrode 14 is thin.

  The reason why the film is partially formed is as follows. The purpose is to achieve both high electron emission performance and long life. The process of determining the life is dominated by disconnection, not destruction itself. The disconnection here means that the number of broken portions of the second electrode 14 gradually increases when the element is driven and grows large individually, so that they are connected like a ring, and the inside of the ring becomes non-conductive. Refers to that. For this reason, when disconnection occurs, the reduction rate of the effective area of the electron-emitting device is accelerated and the life is shortened. As shown in FIG. 5, when the electrode adhesive layer 13a is formed in a striped pattern, destruction is suppressed immediately above the electrode adhesive layer 13a, and disconnection hardly occurs. When the electrode adhesive layer 13a is partially disposed in this way, the effect of extending the life is great. Here, the film formation pattern is preferably linear and multi-connected. In this embodiment, a striped pattern is used for the convenience of production, but the present invention is not limited to this. Further, the area where the electrode adhesive layer 13a is not formed has high electron emission performance. For this reason, the electrode adhesive layer 13a is formed not on the entire surface but on a pattern in which disconnection hardly occurs, so that both high electron emission performance and long life can be achieved at a higher level.

  Next, a method for manufacturing the electron-emitting device 1e in the present embodiment will be described. The manufacturing method of this embodiment is the same as that of Embodiment 1 up to the step of completing the formation of the intermediate layer 12.

First, a metal mask on which a striped pattern having a width of 0.1 mm and a pitch of 0.2 mm is bonded to the substrate 11 on which the intermediate layer 12 is formed, and is introduced into the chamber of the vacuum evaporation apparatus. Next, the inside of the chamber was evacuated by a rotary pump and a cryopump, and when a high vacuum region of about 10 ⁻⁵ Pa was reached, vapor deposition of Ti serving as the electrode adhesive layer 13 was started. The vapor deposition rate at this time was 0.3 nm / sec, and this film thickness was measured using a crystal resonator. When the Ti film was formed to 5.0 nm, it was left for 10 minutes while maintaining a high vacuum without opening to the atmosphere.

Thereafter, deposition of Au was started in a state where a high vacuum region of about 10 ⁻⁵ Pa was maintained. The vapor deposition rate at this time is 0.3 nm / sec. Since deposition of Au tends to raise the temperature in the chamber, the temperature around the holder holding the substrate is cooled by a water cooling method or the like to control the temperature. When Au was deposited to 15.0 nm, it was left as it was for 10 minutes. Thereafter, the vacuum was broken and the atmosphere was introduced, the metal mask for the second electrode was replaced, and the film was again placed in the vapor deposition apparatus. When the high vacuum region of about 10 ⁻⁵ Pa was reached, the deposition of Au to be the electrode adhesive layer 13 was started again. When the Au film was formed to 50.0 nm, it was left as it was for 10 minutes. Thereafter, the vacuum was broken and the atmosphere was introduced, and the completed electron-emitting device 1 was taken out. Thus, the electrode adhesive layer 13 is made of 5 nm of Ti at the bottom and 15 nm of Au at the top. The reason for depositing Au on top of Ti is to prevent Ti from being oxidized because, for the sake of production, it is necessary to take out the electrode adhesive layer 13 into the atmosphere after replacing the metal mask to replace the metal mask. It is.

  By the above-described method, an electron-emitting device 1e in which the second electrode 14 is Au (45 nm) and the electrode adhesive layer 13 is striped Au (15 nm) / Ti (5 nm) was manufactured. In the electron-emitting device 1e after completion, the Au of the electrode adhesive layer 13 and the Au of the second electrode 14 are integrated as a continuous layer.

  In the same manner as in the first embodiment, the forming process is repeated three times. Further, as an endurance test, a negative pulse voltage of −20 V is continuously applied to the first electrode 11 from the power source 2 for 10 hours, and then the second electrode 14 thereafter. The degree of destruction was observed.

The initial electron emission amount of the electron-emitting device 1e was 5.0 × 10 ⁻⁶ A / cm ² at a driving voltage of 20 V (ON), and a large emission amount was obtained as compared with the electron-emitting device 1a. Moreover, it was found by surface observation after the durability test that the surface electrode destruction just above the electrode adhesive layer 13a was suppressed, and the above-described disconnection did not occur. As a result, by adopting this embodiment, high release performance and long life can be realized at a high level at the same time.

  As described above, according to each embodiment, according to the electron-emitting device of the present invention, in the electron-emitting device having the surface electrode, a high amount of electron emission can be obtained, and excessive destruction of the surface electrode can be prevented or destroyed. An electron-emitting device that can be reduced and can have a long lifetime can be obtained.

  The electron-emitting device according to the present invention is, for example, an image display device combined with a charging device of an image forming apparatus such as an electrophotographic copying machine, a printer, or a facsimile, an electron beam curing device, or a light emitter, or emitted. The present invention can be preferably applied to an ion wind generator using an ion wind generated by electrons.

1, 1a, 1b, 1c, 1d, 1e Electron emitting device 2 Power source 3 Electrode 4 Power source 11 First electrode 12, 12a Intermediate layer 13, 13a Electrode adhesive layer 14 Second electrode 121 Insulating resin 122 Insulating fine particle 123 Metal fine particle

Claims (6)

A first electrode; a second electrode; and an intermediate layer between the first electrode and the second electrode. By applying a voltage between the first electrode and the second electrode, the first electrode An electron-emitting device that emits the electrons from two electrodes,
An electron-emitting device comprising an electrode adhesive layer between the second electrode and the intermediate layer.   2. The electron-emitting device according to claim 1, wherein the electrode adhesive layer has a value between bond distances of molecules constituting the second electrode and the intermediate layer.   The electron-emitting device according to claim 1, wherein the electrode adhesive layer is a metal.   4. The electron-emitting device according to claim 1, wherein the electrode adhesive layer has a thickness of 5 nm to 20 nm.   5. The electron-emitting device according to claim 1, wherein the electrode adhesive layer is partially disposed between the second electrode and the intermediate layer. Forming an intermediate layer on the first electrode;
Forming an electrode adhesive layer on at least a portion of the intermediate layer;
Forming a second electrode on at least the electrode adhesive layer. A method for manufacturing an electron-emitting device, comprising: