1. Field of the Invention
The present invention relates to a manufacturing method of an electron-emitting device, a manufacturing method of an electron source, and a manufacturing method of an image display apparatus.
2. Description of the Related Art
There is a field emission type (FE type) electron-emitting device and a surface conduction type electron-emitting device or the like in the electron-emitting device.
In FE type electron-emitting devices, a voltage is applied between a cathode electrode (and an electron-emitting film arranged above it) and a gate electrode, and electrons are extracted into vacuum from the cathode electrode (or electron-emitting film) by the voltage (electric field). For this reason, an operating electric field is greatly influenced by a work function and a shape of the cathode electrode (electron-emitting film) to be used. In general, it is necessary to select the cathode electrode (electron-emitting film) with small work function.
Japanese Patent Application Laid-open No. 9-199001 discloses an electron-emitting apparatus which has a metallic object as a cathode electrode and a semiconductor (diamond, AIN, BN or the like) jointed to the metallic object. Further, the above document discloses a method for terminating surface of a semiconductor film composed of diamond with film thickness of about 10 nm or less with hydrogen so as to make electron affinity of the semiconductor film negative.
The diamond (semiconductor film) whose surface is terminated with hydrogen is a typical material, which has negative electron affinity. An electron-emitting device where surface of the diamond having negative electron affinity is used as an electron-emitting surface is disclosed in U.S. Pat. Nos. 5,283,501, 5,180,951, and “Environmental effect on the electron emission from diamond surfaces” written by V. V. Zhinov, J. Liu et al., J. Vac. Sci. Technol., B16(3), May/June, 1998, pp. 1188-1193.
In the electron-emitting device using diamond, electrons can be emitted from a low threshold electric field (electric field which is minimally required for emitting electrons) and high emission current can be generated.
However, in the case where a semiconductor having negative electron affinity or a semiconductor having very small positive electron affinity is used for electron-emitting device, if once electrons are injected into the semiconductor, the electrons are approximately always emitted. For this reason, in the case that such electron-emitting device is applied to display or electron source, it is occasionally very difficult to control an electron emission amount (particularly switching between on and off).
Therefore, the inventors of the present invention propose an electron-emitting device described in Japanese Patent Application Laid-Open No. 2005-26209 as an electron-emitting device which provides sufficient on/off property and can perform a high-efficient emission of electron with a low voltage. Further, the inventors propose an electron source having the electron-emitting device and an image display apparatus which provides high-contrast in Japanese Patent Application Laid-Open No. 2005-26209.
A manufacturing method of an electron-emitting device described in Japanese Patent Application Laid-Open No. 2005-26209 includes a step of forming a dipole layer on the surface of the insulating layer by chemically modifying a surface of an insulating layer. The chemical modification is carried out by thermally treating a whole portion in a hydrocarbon gas. A temperature necessary for effectively terminating surface of the insulating layer with hydrogen is 600° C. or more.
On the other hand, in the case of that the electron-emitting device are used to display panel, various glasses are generally used as substrates (base) for forming the electron-emitting device. A flexibility point of the glass generally used as the substrates is lower than a flexibility point of quartz and silicon substrates. Concretely, the flexibility point is 550° C. or less.
That is to say, in the case of that the electron-emitting device described in Japanese Patent Application Laid-Open No. 2005-26209 is formed as a display panel on a glass substrate, the surface cannot be sufficiently chemically modified, and thus the property of the electron-emitting device cannot be improved. Further, since a high-temperature process at 600° C. is inserted during the steps, the cost increases.
It is, therefore, an object of the present invention to provide a manufacturing method of an electron-emitting device which has sufficient electron emission characteristic and is simple, a manufacturing method of an electron source and a manufacturing method of an image display apparatus.
A manufacturing method of an electron-emitting device according to the present invention including the steps of: preparing a substrate having a carbon film; and terminating a surface of the carbon film with hydrogen by irradiating a light or particle beam locally to a part of the carbon film in an atmosphere including hydrocarbon or hydrogen or in an atmosphere including both hydrocarbon and hydrogen.
In a manufacturing method of an electron source having a plurality of electron-emitting devices according to the present invention, each of the plurality of electron-emitting devices is manufactured by the manufacturing method of electron-emitting device according to the present invention.
In a manufacturing method of an image display apparatus having an electron source and a light emitting member for emitting light due to irradiation of electrons, the electron source is manufactured by the manufacturing method of an electron source according to the present invention.
According to the present invention, the manufacturing method of the electron-emitting device which has sufficient electron emission characteristic and is simple, the manufacturing method of the electron source and the manufacturing method of the image display apparatus can be provided.
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
A preferable embodiment of the present invention is described as an example in detail below with reference to the drawings. The scope of the present invention is not limited only to sizes, materials, shapes and relative arrangements of components described in the embodiment unless otherwise noted.
An electron-emitting device according to the embodiment of the present invention has a carbon film. A manufacturing method of the electron-emitting device includes a step of forming a dipole layer on a carbon film. The dipole layer is formed (a carbon film whose surface is terminated with hydrogen is formed) by locally irradiating a light or a particle beam to a part of the carbon film in an atmosphere including hydrocarbon or hydrogen or in an atmosphere including both hydrocarbon and hydrogen. For this reason, the terminating process can be executed without thermally damaging a substrate (even a thermally fragile substrate such as glass).
One example of the electron-emitting device according to the embodiment of the present invention is described below. A constitution of the electron-emitting device according to the embodiment of the present invention is not limited to the following constitution, and the device may have any constitution as long as it has a carbon film as an electron-emitting member.
In the electron-emitting device according to the embodiment, electrons are extracted from the electron-emitting member into vacuum by using a quantum-mechanical tunneling of carriers in an insulating layer and a tunneling in vacuum barrier which is reduced by terminating the electron-emitting member with hydrogen.
The electron-emitting device according to the embodiment has a cathode electrode, an insulating layer which covers at least a part of a surface of the cathode electrode and has a dipole layer on its surface, and an extraction electrode. By that a voltage is applied between the cathode electrode and the extraction electrode, electrons are tunneled from the cathode electrode through the insulating layer and a vacuum barrier and the electrons are emitted into vacuum in a state that the vacuum barrier which contacts with the dipole layer is higher than a conduction band in the surface of the insulating layer.
In the electron-emitting device according to the embodiment, the dipole layer is formed by terminating the surface of the insulating layer with hydrogen, and the insulating layer contains carbon as a main component. In the electron-emitting device according to the embodiment, a thickness of the insulating layer is preferably 10 nm or less. At the time of emitting electrons, the surface of the insulating layer preferably has positive electron affinity. Surface roughness of the insulating layer is preferably smaller than 1/10 of the film thickness of the insulating layer in RMS.
An electron emission principle in the electron-emitting device according to the embodiment is described below with reference to
The electron 6 is extracted from the insulating layer 2 into the vacuum by applying a higher potential than an electric potential of the cathode electrode 1 to the extraction electrode 3. A voltage between the cathode electrode 1 and the extraction electrode 3 is a driving voltage.
In
The state of
The film thickness of the insulating layer 2 can be determined by the driving voltage, but it is preferably set to 20 nm or less, more preferably to 10 nm or less. A lower limit, of the film thickness of the insulating layer 2 may be such that when the electron-emitting device is driven, a barrier (the insulating layer 2 and a vacuum barrier) through which the electron 6 supplied from the cathode electrode 1 is tunneled is formed. The lower limit is preferably set to 1 nm or more from a viewpoint of formation reproducibility.
In the electron-emitting device according to the embodiment, the insulating layer 2 always shows positive electron affinity so that a clear on-off ratio of the electron-emitting amount between selection and non-selection which is a conventional problem is secured.
The dipole layer 20 shown in
Therefore, as shown in
As mentioned above, the vacuum barrier 4 is also lowered in conjunction with the application of the driving voltage V [V], and its spatial distance is also shortened similarly to the insulating layer 2. For this reason, the vacuum barrier 4 is brought into a tunnel enabled state, so that the electron emission into vacuum is realized.
One example of the manufacturing method of the electron-emitting device according to the embodiment is described below with reference to
An electrode layer 71 is laminated on a substrate 31 whose surface is sufficiently cleaned. As the substrate 31, any one of quarts glass, glass whose impurity (Na or the like) containing amount is reduced, soda lime glass, a laminated body obtained by laminating SiO2 on surface of a substrate, an insulating substrate made of ceramics or the like is used.
The electrode layer 71 is generally has conductive property, and is formed by a general vacuum deposition technique such as a vacuum evaporation method and a sputtering method. The material of the electrode layer 71 is suitably selected from, for example, metal such as Be, Mg, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, Cu, Ni, Cr, Au, Pt or Pd, or a alloy material. The thickness of the electrode layer 71 is set within a range of several dozen nm to several hundreds μm, and preferably, a range of 100 nm to 10 μm.
As shown in
The material of the insulating layer 2 contains carbon as a main component (carbon film), and the material having smaller dielectric constant is preferable with consideration of concentration of an electric field. The material preferably has resistivity of 1×108 to 1×1014 Ωcm. Concretely, as the insulating layer 2, diamond-like carbon (DLC), amorphous carbon, metal carbide can be used. Particularly, its main component is preferably SP3 carbon.
In order to separate the electrode layer 71 into the cathode electrode 1 and the gate electrode 32, a photoresist 72 is patterned (
An etching process is executed, thereby, as shown in
The surface of the substrate 31 exposed between the cathode electrode 1 and the gate electrode 32 is preferably engraved as shown in
As shown in
Finally, the surface of the insulating layer 2 is terminated with hydrogen by carrying out a heat treatment (terminating process; chemical modification). As a result, the dipole layer 20 is formed on the insulating layer surface. 74 in
In the electron-emitting device according to the embodiment, the insulating layer surface is terminated with hydrogen by carrying out the heat treatment in a hydrocarbon gas. Concretely, the chemical modification is made by locally irradiating a light beam or a particle beam to a part of the carbon film in an atmosphere including hydrocarbon or hydrogen or in an atmosphere including both hydrocarbon and hydrogen. As a result, the chemical modification (terminating process) can be sufficiently made without thermally damaging the substrate. As the light to be locally irradiated, a laser light or the like is suitably selected.
In above description, an example is shown that the dipole layer 20 is formed on surface of the insulating layer on both the cathode electrode 1 and the gate electrode 32. However, in this embodiment, since a part can be locally heated, the dipole layer 20 can be formed only on the insulating layer on the side of the cathode electrode 1.
An example where the electron-emitting device according to the embodiment of the present invention is applied to an electron source and an image display apparatus is described below.
Various types of arrangements of the electron-emitting device are adopted. As one example, a plurality of electron-emitting devices are arranged in X and Y directions in a matrix. One sides of the electrodes of the plural electron-emitting devices arranged in the same row are connected commonly to a wiring in the X direction, and the other sides of the electrodes of the plural electron-emitting devices arranged in the same column are connected commonly to a wiring in the Y direction. This is called simple matrix arrangement.
The electron source of the simple matrix arrangement obtained by arranging the plurality of the electron-emitting devices is described below with reference to
The X-direction wirings 502 are composed of m-numbered wirings Dx1, Dx2, . . . Dxm, and can be composed of conductive metal formed by using the vacuum evaporation method, a printing method or the sputtering method. A material, a film thickness and a width of the wirings are suitably designed. The Y-direction wirings 503 are composed of n-numbered wirings Dy1, Dy2, . . . Dyn, and are formed similarly to the X-direction wirings 502. An inter-layer insulating layer, not shown, is provided between the m-numbered X-direction wirings 502 and the n-numbered Y-direction wirings 503 so as to electrically separate them (m and n are positive integers).
The inter-layer insulating layer, not shown, is made of SiO2 or the like formed by the vacuum evaporation method, the printing method or the sputtering method. For example, the inter-layer insulating layer is formed into a desired shape on a whole or partial surface of the electron source substrate 501 where the X-direction wirings 502 are formed. The film thickness, the material and the manufacturing method are suitably set so as to withstand a potential difference on cross sections between the X-direction wirings 502 and the Y-direction wirings 503. The X-direction wirings 502 and the Y-direction wirings 503 are extracted as external terminals.
The electron-emitting device 504 has a pair of electrodes (gate electrode and a cathode electrode). In the example of
A material composing the X-direction wirings 502 and the y-direction wirings 503, a material composing the wire connections and a material composing the pair of device electrodes may be partially or wholly uniform in constituent element or different from one another. For example, these materials are suitably selected according to the material of the device electrode. If the material composing the device electrode and the material of the wiring are the same, the wiring connected to the device electrode can be the device electrode.
The X-direction wirings 502 are connected to a scanning signal applying unit, not shown. The scanning signal applying unit applies a scanning signal to the electron-emitting device 504 connected to the selected X-direction wirings. On the other hand, the Y-direction wirings 503 are connected to a modulation signal generating unit, not shown. The modulation signal generating unit applies a modulation signal modulated according to an input signal to the respective columns of the electron-emitting devices 504. The driving voltage to be applied to each electron-emitting device is supplied as a difference voltage between the scanning signal and the modulation signal applied to the device.
In the above constitution, individual device is selected by using the simple matrix wiring so as to be capable of being individually driven. The image display apparatus constituted by using the element source is described with reference to
As shown in
The image display apparatus applies a voltage to each electron-emitting device 615 via container external terminals Dox1 to Doxm and Doy1 to Doyn. Each electron-emitting device 615 emits electrons according to the applied voltage.
A high voltage is applied to the metal back 605 or a transparent electrode (not shown) via a high-voltage terminal 614, so that the emitted electrons are accelerated.
The accelerated electrons collide with the phosphor film 604, and light is emitted so that an image is formed.
The image display apparatus according to this embodiment can be used as a display apparatus for television broadcasting, a display apparatus of video conference system or a computer, or an image display apparatus as an optical printer constituted by using a photosensitive drum.
Examples of the present invention are described in detail below.
The insulating layer 2 (electron-emitting film; carbon film; semiconductor layer) having the dipole layer according to the embodiment of the present invention was manufactured according to the manufacturing method shown in
In Example 1, pulsed laser light having a light absorbable wavelength is locally irradiated to the carbon film in a hydrocarbon atmosphere so that the terminating process is executed. That is to say, the carbon film absorbs coherent or non-coherent pulsed laser light, and thus its temperature rises. Since the carbon film is formed not on the entire surface of the substrate, the entire substrate is not heated to high temperature. For this reason, thermal damage on the substrate (change such as warpage or constriction due to heat history) can be reduced.
The manufacturing procedure is described in detail below.
Quartz was used as the substrate 31, and after the substrate 31 was sufficiently cleaned, TiN with thickness of 500 nm was formed as the cathode electrode 1 by the sputtering method (
The formation conditions are as follows:
Rf electric source: 13.56 MHz
Rf power: 7.7 W/cm2
Gas pressure: 0.6 Pa
Atmosphere gas: N2/Ar (N2: 10%)
Substrate temperature: room temperature
Target: Ti
The carbon film was formed into thickness of 4 nm on the cathode electrode 1 by the sputtering method, and the insulating layer 2 was formed (
The surface of the insulating layer 2 was locally heated by using pulsed laser light in a mixed gas atmosphere of methane and hydrogen. As a result, the dipole layer 20 was formed on the surface (
The used pulsed laser light was an YAG laser, and a wavelength was 355 nm which was a third harmonic, a pulse oscillating frequency was 1 to 300 Hz, and laser energy density was 300 to 1000 mJ/cm2 (preferably, 350 to 500 mJ/cm2).
Heat treatment (terminating process) conditions are described below:
Heat treatment temperature: 600° C.
Heating system: laser heating
Processing time: 60 min
Mixed gas ratio: methane/hydrogen=15/6
Heat treatment pressure: 6.65×103 Pa
An electron emission characteristic (voltage-current characteristic) of the insulating layer manufactured in this example was measured. This measurement was taken by arranging an anode electrode (area was 1 mm2) on a position separated from and opposed to the insulating layer and applying a driving voltage between the anode electrode and the cathode electrode. The voltage-current characteristic at this time is shown in
As shown in
As is clear from
As an example 2, a case where instantaneous thermal annealing (RTA, local heating) is carried out using a lamp (typically halogen lamp) which can execute heat treatment only on a desired place is described. Since RTA can be carried out in a short time, improvement of productivity (production speed) is expected in the present invention.
A manufacturing procedure is described in detail below.
Similarly to the first embodiment, it was finished to the step in
This RTA treatment is carried out preferably at temperature of 600 to 800° C. and for short time of about 1 to 240 seconds using the RTA method. At this time, the carbon film is heated to about 600 to 650° C. due to a difference of a heat absorption factor in each materials, but the temperature of the substrate 31 becomes about 300 to 400° C. For this reason, damage on the substrate 31 can be repressed. Since the RTA treatment is carried out in a short time of about 1 to 240 seconds, the temperature of a thermally fragile glass substrate whose distortion point (flexibility point) is 600° C. or less does not rise much. For this reason, the distortion of the glass substrate due to heat can be repressed.
The electron emission characteristic of the insulating layer manufactured in Example 2 was measured. This measurement was taken by arranging an anode electrode (area was 1 mm2) on a position separated from and opposed to the insulating layer and applying a driving voltage between the anode electrode and the cathode electrode. As a result, also when the dipole layer is formed by the local heating using RTA (the insulating layer in Example 2), the electron emission characteristic, which is equivalent to a case (the insulating layer in the conventional example) of the conventional method (Japanese Patent Application Laid-Open No. 2005-26209), was obtained.
According to the manufacturing method of the electron-emitting device in the embodiment of the present invention, the hydrogen terminating process can be executed on a desired portion of the surface of the carbon film. Further, since only the surface of the insulating layer has high temperature, damage on the other layers can be reduced. Since the manufacturing method of the electron-emitting device according to the embodiment of the present invention can be executed in a short time, the productivity increases.
This embodiment describes the case where light of laser or RTA is irradiated locally, but even if a particle beam such as an electron beam, or an ion beam is irradiated, the effect equivalent to this embodiment can be obtained.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Application No. 2007-289651, filed on Nov. 7, 2007, which is hereby incorporated by reference herein in its entirety.
Number | Date | Country | Kind |
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2007-289651 | Nov 2007 | JP | national |